CN102482616B - 平面显示器装置的玻璃基板用清洁剂组成物 - Google Patents
平面显示器装置的玻璃基板用清洁剂组成物 Download PDFInfo
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
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- Surface Treatment Of Glass (AREA)
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Abstract
本发明涉及一种平面显示器装置的玻璃基板用清洁剂组成物,所述组成物包括:包含附加环氧烷的萜型油的非离子型表面活性剂;多元醇系化合物;碱金属氢氧化物;及水,其中,清洁剂组成物的pH为12~14。
Description
技术领域
本发明涉及一种平面显示器装置的玻璃基板用清洁剂组成物,其为低发泡性水性(aqueous)清洁剂。
本申请请求2009年10月30日提出的韩国专利申请第10-2009-0104416号(其在此借引用方式全部并入本申请)的权益。
背景技术
类似于半导体装置,FPD(flat panel display device)使用薄膜形成、曝光、蚀刻等制造。然而在各制程中,大小为1微米或更小的微小粒子(Particle)(如各种有机或无机材料)可能附着在基板表面而不希望地造成污染。如果使附着有这些粒子的基板接受后续程序,则可能发生薄膜的针孔或孔蚀、或线路的中断或桥接,而不希望地降低制造良率。
因此在各程序之间实行用于去除污染物的清洁程序,且因此已提议多种清洁剂。例如韩国未审查专利第2003-0039408号公开了一种水性清洁剂,其包含由附加环氧烷的芳族醇所组成的非离子型表面活性剂、与由附加环氧烷的烃醇(hydrocarbon alcohol)所组成的非离子型表面活性剂。然而此清洁剂因为使用非离子型表面活性剂(其为环氧烷与长链烃的加成物),则在进行喷洒或其它程序时可能起泡而不利。另外,韩国专利第10-0574607号公开了一种酸性pH条件清洁液,其包含去离子水、有机化合物、与铵化合物。然而此清洁液为酸性,且遗憾地在清洁程序的起初阶段无法充分地去除大小为1微米或更小的微小粒子(Particle),如有机或无机材料。另外,日本未审查专利第7-133496号公开了一种清洁剂组成物,其包含由附加环氧烷的长链醇所组成的非离子型表面活性剂、短链二醇醚溶剂、长链二醇醚溶剂、链烷烃系或烯烃系烃、与水。然而在使用烃溶剂时可能发生易燃性及干燥问题。此外,在热烷基的碳数量增加的情形中,清洁剂的黏度可能增加,且其在水中的溶解度可能降低。
发明内容
因而本发明提供一种FPD的玻璃基板用清洁剂组成物,其为可从玻璃基板表面完全地去除污染物,并因此增强清洁效果及生产力的低发泡性水性清洁剂。
本发明的一个方面提供一种FPD的玻璃基板用清洁剂组成物,其pH为12~14,且包含:由下式1表示的包含附加环氧烷的萜型油的非离子型表面活性剂、多元醇系化合物、碱金属氢氧化物、及水:
<式1>
其中,AO为氧化乙烯基、氧化丙烯基、或聚氧化乙烯-聚氧化丙烯嵌段共聚物,及n为1至40。
依照本发明,清洁剂组成物从FPD的玻璃基板表面去除有机污染物及粒子的性能优异。又依照本发明的清洁剂组成物在完成淋洗后不残留残渣,且包括大量去离子水,因此易于处理及环境友善。
附图说明
图1示出了使用实施例9的清洁剂组成物清洁前的接触角的照片;及
图2示出了使用实施例9的清洁剂组成物清洁后的接触角的照片。
具体实施方式
以下详述本发明。
依照本发明,FPD的玻璃基板用清洁剂组成物的pH为12~14,且包括非离子型表面活性剂、多元醇系化合物、碱金属氢氧化物、及水。
在依照本发明所定的FPD的玻璃基板用组成物中,非离子型表面活性剂为由下式1表示的包含附加环氧烷的萜型油的非离子型表面活性剂。
<式1>
在式1中,AO为氧化乙烯基、氧化丙烯基、或聚氧化乙烯-聚氧化丙烯嵌段共聚物,及n为1至40。
由式1表示的非离子型表面活性剂在喷洒程序中产生少量泡沫,如此易于从玻璃基板去除污染物。
由式1表示的非离子型表面活性剂,以按组成物的总重量计为0.01~5重量%,较佳为0.1~2重量%的量使用。如果此成分的量小于以上之下限,则清洁液无法快速地渗透至玻璃基板表面与污染物(如粒子)间的界面中,而不希望地使去除污染物的能力退化。相反地,如果其量超过以上之上限,则透湿性(wetpermeability)变强,且清洁剂组成物可能残留在玻璃基板表面上。又,即使是在已完成淋洗程序之后,表面活性剂仍可能残留在基板上。另因为清洁剂组成物的黏度可能增加,所以产生的泡沫量可能变大,而不希望地使程序作业困难。
由式1表示的非离子型表面活性剂的实施例包括市售产品,如RhodocleanASP、Rhodoclean MSC、Rhodoclean EFC、与Rhodoclean HP(均得自Rhodia)。
在依照本发明的FPD的玻璃基板用清洁剂组成物中,多元醇系化合物的功能为增加玻璃基板表面的可湿性,因此增强其从玻璃基板表面去除油成分(仅使用由式1表示的非离子型表面活性剂难以去除的油成分)的能力。此外,多元醇系化合物可增强依照本发明的清洁剂组成物在水中的溶解度及清洁力。
多元醇系化合物,以按组成物的总重量计为0.01~5重量%,较佳为0.1~3重量%的量使用。如果此成分的量小于以上之下限,则玻璃基板表面的可湿性不足。相反地,如果其量超过以上之上限,则负面地影响成本效益。
多元醇系化合物可为选自由乙二醇、丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、甘油、三羟甲基乙烷、三羟甲基丙烷、季戊四醇、木糖醇、甘露糖醇、山梨糖醇、赤藻糖醇、核糖醇、苏糖醇、阿拉伯糖醇、与塔罗糖醇所组成群组中的一种或更多种。
在依照本发明的FPD的玻璃基板用清洁剂组成物中,碱金属氢氧化物具有高碱性,因而可降低高分子有机污染物或油性有机化合物的分子量,及增加从玻璃基板清除的能力,使得玻璃基板变清洁。
碱金属氢氧化物,以按组成物的总重量计为0.05~5重量%,较佳为0.1~2重量%的量使用。如果此成分的量小于以上之下限,则不易从玻璃基板表面去除粒子或有机污染物。相反地,如果其量超过以上之上限,无法进一步增加清洁效果,且使清洁液变昂贵,因此负面地影响成本效益且造成环境问题。
碱金属氢氧化物可为选自由KOH、NaOH、及其混合物所组成群组中的任何一种,其因为赋予高碱性,且易于取得,及经济上有利而便利。
在依照本发明的FPD的玻璃基板用清洁剂组成物中,水为适用于半导体处理且为18MΩ·cm或更大的去离子水。剩余量均由水组成,使得组成物的总重量为100%。
除了以上的成分,依照本发明的清洁剂组成物可进一步包含典型添加剂。该添加剂可包括螯合剂、pH控制剂等。
依照本发明的清洁剂组成物呈现从FPD的玻璃基板表面去除有机污染物及粒子的优良能力。又,依照本发明的清洁剂组成物在完成淋洗后不残留残渣,且包括大量去离子水,因此易于处理及环境友善。
现在叙述以下实施例及测试例以例证但不视为限制本发明的范围,且可较佳地了解本发明。
实施例1~17及比较例1~4:清洁剂组成物的制备
使用装有搅拌器的混合器,将表1所示成分以表1所示的量混合及在室温以500rpm搅拌1小时,如此制备清洁剂组成物。
表1
注)a)山梨糖醇
b)甘油
c)乙二醇
1)Rhodoclean ASP
2)Rhodoclean MSC
3)Rhodoclean EFC
TMAH:氢氧化四甲铵
测试例:清洁剂组成物的性质评估
<去除空气污染物的能力评估>
将100毫升的实施例1~17及比较例1~4的各清洁剂组成物加入250毫升烧杯中。此时将5公分×5公分玻璃基板在空气中直立3日使其被污染,而评估去除空气污染物的能力。
使用喷洒型玻璃基板清洁用装置,在室温将被污染的基板用实施例1~17及比较例1~4的各清洁剂组成物清洁1分钟。在清洁后将基板用超纯水清洗30秒,然后用氮干燥。去除污染物的程度借由在清洁前后使用接触角测量仪测量接触角,基于接触角的减小量而评估。将结果示于以下表2。
<去除有机污染物的能力评估>
为了评估去除有机污染物的能力,将5公分×5公分玻璃基板用人的指纹污染,及使用喷洒型装置在室温将被污染的基板用实施例1~17及比较例1~4的各清洁剂组成物清洁2分钟。在清洁后将基板用超纯水清洗30秒,然后用氮干燥。去除污染物的程度借由在清洁前后使用接触角测量仪测量接触角,基于接触角的减小量而评估。将结果示于以下表2。
<去除粒子的能力评估>
将玻璃基板用平均粒度为0.8微米的有机粒子的溶液污染,以3000rpm旋转(spin)干燥1分钟,然后使用喷洒型装置在室温用实施例3、4、9、10、17、及比较例2、4的各清洁剂组成物清洁2分钟。在清洁后将基板用超纯水清洗30秒,然后用氮干燥。在清洁前后使用表面粒子计数器(Topcon WM-1500)测量大小为0.3微米或更大的粒子的数量。将结果示于以下表3。
表2
去除空气污染物的能力 | 去除有机污染物的能力 | |
实施例1 | ○ | ○ |
实施例2 | ○ | ○ |
实施例3 | ◎ | ○ |
实施例4 | ◎ | ○ |
实施例5 | ○ | ○ |
实施例6 | ○ | ○ |
实施例7 | ○ | ○ |
实施例8 | ○ | ○ |
实施例9 | ◎ | ◎ |
实施例10 | ◎ | ○ |
实施例11 | ◎ | ○ |
实施例12 | ◎ | ○ |
实施例13 | ○ | ○ |
实施例14 | ○ | ○ |
实施例15 | ○ | ○ |
实施例16 | ○ | ○ |
实施例17 | ◎ | ◎ |
比较例1 | ◎ | △ |
比较例2 | × | △ |
比较例3 | ○ | × |
比较例4 | ○ | × |
<去除空气污染物的能力评估>
◎:优良(减小40°或更多)
○:良好(减小40°~30°)
△:一般(减小30°~20°)
×:不良(减小少于20°)
<去除有机污染物的能力评估>
◎:优良(减小30°或更多)
○:良好(减小30°~20°)
△:一般(减小20°~10°)
×:不良(减小少于10°)
表3
清洁前的粒子数量 | 清洁后的粒子数量 | 去除(%) | |
实施例3 | 2752 | 384 | 86 |
实施例4 | 2854 | 355 | 87 |
实施例9 | 2908 | 427 | 85 |
实施例10 | 2893 | 307 | 89 |
实施例17 | 2912 | 292 | 90 |
比较例2 | 2741 | 1560 | 43 |
比较例4 | 2804 | 1033 | 63 |
参考表2及3可知,实施例1~17的清洁剂组成物能够去除所有类型的污染物,特别是呈现出去除有机污染物的能力,因为接触角减小30°或更多。此外可知去除粒子的能力优异。然而,可知比较例1~4的清洁剂组成物并未显现去除所有类型的污染物的能力,而是仅为指定类型的污染物。去除粒子的能力不优异。
图1示出了使用实施例9的清洁剂组成物清洁前的接触角的照片,及图2示出了使用实施例9的清洁剂组成物清洁后的接触角的照片。
参考图1及图2可知,在清洁后接触角减小,因此可有效地去除空气污染物。
Claims (2)
1.一种平面显示器装置的玻璃基板用清洁剂组成物,其pH为12~14,且其按组成物的总重量计,包含:
0.01~5重量%的由下式1表示的包含附加环氧烷的萜型油的非离子型表面活性剂;
0.01~5重量%的多元醇系化合物,所述多元醇系化合物选自由乙二醇、甘油和山梨糖醇所组成群组中的一种或更多种;
0.05~5重量%的碱金属氢氧化物;及
其余为水,
<式1>
其中,AO为氧化乙烯基、氧化丙烯基、或聚氧化乙烯-聚氧化丙烯嵌段共聚物,及n为1至40。
2.根据权利要求1所述的清洁剂组成物,其中,碱金属氢氧化物选自由KOH、NaOH、及其混合物所组成群组中的任何一种。
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