CN1400959A - 具有抗菌活性的远红外发射粉末以及用含有该粉末的树脂涂覆的生物波钢板 - Google Patents
具有抗菌活性的远红外发射粉末以及用含有该粉末的树脂涂覆的生物波钢板 Download PDFInfo
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- CN1400959A CN1400959A CN01805053A CN01805053A CN1400959A CN 1400959 A CN1400959 A CN 1400959A CN 01805053 A CN01805053 A CN 01805053A CN 01805053 A CN01805053 A CN 01805053A CN 1400959 A CN1400959 A CN 1400959A
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- C—CHEMISTRY; METALLURGY
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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Abstract
本发明公开了远红外发射粉末及具有抗菌活性和远红外发射性能的树脂涂覆的钢板。除具有0.9或更高的发射率外,远红外发射粉末可抑制细菌的生长,其饱和水溶液的pH值为7.5-10.5。在电磁屏蔽钢板上涂覆干厚度为5-60μm的涂层材料而不干扰钢板的固有的电磁屏蔽性能,该涂层材料含有5-100重量份的上述粉末/100重量份树脂。
Description
技术领域
本发明涉及一种具有抗菌活性的远红外发射粉末,该粉末可应用于钢板以使其具有抗菌活性和远红外发射性能。另外,本发明涉及一种钢板,该钢板可屏蔽低频电磁波,并可用在需要抗菌活性和远红外辐射的场合。
背景技术
属于红外辐射的远红外辐射的波长为2.5~20μm。在高于0K的温度下,所有物质都产生远红外辐射,但是这种辐射广泛从被称为远红外发射器的特定陶瓷中产生。按照韩国专利公报95-8584的公开,远红外辐射的能量效率如此之高,归功于其通过应用广泛的辐射传递能量。
例如,远红外辐射对于人体的有益效果使远红外发射器可以应用于桑拿建筑物、电器、普通建筑物等中。
按照韩国专利申请88-1616和95-26761的公开,典型的远红外发射器是硬玉和淡英斑岩。除此之外,已知过渡金属氧化物也具有高远红外发射率(韩国专利公开号95-8584)。因这些远红外发射器几乎不具有导电性和导磁性,预计其具有电磁屏蔽能力。
有多种方法可以使钢板具有远红外发射能力。例如,按照日本专利公开号95-248231和2000-171045的公开,用远红外发射陶瓷涂覆钢板以提高其耐热性和能量效率。按照韩国专利申请90-22365的公开,可通过腐蚀将不锈钢板变为远红外发射器。韩国专利公开号1998-83238介绍了一种制造远红外发射钢板的方法,其中在诸如聚乙烯树脂等热固性树脂中加入含有诸如Al2O3、SiO2等的远红外发射陶瓷的沸石粉末,然后进行热处理。但是,由于选择了不合适的远红外发射器,该钢板在全波长范围中表现出仅0.90以下的远红外发射率。特别是,在已知对人体健康有益的5-8μm的波长带范围内,其远红外发射率仅为约0.5-0.8。
参照图1a和1b,显示了发射曲线。在图4a中常规PCM(预涂覆金属)钢板的发射率对波长作图。图4b示出了PCM钢板和理想体的典型的发射率对波长作图。从曲线中可以看出,这些钢板没有显示出高频远红外发射。另外,不能预计这些钢板屏蔽低频电磁波。
按照条件的需要,需要钢板抑制微生物,以及显示高的远红外发射率。在这一点上,一些现有技术提出在钢板中应用抗菌物质以用于内部装修、厨房用具等。例如,韩国专利公开号1996-58162公开了在磷酸盐材料中浸渍的银(Ag)作为可用于钢板的抗菌物质。类似的,按照日本专利公开特开平8-257493和韩国专利公开号1998-83239的公开,具有抗菌活性的无机物质如Zn和Ag浸渍在具有远红外发射率的沸石载体中。可应用于钢板的抗菌物质的另一个例子是光催化剂如TiO2(日本专利公开2000-63733)。另外,美国专利6,313,664利用具有催化活性的金属与TiO2结合,使钢板具有抗菌活性。应用于钢板的大多数常规抗菌物质是基于金属离子的抗菌活性和TiO2的光学性能。但是,含有抗菌金属离子和光催化剂的载体不仅远红外发射率差,而且非常昂贵。
由于构成时变的、与生物体系具有不同相互作用的电场和磁场,发现电磁波对人体具有有害作用,这导致开发了多种用于屏蔽电磁波的方法和物质。对人体产生不利影响的人造波统称为有害波。
最近的研究证明了低频电磁波对生物体系的有害作用。特别地,一系列提示了输电线周围的电磁场(60Hz)与致癌作用的相互作用的研究在全世界产生重大影响。
除了致癌作用,当长时间暴露于低频电磁波时,发现具有磁性的低频电磁波在人体内产生感应电流,这打破了各种离子如Na+、K+、Cl-等的跨细胞膜生物平衡,对人体的激素分泌和免疫细胞产生不利影响。一项研究报道说磁场改变与睡眠有关的褪黑激素的分泌量,从而导致长期影响健康的失眠。
作为对来自电磁场的不利健康作用的环境因素的反应,最近许多国家通过立法降低从各种电器或电磁器中释放的电磁波的容许水平。另外,有关电磁场的规定用作了电器和/或电磁器的进口壁垒。例如,瑞典和其它欧洲国家禁止进口磁漏2mG或更高的的电视或计算机监视器。
同样地,随着与电磁有关的学术团体(韩国电磁工程协会)和医学团体发挥重要作用,韩国的政府和非政府组织进行了很大的努力以制定一项控制电场和磁场暴露极限的法律(Journal of the KoreaElectromagnetic Engineering Society,第8卷,第2期,1997;White Paperon the Activity at National Assembly of the Committee on the Problems ofHarmful Electromagnetic Waves,1999年12月出版;“EpiodemiologicalInvestigation for the Influence of Electromagnetic Waves on the Body andStudy on the Enactment of Law Regulating Electromagnetic Waves”,Korea Radio Station Management Agency(KORA 99-09,2000年8月))。
为处理这种有害的电磁波,在两方面开发了屏蔽技术:构造和材料。目前使用铜和铝作为电磁波的屏蔽。此外,本发明人在韩国专利申请1999-52018中描述了一种在低频具有优良的磁屏蔽效应的钢材料。但是,这样的非铁材料及具有优良电磁屏蔽性能的钢板不适合作为远红外发射器,因为它们的远红外发射率很差。
发明的公开
本发明人进行了广泛而全面的研究,发现某些碱性氧化物具有优良的远红外发射率,以及对微生物的抑制活性,可以应用于钢板上,从而产生了本发明。
因此,本发明的一个目的是克服现有技术中存在的上述问题,及提供一种具有抗菌活性、其饱和水溶液的pH为碱性,并具有远红外发射活性的远红外发射粉末。
本发明的另一个目的是提供一种树脂涂覆的钢板,该钢板具有抗菌活性及远红外发射活性。
本发明的第三个目的是提供了用含有远红外发射粉末的树脂涂覆的屏蔽电磁波的钢板,该钢板具有屏蔽电磁波及抗菌活性,并具有远红外发射性能。
按照本发明的一个方面,提供一种远红外发射粉末,该粉末具有抗菌活性,其饱和水溶液的pH值范围为7.5-10.5,并显出0.9或更高的远红外发射率。
按照本发明的另一方面,提供一种具有抗菌活性和远红外发射性能的树脂涂覆钢板,其树脂涂层的干厚度为5-60μm,所说的树脂涂层中含有5-100重量份远红外发射粉末/100重量份树脂,所说的粉末的饱和水溶液的pH值范围为7.5-10.5,并具有0.9或更高的远红外发射率。
附图说明
以下结合附图的详细描述可以更清楚地理解本发明的上述及其他目的、特征和其它优点,附图中:
图1a为ZnO粉末和理想黑体的远红外发射曲线;
图1b为MgO粉末和理想黑体的远红外发射曲线;
图2a为显示含有与氢氧化镁和大肠杆菌结合的MgO的标准试样的照片;
图2b为显示培养图2a的标准试样24小时后大肠杆菌生长的照片;
图3a为显示含有与氢氧化锌和绿脓假单孢菌结合的ZnO的标准试样的照片;
图3b为显示培养图3a的标准试样24小时后绿脓假单孢菌的生长的照片;
图4a为常规聚酯PCM板的远红外发射率对波长所作的曲线;
图4b为常规聚酯PCM板和理想黑体的远红外发射率对波长所作的曲线;
图5为聚酯树脂的远红外发射率对波长所作的曲线;
图6a为TiO2粉末的远红外发射率对波长所作的曲线;
图6b为MgO粉末的远红外发射率对波长所作的曲线;
图6c为CaCO3粉末的远红外发射率对波长所作的曲线;
图6d为ZnO粉末的远红外发射率对波长所作的曲线;
图7为用含有MnO和TiO2粉末的聚酯树脂涂覆的生物波(bio-wave)钢板的远红外发射率对波长所作的曲线。
实施本发明的最佳方式
当与水分接触时,某些碱性金属氧化物粉末在其表面具有M(OH)或M(OH)2的形式(式中M为碱金属元素)的氢氧化物。这些氢氧化物碱性弱,但具有优良的远红外发射和有效的抗菌活性。
由于它们在水中的溶解度高,Na2O、K2O和CaO粉末很容易与水分作用而分别形成NaOH、KOH和Ca(OH)2,同时产生大量的热。此外,Na2O、K2O或CaO的水溶液的pH值为11或更高,碱性很强。因此,这些氧化物不适合作为远红外发射粉末,因为它们的碱性很高,这对身体是有害的,尽管粉末形式的Na2O、K2O和CaO具有抗菌活性。
相反,MgO和ZnO很难与水分或水反应。当MgO和ZnO粉末直接与水或水分接触时,它们只有极少量形成氢氧化物,由于这些氢氧化物的存在,粉末表面的pH值范围为7.5-10.5。在碱性氧化物粉末的表面,与水分的反应如下面的化学式1所示:
通常微生物经不起环境变化。当环境的pH进入7.5-10.5的范围时,一些微生物的生长可能会受到有效的抑制。弱的碱性pH范围对人体无害,因此这些氢氧化物或氧化物用来制造类矿泉水、碱性食物、抗酸剂等。
与MgO和ZnO相反,CaCO3不会因改变环境pH而具有抗菌活性。CaCO3粉末自身具有抗菌活性,在水中的溶液度很小。但是,CaCO3的抗菌活性比MgO或ZnO弱。在用与树脂结合的CaCO3涂覆钢板以使其具有抗菌活性时,CaCO3的用量必须比MgO、ZnO、Mg(OH)2和Zn(OH)2更大。另外,MgO、ZnO、Mg(OH)2、Zn(OH)2和CaCO3在远红外波长带均具有0.90或更高的远红外发射率,优选0.92或更高。
按照本发明,具有0.90或更高、优选0.92或更高的远红外发射率,并具有7.5-10.5的pH或具有天然的抗菌活性的陶瓷粉末可以用作抗菌、远红外发射粉末(下文仅称作“发射粉末”)。
仅作说明而非限制的发射粉末的例子包括MgO、Mg(OH)2、ZnO、Zn(OH)2、CaCO3粉末或这些粉末的混合物。
按照本发明的一个实施方案,在发射粉末中优选含有17重量%的抗菌且远红外发射性的MgO、Mg(OH)2、ZnO、Zn(OH)2、CaCO3或它们的混合物。如果氧化物或氢氧化物的用量低于17重量%,其(粉末)不显示优良的远红外发射率。
发射粉末优选具有1.0m2/g或更大的比表面积。另外,优选粒子尺寸为100目或更小的发射粉末。当与粘合剂结合涂覆时,比表面积小或粒子尺寸大的远红外发射粉末使涂层不均匀。
本发明的发射粉末可以通过任何已知的方法制备。例如,通过来自钢铁厂的碱性耐火材料的水化作用可以获得Mg(OH)2。详细来说,当用作钢铁厂的碱性耐火材料的氧化镁(MgO)于水溶液中在100℃或更高温度被加热和老化时,在耐火材料的表面形成氢氧化镁。另外,可以从海水获得氢氧化镁。
由于含有MgO、Mg(OH)2、ZnO、Zn(OH)2、CaCO3或它们的混合物的粉末为白色,将粉末与有色颜料混合而保持颜料的颜色。因此,可以获得理想颜色的将要涂覆到基材如钢板和塑料上的远红外发射粉末。
除了具有优越的远红外发射和抗菌活性,含有MgO、Mg(OH)2、ZnO、Zn(OH)2、CaCO3或它们的混合物的粉末对人体无害。因此,本发明的发射粉末与涂料或树脂结合,可以应用于任何需要抗菌活性和健康的远红外发射的场合。本发明发射粉末的说明性而非限制性的应用实例包括树脂涂覆的钢板、壁纸、家具和塑料管。
应用于钢板时,如上所述,发射粉末与树脂结合。应用于钢板的任何树脂可用来与本发明的发射粉末结合。可用于本发明的说明性而非限制性的树脂的例子包括聚酯树脂和丙烯酸树脂。
按照本发明,基于100重量份树脂,发射粉末的用量为5-100重量份,优选为15-100重量份。例如,当发射粉末的用量低于5重量份时,导致较差的抗菌活性和远红外发射性能。而随着树脂中的发射粉末的含量增加时,远红外辐射也增强。仅仅考虑远红外辐射因素,最好使用更多的发射粉末。但是,在100重量份树脂中超过100重量份的发射粉末时会导致涂层的粘结性能、与其它组分如颜料的相容性变差。
但是,临界抗菌活性所需的发射粉末量随发射粉末的不同而不同。例如,使树脂涂覆的钢板具有90%或更高的抗菌能力所需的最小发射粉末量取决于所用的发射粉末。详细地说,为使钢板具有90%或更高的抗菌能力,基于100重量份树脂,MgO或Mg(OH)2的用量必须为5重量份或更高,ZnO或Zn(OH)2的用量为20重量份或更高,CaCO3的用量为30重量份或更高。
按照本发明,用于涂覆钢板的树脂组合物除含有发射粉末,根据情况需要还可以含有固化剂、消光剂、分散剂和其他添加剂。
当含有远红外发射粉末的树脂涂覆在钢板上时,钢板的远红外发射率随所得涂层的变厚而增加至某一程度。例如,当含有发射粉末的涂层组合物以5μm的干厚度涂覆在钢板上时,涂层的抗菌能力为90%或更高,远红外发射率为0.85或更高。干厚度为15μm时,涂层的远红外发射率为0.90或更高。但是,远红外发射率一直增加,直到干厚度达到60μm。超过60μm的干厚度使涂层的粘结力下降,而不增加远红外发射率。对于PCM(预涂金属)钢板的情况,优选涂层的干厚度小于30μm。考虑到上述条件,含有发射粉末的树脂优选在钢板上涂覆到5-60μm的干厚度,更优选为15-30μm的干厚度。
在树脂涂层中,优选远红外发射粉末的含量大约为25-50重量%。例如,如果远红外发射粉末的含量低于25重量%,发射率变差。另一方面,当使用超过50重量%的发射粉末时,发射率也不会进一步增加。
在对人体有益的5-8μm的波长带上,聚酯树脂的远红外发射率为0.5-0.8,这与在5-20μm范围之外的其他波长带上的远红外发射率相比显著的差,如图5所示。因此,当使用聚酯树脂时,需要使用在5-8μm的波长带上具高远红外发射率的发射粉末,从而需要聚酯树脂涂覆的钢板在5-8μm的波长带上具有0.85或更高的远红外发射率,在5-20μm的远红外全波长带之外的其他范围的远红外发射率为0.90或更高。
在5-8μm的波长带上,MgO、Mg(OH)2、ZnO、Zn(OH)2和CaCO3均具有0.90或更高的远红外发射率。因此,在本发明中,将选自MgO、Mg(OH)2、ZnO、Zn(OH)2、CaCO3及它们的混合物中的任何一种与聚酯树脂结合并应用于钢板,都可取得在5-8μm的波长带上的理想远红外发射率。
按照本发明,含有远红外发射粉末的的聚酯树脂被涂覆到钢板上至干厚度为15-60μm,优选干厚度为15-30μm。例如,如果涂层厚度低于15μm,得不到充足的远红外发射率。另一方面,超过60μm的涂层厚度对钢板的粘结性能变差。
当用与在5-8μm的波长带上具有0.90或更高的远红外发射率的远红外发射粉末混合的聚酯树脂涂覆钢板时,发现钢板在5-20μm的远红外全波长带的远红外发射率平均为0.90或更高,在5-8μm的波长带上其远红外发射率为0.85或更高。
应该理解本发明的发射粉末并不局限于用于本发明的钢板。如果本发明的发射粉末施用于其上,可应用任何钢板。另外,将与本发明的远红外发射粉末混合的树脂涂覆到电磁屏蔽钢板上,从而制成生物波钢板,该钢板在抗菌活性和远红外发射方面均很优越,并具有优良的电磁屏蔽效果。本文所用的术语“生物波钢板”是指可屏蔽有害的电磁波(例如,60Hz的人造电磁场)并发射有益的远红外辐射的钢板。
可用于本发明的电磁屏蔽钢板的例子是在60Hz的时变磁场中具有2000或更高的最大磁导率的钢板,但不限于此。
含有95重量%或更高的铁及0.02重量%或更低的碳的钢板,在60Hz的时变磁场中能够显示2000或更高的最大磁导率。
碳含量超过0.02重量%会降低时变磁场(60Hz)中的最大磁导率,使电磁屏蔽效果减弱。可用于本发明的钢板是含有0.02重量%或更低的碳、95重量%或更高铁的冷轧钢板,和含有0.5-3.5重量%硅的硅钢板。这些钢板可以电解方式或热浸方式镀锌、镀铬或涂覆树脂。
抗菌性发射粉末和生物波钢板可用来控制或除掉真菌,特别是大肠杆菌和绿脓假单孢菌。因此,本发明的生物波钢板不仅可以用在需要电磁场屏蔽和远红外发射的地方,而且可以用在需要除掉大肠杆菌和绿脓假单孢菌的地方。
在对本发明作了总的描述之后,参照下面的特定具体实施例可以进一步理解本发明,这些实施例仅出于说明的目的,如无另外指明,无意限制本发明。实施例1
在100g水中分别加入下表1所列的各种碱性氧化物和氢氧化物30g。加入碱性氧化物或氢氧化物后,测量水溶液的pH值,结果列在表1。在加入碱性氧化物或氢氧化物之前,预先测得蒸馏水的pH为6.7。
还测得了碱性氧化物和氢氧化物的远红外发射率,结果列在表1。为此,借助于远红外分析仪,对表1所列的各种氧化物和氢氧化物的远红外发射率进行测量,然后根据波长在50℃使用该分析仪测量理想黑体的远红外发射率。远红外发射率定义为样品的发射率与理想黑体的发射率的面积比。在图1a和图1b中分别给出了氧化锌和氧化镁的发射谱,同时给出了理想黑体的发射谱。
按照韩国建筑材料学会的KICM-FIR-1002,通过摇瓶法测量MgO和ZnO粉末的抗菌活性。
大肠杆菌(ATCC 25922)和绿脓假单孢菌(ATCC 15422)与含有MgO和ZnO的发射粉末混合,制得标准试样,然后在肉汤中培养。发射粉末对细菌的抑制率表示成活细胞计数占标准试样的总活细胞计数的百分数。结果示于下表1。另外,在培养之前以及培养24小时后,标准试样中的试验细菌示于图2a和3b。
表1
材料号 | 粉末 | 饱和水溶液的pH值 | 远红外发射率 | 大肠杆菌死亡率(%) | 绿脓假单孢菌死亡率(%) |
1 | ZnO | 7.65 | 0.930 | 99.7 | 99.7 |
2 | MgO | 10.25 | 0.933 | 99.7 | 99.7 |
3 | Zn(OH)2 | 7.75 | 0.935 | 99.7 | 100 |
4 | Mg(OH)2 | 10.45 | 0.941 | 100 | 100 |
C.1 | TiO2 | 6.7 | 0.923 | 81.5 | 0 |
C.2 | Al2O3 | 6.7 | 0.923 | 0 | 0 |
C.3 | SiO2 | 6.7 | 0.918 | 10.5 | 0 |
C.4 | CaO | 12.35 | 0.915 | 100 | 100 |
C.5 | Na2O | >14 | 0.908 | 100 | 100 |
C.6 | Ca(OH)2 | 12.57 | 0.918 | 100 | 100 |
C.7 | NaOH | >14 | 0.909 | 100 | 100 |
从表1看出,白色的Al2O3、TiO2和SiO2粉末即使溶解时对蒸馏水的pH也没有影响。碱性氧化物ZnO、MgO、CaO和Na2O的水溶液具有碱性pH,因为它们部分溶解于其表面,分别形成氢氧化物Zn(OH)2、Mg(OH)2、Ca(OH)2和NaOH。而且,Zn(OH)2、Mg(OH)2、Ca(OH)2和NaOH粉末各自溶解的量与其相应的氧化物在水中的溶解量相同,然后测量所得水溶液的pH值。从表1的数据明显可以看出,氧化物的水溶液具有与其相应的氢氧化物粉末的水溶液几乎相同的pH值。这是因为当与水分接触时,如上所述,碱性氧化物ZnO、MgO、CaO和Na2O在其表面上形成氢氧化物,这些氢氧化物使溶液的pH值增大。
强碱性的CaO、Na2O、Ca(OH)2和NaOH在实际应用中是不利的,原因是它们可以对人体造成不利影响。相反,ZnO、MgO、Zn(OH)2和Mg(OH)2的碱性足够弱,不会对人体产生不利影响,但在足以抑制细菌生长方面很有效。实施例2
将MgO置入高压釜中,然后在110℃下,使其水化不同的时间,得到具有不同Mg(OH)2浓度的试样。通过热解重量分析法测量粉末中的Mg(OH)2含量。水化含量表示为进行热解重量分析时,重量变化占理论重量变化( ,30.8重量%)的百分数。
表2
MgO的颗粒尺寸和Mg(OH)2含量随水化时间的变化
材料号 | MgO的初始颗粒尺寸 | 水化时间 | ||
1小时(重量%) | 2小时(重量%) | 6小时(重量%) | ||
C.8 | <100目 | 10 | 14 | 25 |
5 | 100~200目 | 17 | 28 | 43 |
6 | 200~325目 | 31 | 47 | 54 |
7 | >325目 | 60 | 77 | 88 |
从表2中看出,随水化时间的增加,水化为Mg(OH)2的MgO增多。还发现形成的Mg(OH)2的含量取决于初始MgO颗粒尺寸。因此,将MgO粉化为更细的颗粒能够保证更大的Mg(OH)2含量。
当MgO的颗粒尺寸为大约100目或更大时,即使时间延长,所产生的Mg(OH)2的量也不会大到显示出充足的抗菌活性和远红外发射。因此,优选将MgO粉化为100目或更小的颗粒尺寸。实施例3
测定了实施例2的含有由MgO水化生成的Mg(OH)2每个试样的颗粒尺寸,结果列于下表3。颗粒尺寸的测量采用比表面积分析仪(Micromeritics Inc.制造)进行。
表3
材料号 | 初始颗粒尺寸 | 比表面积随水化时间的变化(m2/g) | |||
0小时 | 1小时 | 2小时 | 6小时 | ||
C.8 | <100目 | 0.3 | 0.68 | 0.79 | 0.76 |
5 | 100~200目 | 0.53 | 1.03 | 1.21 | 1.22 |
6 | 200~325目 | 0.67 | 1.68 | 2.45 | 2.38 |
7 | >325目 | 0.98 | 3.72 | 4.11 | 3.99 |
从表3的数据明显可以看出,粉末的比表面积随MgO水化时间的延长而增大。这是由于水化产生的微细的Mg(OH)2。但是,水化6小时后,发现比表面积不再增大,原因是在长时间的水化过程中,已经形成的Mg(OH)2在生长。
同时,初始颗粒尺寸100目的MgO粉末得到的水化含量不超过30%,比表面积也不会达到1.0m2/g,即使水化时间长达6小时也不行。实施例4
借助于傅立叶变换红外光谱仪(Midac Corporation制造),评价每个含有Mg(OH)2的试样的远红外发射率。试样的远红外发射率及其制备条件、Mg(OH)2的含量总结在下表4中。
试样的远红外发射率表示为在50℃下,试样的发射率对波长所作的发射曲线下覆盖的面积与理想黑体的发射曲线覆盖的面积之比。在这一点上,试样的发射率对远红外发射带(2.5-20μm)中的波长所作的曲线下覆盖的面积定义为试样的远红处能。
表4
材料号 | 初始颗粒尺寸(目) | Rxn时间(小时) | Mg(OH)2(重量%) | 比表面积(m2/g) | 远红外发射率 |
C.9 | <100 | 6 | 25 | 0.76 | 0.925 |
8 | 100~200 | 1 | 17 | 1.03 | 0.923 |
9 | 100~200 | 2 | 28 | 1.21 | 0.928 |
10 | 200~325 | 1 | 31 | 1.68 | 0.929 |
11 | 100~200 | 6 | 43 | 1.22 | 0.933 |
12 | 200~325 | 2 | 47 | 2.45 | 0.935 |
13 | 200~325 | 6 | 54 | 2.38 | 0.938 |
14 | >325 | 1 | 60 | 3.72 | 0.941 |
15 | >325 | 2 | 77 | 4.11 | 0.944 |
16 | >325 | 6 | 88 | 3.99 | 0.947 |
C.10 | >325 | 0 | 60 | 0.98 | 0.916 |
从试样8-16可以看出,远红外发射率随Mg(OH)2含量的增加几乎呈直线增加。Mg(OH)2含量的增加使微细颗粒的数量增加,并因此使比表面积增加。这说明含有Mg(OH)2的粉末可以应用于远红外辐射涂料。相反,对比例9尽管远红外发射率优良,但不适合在涂料中应用,原因是它的比表面积小。实施例5
评价商购试剂级、纯度为99%或更高的MgO粉末和从海水制得的试剂级Mg(OH)2粉末的远红外发射率。通过傅立叶变换红外光谱仪测量,发现目前商用的MgO的远红外发射率为0.904。另一方面,测得从海水制得的Mg(OH)2粉末的远红外发射率为0.946,仍然比商购的MgO的远红外发射率值高。根据这些结果,可以理解含有Mg(OH)2的远红外发射粉末不限于MgO水化制得的Mg(OH)2,而且也可以从海水中提取Mg(OH)2。实施例6
如下表5所示,远红外发射粉末与聚酯树脂结合,制备涂层材料。此后,使用刮条涂布机将其以不同的干厚度涂覆在电磁屏蔽钢板上,每块钢板在时变低频磁场中的最大磁导率为3000,碳含量为0.003%。形成的干厚度也示于下表5中。施用涂层材料后,在225℃下热固化钢板上的涂层,制备聚酯树脂涂覆的钢板。
评价聚酯树脂涂覆的钢板在5-20μm的波长带上的远红外发射率,结果列在下表5中。
为测试钢板的抗菌活性,使用KICM-FIR-1002的压缩法。在标准试样(不含抗菌陶瓷)和含有抗菌发射粉末的试验试样中接种大肠杆菌(ATCC 25922)和绿脓假单孢菌(ATCC 15422),然后用其他试样覆盖试验试样,之后在37℃下培养24小时。通过测量试验试样中的活细胞对标准试样中的活细胞的百分比,得到细菌的死亡率,结果列在下表5。
表5
材料号 | 发射粉末 | 粉末(重量份/100重量份PE) | 涂层厚度(μm) | 远红外发射率 | 大肠杆菌死亡率(%) | 绿脓假单孢菌死亡率(%) |
C.11 | 无 | 0 | 20 | 0.834 | 0 | 0 |
17 | MgO | 30 | 5 | 0.867 | 99.3 | 93.4 |
18 | MgO | 30 | 10 | 0.895 | 99.9 | 99.3 |
19 | MgO | 5 | 20 | 0.868 | 98.5 | 93.6 |
20 | MgO | 10 | 20 | 0.890 | 98.9 | 94.9 |
21 | MgO | 20 | 20 | 0.923 | 99.3 | 93.7 |
22 | MgO | 30 | 20 | 0.924 | 99.3 | 99.3 |
C.12 | ZnO | 15 | 20 | 0.904 | 29.7 | 88.7 |
23 | ZnO | 25 | 20 | 0.910 | 99.7 | 93.6 |
24 | ZnO | 35 | 20 | 0.912 | 99.6 | 93.8 |
C.13 | CaCO3 | 10 | 20 | 0.897 | 24.5 | 20.0 |
C.14 | CaCO3 | 20 | 20 | 0.916 | 96.7 | 80.6 |
25 | CaCO3 | 30 | 20 | 0.925 | 98.7 | 99.3 |
从表5明显可以看出,发现用比较材料号11处理的钢板远红外发射率极差,且没有抗菌活性。
从材料号17和18可以看出,随涂层厚度的增加,远红外发射率增加。但是,抗菌活性与涂层厚度无关。甚至厚度为5-10μm时,也能得到超过90%的死亡率。另外,尽管材料号17和18远红外发射率有某种程度地不佳,仍然显示超过90%的死亡率。基于这样的性能,材料号17和18可以应用作耐指纹涂层和薄膜涂层,以及PCM涂层。但是,材料号17和18的远红外发射率也超过0.85,满足远红外发射器的最低要求。
每100重量份聚酯树脂含5-10重量份MgO足以得到90%或更高的死亡率。用材料号19和20涂覆的钢板的远红外发射率低至0.85-0.90,但对细菌具有有效的抑制活性。但是,优选MgO的用量是每100重量份树脂10重量份或更高,以取得90.0或更高的远红外发射率。
对于100重量份树脂,大肠杆菌和绿脓假单孢菌的90%或更高的死亡率需要使用20重量份或更多的ZnO(材料号23和24),或30重量份或更多的CaCO3(材料号25)。实施例7
用韩国专利公开1998-8329号中描述的PCM涂层法制造的远红外发射钢板在5-8μm的波长带上具有低至0.5-0.8的远红外发射率,如图4a和4b所示。这被认为归因于这样的一个事实,即聚酯树脂在5-8μm的波长带上的远红外发射率低,如图5所示。
在特定的波长带上测定多种材料的远红外发射率,结果如图6a至6d所示,并总结于下表6中。
表6
材料号 | 发射器 | 备注 | 远红外发射率/5-8μm | 远红外发射率/5-20μm |
常规 | PCM板 | 韩国专利公开号1998-8329 | 0.5-0.8 | <0.90 |
C.15 | PCM树脂 | 聚乙烯 | 0.70 | 0.829 |
C.16 | TiO2 | 粉末 | 0.830 | 0.923 |
C.17 | Al2O3 | 粉末 | 0.823 | 0.923 |
C.18 | SiO2 | 粉末 | 0.870 | 0.918 |
26 | ZnO | 粉末 | 0.901 | 0.930 |
27 | MgO | 粉末 | 0.925 | 0.943 |
28 | CaCO3 | 粉末 | 0.923 | 0.940 |
29 | MgO+TiO2 | MgO 50重量%TiO2 50重量% | 0.912 | 0.928 |
从表6可以看出,测定了多个远红外发射率,其按照波长带随发射器的不同而不同。发现MgO、CaCO3和ZnO(材料号26和28)和至少含有这些氧化物之一的混合物(材料号29)在5-20μm的波长带上显示出优良的远红外发射率。即使波长带缩窄至5-8μm的范围,其远红外发射率仍然很优良。因此,发射粉末MgO、CaCO3和ZnO可用于提高聚酯树脂在5-8μm的波长带上的发射。实施例8
发射粉末以预定量与用于PCM的聚酯树脂结合,制备涂层材料。发射粉末的种类和用量见下表7。
然后,使用刮条涂布机将涂层材料以不同的干厚度涂覆在电磁屏蔽钢板上,每块钢板在低频最大磁导率为3000,碳含量为0.003%。形成的干厚度也列在下表7中。施用涂层材料后,在225℃下热固化钢板上的涂层以制备聚酯树脂涂覆的钢板。评价聚酯树脂钢板在波长带上的远红外发射率,结果列在下表7中。
表7
材料号 | 树脂中的粉末 | 粉末(重量份/100重量份PE) | 涂层厚度(μm) | 远红外发射率/5-8μm | 远红外发射率/5-20μm |
C.19 | 无 | 0 | 20 | 0.721 | 0.834 |
C.20 | TiO2 | 30 | 20 | 0.742 | 0.890 |
C.21 | Al2O3 | 30 | 20 | 0.728 | 0.902 |
C.22 | MgO | 10 | 20 | 0.790 | 0.890 |
C.23 | CaCO3 | 30 | 10 | 0.798 | 0.903 |
C.24 | CaCO3 | 30 | 30 | 0.860 | 0.927 |
30 | MgO | 20 | 20 | 0.858 | 0.923 |
31 | MgO | 80 | 20 | 0.868 | 0.927 |
32 | CaCO3 | 30 | 20 | 0.859 | 0.925 |
33 | ZnO | 25 | 25 | 0.857 | 0.912 |
34 | MgO+TiO2 | MgO 25TiO2 25 | 25 | 0.854 | 0.916 |
从对比材料号19可以看出,用不含任何远红外发射粉末的聚酯树脂涂覆的钢板在5-8μm的波长带上具有低的远红外发射率,原因是聚酯树脂本身的远红外发射率低。在聚酯树脂中含有Al2O3或TiO2的情况下(对比材料号20和21),在5-20μm的波长带上测得的远红外发射率平均较高,但当波长带缩窄至5-8μm时,远红外发射率很差。
相反,从材料号30-35可以看出,当含有MgO、CaCO3和ZnO时,即使用聚酯树脂涂覆,测定显示钢板具有0.85或更高的远红外发射率,原因是远红外发射粉末在5-8μm的波长带上具有优良的远红外发射率,补偿了聚酯树脂低劣的发射率。
当相对于聚酯树脂发射粉末的用量太少时,例如,每100重量份聚酯树脂10重量份用量,如对比材料号8所示,不能得到足够的远红外发射性能。另一方面,发射粉末用量过多时,例如,每100重量份聚酯树脂100重量份发射粉末,会带来与其它添加剂的相容性的问题,以及使涂布性能劣化。
如图7所示,象材料号35那样用含有MgO与TiO2的混合物的聚酯树脂涂覆钢板时,也检测到在5-8μm的波长带上具有优良的远红外发射率。实施例8
测量了按照实施例8的表7所示的条件涂覆的钢板,以及碳含量为0.003重量%、在时变磁场中的最大磁导率为3000的冷轧钢板在60Hz的电磁屏蔽效率和屏蔽效果。
由相同的材料制成的所有试样,冷轧钢板和树脂涂覆的钢板显示的电磁屏蔽效率分布在94.5至95.5%的范围中。考虑到试验误差,这些值基本是相等的。也发现电磁屏蔽效果分布在99至99.2%的窄范围内。
即使用含有这样的远红外发射粉末的聚酯树脂涂覆,钢板固有电和磁的屏蔽性能也不会改变。因此,本发明的远红外发射粉末可以应用于电磁屏蔽钢板以生产生物波钢板。实施例9
也测定了60Hz下时变磁场中的最大磁导率。结果总结在下表8中。
表8
材料号 | 板 | 组成和性能 | 最大磁导率 | 屏蔽效率(%) |
C.24 | 纯铜 | Cu≥99.9% | 1 | 0.4 |
C.25 | 纯铝 | Al≥99.9% | 1 | 0.3 |
C.26 | 冷轧钢板 | 0.04%C-99%≤Fe | 1350 | 74.8 |
36 | 冷轧钢板 | 0.003%C-99%≤Fe | 3700 | 96.4 |
37 | 冷轧钢板 | 0.02%C-99%≤Fe | 2100 | 90.4 |
38 | 硅钢板 | 99%Fe-1%非定向硅 | 4800 | 98.2 |
39 | 硅钢板 | 97%Fe-3%定向硅 | 18000 | 99.0 |
C.27 | 不锈钢板 | 70%Fe-18%Ni-8%Cr-4%其他元素 | 12 | 1.55 |
C.28 | 坡莫合金 | 60%Ni-30%Fe-10%其他元素 | 25000 | 99.3 |
纯铜和纯铝板(对比材料号24和25)均具有优良的导电性,但最大磁导率太差而不适用于低频磁场。对比材料号27的不锈钢板也不适用于本发明,原因是其最大磁导率在60Hz的时变磁场中太低。当含有超过0.02重量%的碳时,象对比材料号26那样,冷轧钢板在60Hz的时变磁场中的最大磁导率显著降低,因此不适合作为生物波钢板。坡莫合金如对比材料号28显示出极高的磁导率,但除在经济上不合适以外,其Fe含量也太低。实施例10
将含有Mg(OH)2的粉末(远红外发射率0.941)、硬玉粉末(远红外发射率0.934)和淡英斑岩粉末(远红外发射率0.956)加工成比表面积为1.0m2/g或更大的微细粉末。然后,将这些发射粉末以特定的比例与有机涂层材料混合,有机涂层材料例如,诸如那些含有丙烯酸树脂涂料的典型涂料、稀释剂、二甲苯溶剂等。含有发射粉末的涂料以不同的厚度涂覆到实施例9的材料号36的钢板上。干燥后,借助于傅立叶变换红外光谱仪(Midac Corporation制造),按涂层厚度评价如此形成的含有不同的发射粉末量的涂层的远红外发射率。将远红外发射粉末在涂层(为蒸发稀释剂而干燥后的)中的重量百分数(下文称“涂层中的发射器含量”),以及其依赖于涂层厚度的远红外发射率归纳列在下表9中。
表9
材料号 | 粉末 | 涂层中的发射器(wt%) | 涂层厚度(μm) | 远红外发射率 |
C.29 | 无 | 0 | 0 | 0.759 |
C.30 | 无 | 0 | 30 | 0.838 |
C.31 | Mg(OH)2 | 10 | 30 | 0.877 |
40 | Mg(OH)2 | 25 | 30 | 0.921 |
41 | Mg(OH)2 | 33 | 30 | 0.937 |
42 | Mg(OH)2 | 50 | 30 | 0.940 |
C.32 | Mg(OH)2 | 67 | 30 | 0.939 |
43 | Mg(OH)2 | 33 | 10 | 0.890 |
44 | Mg(OH)2 | 33 | 20 | 0.930 |
45 | Mg(OH)2 | 33 | 60 | 0.941 |
C.33 | Mg(OH)2 | 33 | 90 | 0.941 |
46 | 硬玉粉末 | 33 | 30 | 0.930 |
47 | 淡英斑岩 | 33 | 30 | 0.940 |
从表9的数据明显可以看出,纯粹的冷轧钢板(对比材料号29)和仅用不含远红外发射粉末的有机涂料涂覆的冷轧钢板(对比材料号30)的远红外发射率很差。发现用发射粉末涂覆钢板的远红外发射率大大地依赖于涂层中的发射器含量。当涂层中的发射器含量为10重量%或更低时,就象对比材料号31那样,钢板的发射率在发射效率方面有所降低。另一方面,当涂层中的发射器含量超过60重量%时,如对比材料号32,或涂层厚度超过60μm,如对比材料号33,不能进一步提高钢板的远红外发射效率,并观察到涂层的粘结力劣化。
相反,具有含有发射粉末的16-60μm厚涂层的钢板,如材料号40-47,表现出优良的发射效率。实施例11
磁场屏蔽试验结果显示,实施例10中材料号40-47的钢板的低频磁场屏蔽效率范围是90至91%,考虑到实验误差,该值与材料号37的钢板的值是相等的。因此,本发明的钢板可以用作屏蔽有害波长并发射有益的远红外辐射的生物波钢板。
工业实用性
如上文所述的本发明的远红外发射粉末具有优良的抗菌活性和远红外发射性能。而且远红外发射粉末可以应用于电磁屏蔽钢板而不会干扰钢板的固有电磁屏蔽效果。因此,本发明提供了屏蔽有害的低频电磁波、发射有益的远红外辐射、且对细菌的生长具有抑制活性的生物波钢板。
以示例的方式描述了本发明,应该理解所用的术语是为了进行描述而非限制。通过以上的教导,本发明的多种改进和变化是可能的。因此,应该理解在附带的权利要求的范围内,可在具体描述的范围之外实践本发明。
Claims (22)
1.一种远红外发射粉末,其具有抗菌活性,其在饱和水溶液中的pH值范围是7.5-10.5,并具有0.9或更高的远红外发射率。
2.权利要求1所述的远红外发射粉末,其中远红外发射率为0.92或更高。
3.权利要求1所述的远红外发射粉末,其中粉末的颗粒尺寸为100目或更小。
4.权利要求1所述的远红外发射粉末,其中粉末的比表面积为1.0m2/g或更大。
5.权利要求1-4任一项所述的远红外发射粉末,其中所述的粉末由选自氢氧化镁、氧化镁、氢氧化锌、氧化锌、碳酸钙、它们的混合物及含有部分这些物质的颗粒的材料制成。
6.权利要求5所述的远红外发射粉末,其中所述的粉末由氢氧化镁制成。
7.权利要求5所述的远红外发射粉末,其中所述的粉末含有至少17重量%的选自氢氧化镁、氧化镁、氢氧化锌、氧化锌、碳酸钙及它们的混合物的一种组分。
8.具有抗菌活性和远红外发射性能的树脂涂覆钢板,其具有干厚度为5-60μm的树脂涂层,所说的树脂涂层含有5-100重量份的远红外发射粉末/100重量份树脂,所说的粉末在其饱和水溶液中的pH值范围是7.5-10.5,并具有0.9或更高的远红外发射率。
9.权利要求8所述的树脂涂覆钢板,其中远红外发射率为0.92或更高。
10.权利要求8所述的树脂涂覆钢板,其中树脂涂层的厚度为15-30μm。
11.权利要求8所述树脂涂覆钢板,其中远红外发射粉末由选自氢氧化镁、氧化镁、氢氧化锌、氧化锌、碳酸钙、它们的混合物及含有部分这些物质的颗粒的材料制成。
12.权利要求8-11任一项所述的树脂涂覆钢板,其中所述的钢板具有0.85或更高的远红外发射率,对细菌生长的抑制效率为90%或更高。
13.权利要求12所述的树脂涂覆钢板,其中远红外发射率为0.90或更高。
14.权利要求8或12所述的树脂涂覆钢板,其中远红外发射粉末为氧化镁,其用量为每100重量份树脂5-100重量份,以及对细菌的抑制活性的抑制效率为90%或更高。
15.权利要求8或12所述的树脂涂覆钢板,其中远红外发射粉末为氧化锌,其用量为每100重量份树脂20-100重量份,对细菌的抑制活性的抑制效率为90%或更高。
16.权利要求8或12所述的树脂涂覆钢板,其中远红外发射粉末为碳酸钙,其用量为每100重量份树脂30-100重量份,对细菌的抑制活性的抑制效率为90%或更高。
17.权利要求8所述的树脂涂覆钢板,其中树脂为聚酯,远红外发射粉末具有0.90或更高的远红外发射率,以及干厚度为15-30μm。
18.权利要求17所述的树脂涂覆钢板,其中钢板在远红外全波长带上平均具有0.90或更高的远红外发射率,在5-8μm范围的远红外波长带上的远红外发射率为0.85或更高。
19.权利要求8或17所述的树脂涂覆钢板,其中钢板在60Hz的时变磁场中具有2000或更高的最大磁导率。
20.权利要求19所述的树脂涂覆钢板,其中钢板为冷轧钢板,或含碳量为0.02重量%或更低,含铁量为95重量%或更高,或被冷轧钢板覆盖的钢板。
21.权利要求19所述的树脂涂覆钢板,其中钢板为含有0.5-3.5重量%硅的硅钢板,或被硅钢板覆盖的钢板。
22.权利要求8或17所述的树脂涂覆钢板,其中涂层含有25-50重量%的远红外发射粉末。
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- 2002-08-12 NO NO20023814A patent/NO20023814L/no not_active Application Discontinuation
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CN107056286A (zh) * | 2017-04-25 | 2017-08-18 | 南昌大学 | 一种提高力学性能和抗菌能力的陶瓷复合物制作方法 |
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CN108611483A (zh) * | 2018-04-24 | 2018-10-02 | 广州才是科技有限公司 | 一种远红外线能量源设备及制作抗菌抑菌不锈钢材料的方法 |
CN108652380A (zh) * | 2018-08-16 | 2018-10-16 | 尚赫(天津)科技开发有限公司 | 一种带远红外功能的保温杯、远红外钢及其制备方法 |
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