CN1181787A - 聚合物、金属或陶瓷表面的改性 - Google Patents
聚合物、金属或陶瓷表面的改性 Download PDFInfo
- Publication number
- CN1181787A CN1181787A CN96193367A CN96193367A CN1181787A CN 1181787 A CN1181787 A CN 1181787A CN 96193367 A CN96193367 A CN 96193367A CN 96193367 A CN96193367 A CN 96193367A CN 1181787 A CN1181787 A CN 1181787A
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- ion
- angle
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Classifications
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/263—Bombardment with radiation with high-energy radiation
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
- B29C2035/0872—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using ion-radiation, e.g. alpha-rays
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Structural Engineering (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Textile Engineering (AREA)
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- High Energy & Nuclear Physics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Physical Vapour Deposition (AREA)
Abstract
本发明涉及使聚合物、金属和陶瓷表面改性的方法,它包括在真空条件下将带有能量的离子颗粒从预定的距离(照射距离)照射在所述表面上,同时将反应性气体吹在所述表面上,从而减小湿润角或增加该表面的粘附强度,并涉及具有以这种方法改性了的表面的聚合物、金属或陶瓷。
Description
本发明的背景
技术领域
本发明涉及聚合物、金属或陶瓷表面改性的方法,及具有以此方法改性表面的聚合物、金属或陶瓷,其中,该方法包括:在真空条件下,随着对聚合物、金属或陶瓷的表面吹送反应性气体,对该表面照射带有能量的颗粒,以便减小湿润角及提高其表面的粘附强度。该湿润角在鉴定被改性的表面状况方面是个重要的因素。减小湿润角则意味着该表面吸收水份,还意味着此表面具有亲水性。因此,当在这类表面上施以含水的着色剂时,铺散现象的发生就增加了,与其它材料的粘附强度就加大了,而因水在空气中的冷凝而产生的光散射则受到抑制。如上所述,可通过减少湿润角来改善表面状况。
对现有技术的描述
通常,改变湿润角一直是通过1)使表面变粗糙,2)表面清洗,3)提供带有亲水官能团的覆层,4)直接合成带有亲水官能团的表面,而粘附强度的提高则是以类似于改变湿润角时所用的方法完成的,即,1)在两种需连接的材料之间形成化学键,2)清洗表面,3)施加一种与该需连接的材料粘附的物料,4)形成带有官能团的表面,该官能团是用于促进与该需被粘附的材料的化学结合的(主要是亲水官能团)。
具体地讲,在改善聚合物表面方面的,目前用来减小湿润角的方法的例子包括:合成带有亲水官能团的表面,高压电晕放电和直流等离子体放电。
在它们之中,高压电晕放电是这样一种方法:其中,将聚合物试样置于一真空室中,该室中被充以反应性气体,直至达到大气压力为止,然后,以自电极放射出来的电子使该试样离子化,结果形成带有负电荷和正电荷的等离子体,其电-磁量与电子的电-磁量相等(下文称之为“冷等离子体”),然后,所形成的反应性气体离子幕化试样的表面上起反应,从而使其表面改性。尽管这种方法广泛地用于使聚合物表面改性,如在日本专利公告No.60-13823(1985.1.24)所公开的那样,只公开了通过采用高压电晕放电,在大气压下,用氯气处理乙烯基氯表面的方法,按此方法,湿润角从73°减到32°,而湿润角的这样的减小是不明显的。
虽然此方法与高压电晕放电方法相类似,但直流等离子体放电采用了通过辉光放电产生的等离子体(即称为“热等离子体”),即,被电离的反应气体,它们是在将反应气体加入0.01-5托的真空室中后形成的(大气压为760托)。然而,这种方法未显示出在减小湿润角方面的充分的效果。比如,日本专利公告No.61-171740(1986.8.2)公开了:发现在0.1托的压力下的氩气中使聚甲基丙烯酸甲酯(PMMA)聚合物表面改性后测得的湿润角为40℃,而在用水洗此PMMA聚合物表面数次后,该湿润角增加到60°。同时,在0.1毫巴(大气压力为1013毫巴)的压力下,在氧气气氛中使BX3聚合物表面改性后,当以所加的10-100W的电压处理160秒时,所测得的湿润角在48°-20°之间[D.W.Fakes,J.M.Newton,J.F.Wattes及M.J.Edgell,Surface and Interface Analysis,vol,10416-423(1987)]。
上述的常规方法不能明显地减小湿润角,因此,在聚合物表面上铺散含水着色剂、提高与其它极性材料的粘附强度及抑制由于水在空气中冷凝而产生的光散射的效果不足。此外,若用常规技术减小湿润角,如在用聚四氟乙烯的(PTFE)的情况下,湿润角的改变会趋近与随表面改性时间增加的相应的某个值,因此,与水所成的湿润角在采用氢等离子体时则从约95°变到约50°[D.T.Clark及D.R.Hutton,J.Polym.Sci.,Part A.25,2643(1987)],或在采用水蒸汽等离子体时,由约110°变到约70°。[D.Yousian及H.J.Griesser,Polymer,32(6)1126(1987)]。
通过对聚合物、金属或陶瓷的表面照射带能量的离子颗粒,同时在真空条件下对此表面吹送反应性气体,从而大大地减小湿润角及提高该表面的粘附强度而使此表面改性。
本发明简述
因此,本发明的目的在于提供一种在真空条件下,通过向聚合物、金属或陶瓷的表面照射带能量的离子颗粒,同时对该表面吹送反应性气体,从而减小该表面的湿润角及提高其粘附强度而使此表面改性的方法。
本发明的另一目的在于提供具有以上述方法改性其表面的聚合物、金属和陶瓷。
附图简述
图1是用于本发明的表面改性方法的表面处理装置的示意性剖视图。
图2是说明实施例1-1的试样1-1和1-2的湿润角测量结果的曲线图。
图3是说明实施例1-1的试样1-3-1-10的湿润角测量结果的曲线图。
图4是说明关于实施例1-2的试样1-5(离子照射=1016离子/cm2)的,为鉴定湿润角减小的测试结果的曲线图。
图5是试样1-5(离子照射=1016离子/cm2)与未经照射的试样对比的ESCA表面分析结果的曲线图。[A:未经照射的试样的C1(碳1)分析的结果/B:试样1-5的C1分析结果]
图6是试样1-3(离子照射=5×1016离子/cm2)和试样1-5(离子照射=5×106离子/cm2与实施例1-4的表面改性前的试样相比的显微照片。
[A:表面改性前的试样/B:试样1-3/C:试样1-5]
图7是展示用试样1-5透明胶带作的剥离试验结果的照片。
图8是说明实施例2-1的试样2-1和2-2的湿润角测量结果的曲线图。
图9是说明实施例2-1的试样2-3-2-6的湿润角测量结果的曲线图。
图10是说明实施例2-2的试样2-4(离子照射=1016离子/cm2)的湿润角测量结果的曲线图。
图11是说明试样3-1至3-10及3-12至3-16的湿润角测量结果的曲线图。[A:试样3-1至3-4/B:试样3-5至3-9/C:试样3-10及3-12至3-16]
图12是展示在表面改性之前和之后,对PE膜表面喷水后的表面状况的照片。[A:表面改性之前/B:表面改性之后(圆形部位)]
图13是说明实施例3-2的试样3-1、3-2、3-11及3-14的湿润角测量结果的曲线图。
[A:试样3-1的大气暴露/B:贮于水中的试样3-1和3-2/C:试样3-11和3-14的大气暴露/D:贮于水中的试样3-11]
图14是展示试样3-1和3-2的ESCA表面分析结果的曲线图图。
[A:试样3-1的C1分析结果/B:试样3-2的C1分析结果/C:试样3-2的O1(氧1)分析结果]
图15是展示试样3-10和3-11的ESCA表面分析结果的曲线图图。
[A:试样3-10和3-11的C1分析结果/B:试样3-10和3-11的C1分析结果]
图16是展示试样3-1和3-2的用透明胶带作的剥离试验结果的照片,根据实施例3-4,该试样沉积了铝。
图17是展示用沉积了铜的试样3-1和3-2的用透明胶带作的剥离试验结果的照片。
图18是说明实施例3-5的试样3-1和3-2的粘附强度测试结果的曲线图图。
详述本发明
本发明将详述如下。
用于本发明中的术语“湿润角”被定义为:在置于表面上的水滴在切线与存有该水滴的表面本身间所成的角。此切线是从该水滴与该表面相接触的一点画引出的。比如,假设置于表面上的水滴为一完整的球形,则位于水与此表面相接触的点处的切线将落在此表面本身上(在一个单点处)。即,在该表面上的是完整球形的水滴的切线与包含此水滴的表面本身间形成角应为180°。而现实是,放在表面上的水因其在此表面上铺散而不是一完整的球形。由上可知,此水滴会形成一个圆,而可在沿这样的圆的周围上的多个点处形成多条与该水滴表面同样相切的线。在这种切线之一条和包括着水滴的表面间形成的角被称为湿润角。
减小湿润角则意味着该水滴广而地铺展在材料表面上,因此该表面的吸收性即亲水性就提高了。湿润角是通过用ERMA接触量角器,借助显微镜,测量在将蒸馏3次的水0.05ml滴在该表面上的四个不同部位上后,在切线和该表面间形成的角而测得的,然后用此四处的测值的平均值为湿润角。
当按本发明方法的某种条件将带有能量的离子颗粒照射在聚合物、金属或陶瓷的表面上时,其中有的该化学键,如碳-碳、碳-氢和碳-氧则因与偶迂的高能离子颗粒碰撞而断裂,并因而活化。接着,这些活化的基团彼此间反应,或与该照射的离子颗粒,或与直接吹送到该表面上的反应性气体如氧、氮等反应,从而使该活化基团和反应性气体结合而在此表面上形成亲水基团。
由于这样的事实:在随着对该表面吹送反应性气体的同时照射离子后,所测的湿润角减小,则在此表面上形成亲水基团是可以预见的,而且这还可通ESCA(用于化学分析的电子光谱)得到证实。按ESCA,与未经照射的聚合物、金属或陶瓷相比,以气体环境照射过的聚合物、金属或陶瓷的亲水官能峰的峰值升高,证明了由于照射处理亲水基团在其表面上产生。
在本发明中,减小湿润角意味着在聚合物、金属或陶瓷表面上形成了亲水基团,而亲水基团的形成又意味着减小了湿润角。比如,当如前述那样,当对表面照射带有能量的离子颗粒时,在该聚合物表面上的该分子聚合物链被断开,而带有能量的照射离子颗粒持续进行这种链断开,直至这些颗粒失去其全部能量为止。在链已断开的部位,即活化部位,吹在该聚合物周围的反应性气体会借助其反应途径而反应,结果形成如羰基、酯、羟基、羧基、氨基、硝基等之类的亲水基团。
任何的含有碳、氧、氮、氟、硅等键的聚合物都可用于本发明的使聚合物表面改性的方法。
作为这类聚合物的具体例子,可以使用聚碳酸酯、聚亚甲基丙烯酸甲酯、聚酰亚胺、聚四氟乙烯、聚偏氟乙烯、聚对苯二甲酸乙酯聚乙烯和硅橡胶、天然橡胶、合成橡胶、乙酸纤维素、再生的乙酸酯、聚丙烯、聚苯乙烯、丙烯腈-丁苯的共聚物、酰胺、环氧树脂、聚氯乙烯、聚乙烯醇、聚亚甲基、聚亚苯基氧、聚砜、酚醛、蜜胺树脂、丁腈橡胶、丁苯橡胶及这些聚合物的混合物等。
按本发明改性的PMMA的湿润角下降到8°,而PC的湿润角下降到12°。在PI的情况下,该聚合物表面的湿润角减小得如此显著,以致使滴在该聚合物表面上的水滴持续流动,从而使得此湿润角测不出来,因此,该聚合物表面的亲水性被提高,并可得到上述的优点。此外,这种经改性的聚合物的湿润角甚至在用水洗后仍保持不变,这表明在该表面上形成的亲水基团是非常稳定的。
按本发明的一实施方案,带有能量的离子颗粒的照射量为1014-5×1017离子/cm2,而离子颗粒的能量为0.5KeV-2.5KeV,最好是约1KeV。特别是,离子颗粒的能量和能量密度依表面材料而变。若离子颗粒的照射量和能量超出某种范围,则出现对此表面的无益的破坏,如溅射效应(其中该表面部分分离),材料的键的不希望的断开及其它的不希望的效果。
通过将包括原子、分子的颗粒和气体引入可电离的离子枪可得到离子束。
至于离子枪,冷中空阴极型、考夫曼型、高频型等的都可用。任何可离子化的颗粒,如氩、氧、氪、空气、氧和氮的混合气体,或它们的任何的混合气体都可用。如上所述,通过对此离子束加电压,使该离子颗粒获得能量。通过调节该离子束的电流、可控制离子颗粒的照射量。可根据放电电流、放电电压、加速电压等控制该离子束的电流。
当将该离子颗粒照射在材料如聚合物、金属或陶瓷的表面上时,这些颗粒中的一部分在该表面上直接反应,但大部分颗粒被用于使其中的化学键断开。一旦引入了上述的反应性气体,该真空室中的压力就由原来的10-5-10-6的真空状态升到10-4-5×10-4,然后保持此压力。上述真空状况是为产生带能量的颗粒而适当地设定的。一般说来,在低真空的条件下,若真空室内的压力变得过高,则因施于离子束上的高电压(0.5-2.5KeV)而出现电弧放电,而且来自此离子束的离子颗粒与其它的剩余的气体颗粒碰撞,从而在该颗粒到达该表面前的某一段距离前被阻止其继续前进,因此所产生的离子不能有效地到达该表面。在此情况下,从离子枪到该表面的距离必须缩短,以保证该离子颗粒到达该聚合物表面。换言之,产生离子的气体的引入量必须被控制,以便根据材料的利用精度保持真空状态。
按本发明的另一实施方案,反应性气体是能产生亲水官能的适宜的气体,比如是氧、氢、氮、一氧化碳、氨及任何的混合气体等。为保持适当的压力以便在真室中产生等离子体及使用于形成亲水基团所需的反应气体足量,则将这些反应性气体的引入量限于1-8ml/分的范围。对于引入此反应性气体而言,在照射带能量的颗料的过程的同时将反应性气体直接吹送在该表面上是有益的。
按本发明的另一实施方案,当以1-30μl/cm2的离子束电流密度照射带能量的离子颗粒时,照射距离依真空度而定,该距离在5×10-3托或更小时,最好为25cm或更短,在5×10-3-1×10-6托的高真空时,则为25-55cm,而在10-6托或更高的超高真空下,可达到55cm或更长的距离。当带有能量的颗粒到达此要被改性的表面时,该离子颗粒所需的“平均自由途径”将随该真空室内的压力大小而变。因此,根据各种真这度范围得到上述定义的距离。如上所述,因为离子颗粒的能量低到0.5-2.5KeV,所以可适当地调整此照射距离。
如图1中所描绘的,本发明的用于聚合物、金属或陶瓷表面改性方法中的装置由与电源(未示出)相连的,用于产生带有能量的离子颗粒的离子枪、朝向该枪定位的试样固定架(5)、用于引入适量气体,以便在试样表面上产生反应性的官能团的,设有控制单元的反应性气体引入器(3)和包围上述部件的真空室(1)组成。在该真空室中,设有真空计(4)以便使该真空室中的真空条件不变。
采用本装置的使优选材料的表面改性的方法具体包括如下步骤:
1.用肥皂水、有机溶剂(甲醇、异丙醇)等清洗此表面,以此既能进行有效地清洗,又不损伤表面。另外,可用带有能量的颗粒照射表面而去除表面杂质。
2.若需要,将该材料于干燥炉中(60℃)贮放过夜,以便去除吸附于其表面上的不希望的物料。
3.然后将此清洁地洗过的材料置于保持真空压力为10-5-10-6托的真空室中。
4.借助气体引入器(3)将反应性气体引至该材料周围,同时在1-8ml/分的范围内改变反应性气体的引入量。
5.通过将工作气体引入离子枪(2)中而产生带能量的颗粒。于此时,适当调节与离子枪相连的电源(未示出)以使该颗粒具有0.5-2.5KeV的能量。
6.通过改变该离子束的电流,以1014-5×1017离子/cm2的照射量将此具有能量的颗粒照射在其表面上。最佳实施方案的描述
下面参照后面的实施例更详细地描述采用上述装置的使聚合物、金属、陶瓷表面改性的方法。但是,无意将本发明的范围限于这些实施例。实施例11)聚合物PC的表面改性
将用肥皂水或有机溶剂如甲醇或异丙醇洗过的市售的聚合物PC切成10×10×3mm3的试样。将此试样于湿度保持在60℃的干燥炉中贮放过夜,以去除吸附在该表面上的不希望的物料。将所得的聚合物试样放入压力保持在10-5-10-6托的真空室中,然后在表1中所述的条件下分别经离子枪和气体入口引入产生离子的气体和反应性气体,以便进行表面改性。于此时,适当控制工作气体的引人量,以便将真空室中的真空保持在1×10-4-5×10-4托。对于按各个条件经表面处理的试样,用ERMA湿润角量角器测其湿润角,然后将结果绘于图2(试样1-1和1-2)及图3(试样1-3至1-10)中。
表1
No. | 离子颗粒 | 离子能量KeV | 离子照射量离子/cm2 | 反应性气体 | 反应性气体量ml/分 |
1-11-21-31-41-51-61-71-81-91-10 | Ar+Ar+Ar+Ar+Ar+Ar+O2 +O2 +Ar+Ar+ | 0.5-1.50.5-1.511111111 | 101610161014-5×10171014-5×10171014-5×10171014-5×10171014-5×10171014-5×10171014-5×10171014-5×1017 | -O2-O2O2O2-O2H2N2 | -4-246-444 |
图2是说明湿润角随离子颗粒的能量改变而改变的结果的曲线图。
当在该聚合物表面周围吹氧时,显示出,与典型的湿润角改变(主要是40°-50°)相比,出现了明显的湿润角减小。尤其是,在离子颗粒能量为1KeV时,达到了最小湿润角。
图3是说明试样1-3至1-10的湿润角依离子能量为1KeV时的照射变化而变化的结果的曲线图,而试样1-3、1-4、5和6,其于离子能量为1KeV时,依据照射量变化而产生的湿润角变化,在氧量为4ml/分时,即反应性气体在试样周围流动时,有最小值,而且还在1014离子/cm2时显示出最小值。
还有,试样1-3和1-7、1-5和1-8是惰性气体和反应性氧气照射在该表面上时的对比情况,虽然在将氩离子照射在该表面上的情况下小有区别,但当照射带有能量的离子颗粒,同时将氧吹送在试样周围时,则显示出湿润角的减小是相近的。另一方面,仅照射氩离子的对比例(1-3)的湿润角变化在5×1014Ar+/cm2时减到50°,而且还显示出,依据照射量的加大,湿润角几乎没有区别。反之,在按照本发明的实施例(1-4)中,照射氩离子,同时吹氧,都显示出湿润角根据氩离子照射量的增加有明显的减小,以及湿润角的明显减小。
尤其是,最小湿润角(12°)在照射量为1016Ar+离子/cm2时出现。这些结果意味着,带有能量的离子颗粒的量和能量本身是重要因素,而在试样周围引入反应性气体也起着重要作用。除此之外,当试样1-3与试样1-8,9和10对比时,则显示出:反应性气体的反应度或负电性(氧>氮>氢),很符合湿润角的变化。2)湿润角鉴定试验
将按上述试验1)进行过表面处理的并有最高湿润角减小的试样1-5(离子照射量=1016离子/cm2)暴露于空气中,然后在这段时间过程中测湿润角。以一段恒定的时间还将同样的试样浸在1%的稀盐酸中,然后用干燥氮气干燥并再次测量湿润角。
图4说明了所测的湿润角的结果。
如图4中所示,在暴露于空气中的试样中,湿润角随时间加大,而浸于1%的稀盐酸中的试样保持最小的湿润角,而无湿润角的明显改变。这些结果证实了:在该聚合物的表面上已形成了亲水性官能团。因此,对暴露在空气中的试样而言,被认为:在该聚合物表面上形成的亲水性官能团随时间朝着具有很多极性官能团的该聚合物基剂的方向回转,然而在浸于1%稀盐酸的试样中,这种回转由于HCl溶液中的高极性而得以防止。3)亲水官能团形成的检验试验
对与未照射离子的试样对比的试样No.1-5(离子照射量=1016离子/cm2)进行ESCA表面分析。结果示于图5。
在图5中,从相对于碳的ESCA分析结果显示出:在286eV和287.73eV时形成了相当多的亲水官能团。还有,从相对于氧的ESCA分析结果显示出:当按本发明使聚合物表面改性时,氧与该表面分子反应,结果在其中结合,从而使对该表面起亲水作用的氧量增加了约2倍或更多。4)表面粗糙度试验
对于未照射离子的试样及经表面处理的试样1-3离子照射量=5×1016离子/cm2)和1-5离子照射量=5×1016离子/cm2),用AFM(原子力显微镜)观察其表面,然后将结果示于图6中。
在图6中,当对表面改性前,该表面粗糙度约为14埃(参见图6A)的试样仅照射氩离子时,其表面粗糙度增加到约22-27埃(参见图6B),而当在氧气氛下进行表面改性时,则发现表面粗糙度类似于上述结果,在26-30埃的范围内(见图6C)。表面粗糙度的这种变化,与常规表面改性法相比,有很大不同,在常规改性法中的表面粗糙度主要仅改变几个μm单位。换言之,当已进行了常规表面改性的改善粘附强度时,对于作为光学存储装置的这类领域中的用途而言,该光学存储装置每单位面积贮藏信息的能力很大程度上受表面粗糙度的限制。但是,按本发明的表面改性法,表面粗糙法变化不大,从而将本发明的经改性的聚合物用于光学存储装置用途时,可期望存储能力几乎未减少。5)用透明胶带进行的剥离试验
用热蒸镀将铝蒸发在未照射离子的试样和分别以1015、1016和1017离子/cm2照射离子的经表面改性的试样1-3和1-5上(1000埃),然后用透明胶带对上述试样进行剥离试验,其结果示出图7中。
在图7A中,显示了在未经照射的试样的情况下(图7A左侧),金属被完全分离,而当仅照射氩离子时,铝被透明胶带部分或全部剥离。但当表面按本发明在氧气氛下改性后沉积铝时,则沉积的铝未被剥离(图7A右侧)。实施例2 聚合物PMMA的表面改性1)表面处理
按与实施例1-1相同的程序,在表2中所述的条件下对市售的PMMA进行表面处理,然后测量湿润角,结果示于图8(试样2-1和2-2)和图9(试样2-3至2-6)中。
表2
No. | 离子颗粒 | 离子能量 | 离子照射量离子/cm2 | 反应气体 | 反应气体量,ml/分 |
2-12-22-32-42-52-6 | Ar+Ar+Ar+Ar+O2 +O2 + | 0.5-1.50.5-1.51111 | 101610161014-5×10171014-5×10171014-5×10171014-5×1017 | -O2-O2-O2 | -4-4-4 |
图8是说明相对于离子颗粒的能量改变的湿润角改变的结果的曲线图。当在该聚合物表面周围吹氧时,有湿润角的明显改变,而且可看到比一般的湿润角减小(大部分是40°-50°)相比有明显的湿润角减小。尤其是,以1KeV的离子颗粒能量可得到最小的湿润角。
图9是说明以1KeV离子颗粒能量,依据离子照射变化,由试样2-3至2-6的湿润角变化结果的曲线图。而试样2-2和2-4、2-5和2-6是对比例,其中惰性气体氩和反应性气体氧被照射在此表面上,虽然在该表面照射氧离子的情况下和照射氩离子的情况下小有区别,但当照射带有能量的离子颗粒,同时在试样周围吹送氧气时,对观察到类似的湿润角减小。除了其中仅照射5×1017Ar+/cm2的氩的对比例的湿润角减小到约50°之外,在照射量增加时未见到进一步值得注意湿润角变化。相反,而符合本发明的,其中照射氩离子同时又吹氧的实施例(2-4),则观察到湿润角依据氩离子照射量的增加而明显减小。尤其是在照射量为1016Ar+离子/cm2,见到8°的最小湿润角。上述的这些结果意味着:带能量的离子颗粒的量及这种能量本身是重要因素,而试样周围的反应性气体也起着重要使用。2)湿润角鉴定试验
表面已如上述试验1)进行了处理的试样2-4(离子照射量=1016离子/cm2)在暴露于空气中时有最大的湿润角减小,而后在这段时间过程中测量此湿润角。还将同样的试样以恒定的时间浸于1%的稀盐酸中,用干氮气干燥,然后测量湿润角。测得的湿润角结果示于图10中。
如于图10中所示,得到了与图4所示的实施1-2中的相似的结果。3)用透明胶带作的剥离试验
如于图7B中所示,在PMMA被改性的情况下,薄膜完全分离(图7左侧),而在通过吹氧改性的情况下,仅在施加了10次或更多次分离后才达到有效剥离。实施例3其它聚合物的表面改性处理1)表面处理
如实施例1-1一样,在表3中所列的条件下,对市售的聚合物PTFE、硅橡胶、PI和PEI进行表面处理。其结果示于图11中。
表3
号 | 聚合物种类 | 离子颗粒 | 离子能量KeV | 离子照射量离子/cm2 | 反应性气体 | 反应性气体量,ml/分 |
3-13-23-33-43-53-63-73-83-93-103-113-123-133-143-153-16 | 聚四氟乙烯聚四氟乙烯硅橡胶硅橡胶PIPIPIPIPIPETPETPETPETPET | Ar+Ar+Ar+Ar+Ar+O2 +Ar+O2 +Air+Ar+Ar+Kr+Kr+O2 +Ar+Ar+ | 111111111111111I | 1014-10171014-10171014-10171014-10171014-10171014-10171014-10171014-10171014-10171014-10171014-10171014-10171014-10171014-10171014-10171014-1017 | -O2-O2--O2O2--O2-O2-O2O2 | -4-6--44--6-6-24 |
如于图11中所示,在通过吹反应性气体如氧等于试样周围而进行如上所述的照射的情况下,所得的结果与上述实验相似,因而这证明用任何带能量的离子颗粒(Air+、Kr+、O2 +等)而不限于氩离子所进行的表面改性处理可用于全部聚合物上。实际上,在PE的情况下,在向其中喷水时,水滴在符合本发明的改性了的聚合物表面完全铺散开未(示于图12B,圆形部位(照片下部))结果形成透光的镜子样的表面,而在未改性的表面上,水滴在其上形成,因而出现光散射(图12A)。这证明了在PE情况下的优越的表面改性效果。2)鉴定湿润角的试验
按上述程序1),将试样3-1(离子照射=1014、1016、1017)、3-2(离子照射=1014、1016、1017)、3-11(离子照射=1014、1016、1017)暴露于空气中,然后按时间测其湿润角,在将试样3-1(离子照射=1014、1016、1017)、3-2(离子照射=1014、1016、1017)及3-11(离子照射=1014、1016、1017)贮放一段时间后,测量其湿润角。结果示于图13A、B、C和D中。
如于图13A中所示,仅用氩离子表面改性的PTFE试样(3-1),在暴露于空气中的过程中湿润角稍有增加,但变化不大。但是,若将这些试样贮于水中然后干燥,则被测得的湿润角随时间的延续而减小(图13B)。反之,已通过吹氧而进行了表面改性的试样(3-2)的湿润角,如图13B中所示,在将该试样贮于水中时,则明显减小。
在图13C中,已通过吹氧而进行了表面改性的试样(3-11)的湿润角随时间的延续持续增大,因而其表面变为疏水性,而若将这些试样贮在水中,则其湿润角不变并保持定值(图13D)。但是,仅用氧离子束来照射过的试样(3-14)被暴露于空气中时,其湿润角随时间的延续几乎保持不变。
由于对进行了常规表面处理的试样进行了相似的试验,即贮放于水中,湿润角最多增大到原值。这被解释为这样一种现象:其中虽然已形成某些亲水官能团,但该聚合物表面受到离子束或等离子体放电的严重损坏,结果被溶于水中[聚合物,第21卷,895,1908]。因此,从按本发明表面改性的聚合物的观点看,甚至在将该聚合物贮于水中,也保持减小了的湿润角,所以本发明有别于常规的表面处理方法。3)亲水基团形成的检测试验
以ESCA对已经1015、1016、1017离子/cm2离子照射而表面改性的试样3-1和3-2进行表面分析,其结果被示于图14中。此外,对经1014、1016、1017离子/cm2的离子照射的表面改性的试样3-10和3-11,以及未经离子照射的试样作ESCA表面分析,其结果表示于图15。
图14A和14B展示了用ESCA进行的相对聚四氟乙烯的对比分析结果。292eV的碳峰是C-F键合的峰,而当照射氩离子同时在试样周围吹O2时备种新键如C-O、C=O、COO等在C-C键(284eV)之间形成。在氧键峰的情况下,原聚四氟乙烯中不存在的新的氧键得以产生(图14C)。
在展示PET的ESCA分析结果的图15A中,当只对该表面照射氩时,288e V和286eV的结合能,即C=O,C-O键处的峰减小,而当在照射氩的同时在该聚合物周围吹氧时,在该表面上存有亲水官能团的288eV和286eV部位峰变宽。另一方面,在氩照射量为1017离子/cm2的情况下,亲水基团的数目因照射离子数的增加而减少。另外,作为附加的结果,在针对氧的ESCA分析结果中,当只对该表面照射氩时,则发现氧的量在最高为1016离子/cm2的范围内减少。这证明了在该聚合物表面上生成了亲水官能团。4)用透明胶带作的剥离试验
通过将铝(2000埃)和铜(2000埃)沉积在未照射离子的试样上和经以1015、1016及1017离子/cm2的离子照射的表面处理的试样3-1和3-2上,然后将透明胶带的剥离试验示于图16和17。
在图16和17中,所展示的是当只照射氩离子时,铝和铜被透明胶带部分或完全剥离。但是,当在该表面按本发明用吹氧改性后沉积此金属时,这类金属未被剥离。5)通过粘附进行的粘附强度试验
如于图18中所示,将粘附剂(Crystal Bond Buehler,Thermoplastic Cement No.40-8100)涂在经表面改性的聚四氟乙烯试样3-1和3-2的两侧,然后检测其粘附强度。其结果示于图18中。
如于图18中所示,仅用本实验的氩照射进行的表面改性使粘附强度提高,而在以吹氧进行的表面改性的情况下,粘附强度进一步提高。
因此,按照本发明的使聚合物、金属和陶瓷的表面改性的方法,在其表面上形成了亲水基团,从而明显地减小了与水的湿润角,因而该方法可广泛地用于各种应用领域,这是因为它提供了含水着色剂增加或铺散的效果,提高了与其它材料的粘附强度及抑制了光散射。尤其是,在将该聚合物和于制造反射镜的场合下(该镜是由金属箔及透明聚合物材料构成的),提供了非常清洁的表面,并具有优越的粘附强度。还有,若用湿法涂覆其它材料以产生亲水官能团,则可得到非常平滑和湿的涂层,这与以在医用聚合物领域中一直很重要的常规方法获得的常规的不均匀的涂层相比,是很大的改进。本发明的方法在制备医用聚合物方面也是有用的。
Claims (9)
1.使聚合物、金属和陶瓷表面改性的方法,它包括在真空条件下,从预定的距离(照射距离)对所述表面照射具有能量的离子颗粒,同时直接对所述表面吹反应性气体,从而减小该表面的润润角或提高其粘附强度。
2.权利要求1的方法,其中该反应性气体选自由氧、氮、氢、氨、一氧化碳和这些气体的任何的混合物所构成的物组。
3.权利要求1的方法,其中该反应性气体的引入量为1-8ml/分。
4.权利要求1的方法,其中该聚合物选自由聚碳酸酯、聚亚甲基丙烯酸甲酯、聚酰亚胺、聚四氟乙烯、聚偏氟乙烯、聚对苯二甲酸乙酯聚乙烯和硅橡胶、天然橡胶、合成橡胶、乙酸纤维素、再生的乙酸酯、聚丙烯、聚苯乙烯、丙烯腈-丁苯共聚物、酰胺、环氧树脂、聚氯乙烯、聚乙烯醇、聚亚甲基、聚亚苯基氧、聚砜、酚醛、蜜胺树脂、丁腈橡胶、丁苯橡胶及上述聚合物的混合物所组成的物组。
5.权利要求1的方法,其中该具有能量的离子颗粒选自由氩、氧、空气、氪及其任何的混合物所构成的物组。
6.权利要求1的方法,其中该离子颗粒的能量为0.5-2.5KeV。
7.权利要求1的方法,其中该具有能量的离子颗粒的照射量为1×1014-5×1017离子/cm2。
8.权利要求1的方法,其中当将该具有能量的离子颗粒照射在该表面上时,照射距离依真空度而定,而在5×10-3-1×10-6托的高真空时此距离为22-55cm,在10-6托或更高的超高真空时为55cm以上,在5×10-3托或更小的低真空时为小于25cm。
9.具有这样有面的聚合物、金属或陶瓷,通过在真空条件下对该面照射具有能量的离子颗粒,同时对该表面直接吹反应性气体而使该表面上的湿润角减小或粘附强度增大。
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Cited By (3)
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-
1996
- 1996-02-28 US US08/608,054 patent/US5783641A/en not_active Expired - Lifetime
- 1996-02-29 JP JP53163596A patent/JP3213005B2/ja not_active Expired - Lifetime
- 1996-02-29 BR BR9608228A patent/BR9608228A/pt not_active IP Right Cessation
- 1996-02-29 DE DE69617221T patent/DE69617221T2/de not_active Expired - Lifetime
- 1996-02-29 WO PCT/KR1996/000032 patent/WO1996033293A1/en active IP Right Grant
- 1996-02-29 ES ES96906089T patent/ES2164873T3/es not_active Expired - Lifetime
- 1996-02-29 AU AU49569/96A patent/AU4956996A/en not_active Abandoned
- 1996-02-29 EP EP96906089A patent/EP0822995B1/en not_active Expired - Lifetime
- 1996-02-29 CN CN96193367A patent/CN1107124C/zh not_active Expired - Lifetime
- 1996-04-19 KR KR1019960011995A patent/KR100324619B1/ko not_active IP Right Cessation
- 1996-04-19 KR KR1019960011994A patent/KR100316586B1/ko not_active IP Right Cessation
- 1996-04-19 KR KR1019960011996A patent/KR100288500B1/ko not_active IP Right Cessation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102926197A (zh) * | 2012-11-15 | 2013-02-13 | 杭州水处理技术研究开发中心有限公司 | 一种用于离子交换膜制备的支撑布制造方法 |
CN102926197B (zh) * | 2012-11-15 | 2014-05-07 | 杭州水处理技术研究开发中心有限公司 | 一种用于离子交换膜制备的支撑布制造方法 |
CN109353036A (zh) * | 2018-10-31 | 2019-02-19 | 东莞太洋橡塑制品有限公司 | 亲水基硅胶表面处理工艺 |
CN112921444A (zh) * | 2021-03-09 | 2021-06-08 | 许玉华 | 一种抗紫外功能纤维及其制备工艺 |
CN112921444B (zh) * | 2021-03-09 | 2023-02-03 | 无锡市世纪风服饰有限公司 | 一种抗紫外功能纤维及其制备工艺 |
Also Published As
Publication number | Publication date |
---|---|
BR9608228A (pt) | 1998-12-29 |
US5783641A (en) | 1998-07-21 |
JP3213005B2 (ja) | 2001-09-25 |
KR960039135A (ko) | 1996-11-21 |
KR100288500B1 (ko) | 2001-05-02 |
EP0822995A1 (en) | 1998-02-11 |
CN1107124C (zh) | 2003-04-30 |
KR100316586B1 (ko) | 2002-02-28 |
JPH11501696A (ja) | 1999-02-09 |
DE69617221T2 (de) | 2002-05-08 |
AU4956996A (en) | 1996-11-07 |
DE69617221D1 (de) | 2002-01-03 |
EP0822995B1 (en) | 2001-11-21 |
ES2164873T3 (es) | 2002-03-01 |
WO1996033293A1 (en) | 1996-10-24 |
KR960037742A (ko) | 1996-11-19 |
KR100324619B1 (ko) | 2002-10-12 |
KR960039134A (ko) | 1996-11-21 |
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