CN87102398A - 用于磁性记录媒介的全氟聚醚基内润滑剂 - Google Patents
用于磁性记录媒介的全氟聚醚基内润滑剂 Download PDFInfo
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Abstract
具有极性或非极性的氢化端基的双功能全氟聚醚基化合物适宜用作磁性记录媒介活性层的化学配方的内润滑剂,其特征在于,在20℃时在甲乙酮中的溶解度为0.05%至2%(重量)。
Description
本发明涉及采用内润滑剂的,以磁性颜料为基础的磁性记录媒介(片或带)的润滑作用。按照下文的规定,这种内润滑剂是由在构成磁性层的聚合物基体中具有全氟聚醚基结构,具有氢化端基以及具有临界溶解度的一些化合物所组成的。
众所周知,在属于粉粒或颜料型的磁性媒介的范围内,该磁性记录媒介包括散布在刚性或柔性基质上的磁性材料层。
上述的磁性材料层是由磁性的氧化物粉粒和/或散布在热塑性或热固性聚合物粘结剂上的金属粉粒组成的。磁性材料层的基质可以是聚乙烯、聚氨酯、环氧树脂或苯酚环氧树脂材料,或其适当的混合物。
在这些配方中还含有其他一些化合物,它们的作用是提高磁性颜料的湿润性和弥散度,或起润滑剂的作用以便于读头在磁性媒介上的滑动。
这些化合物一般被称为“内润滑剂”。内润滑剂必须具有一些典型性能;它必须部分地溶解于树脂而且与树脂是混容的,但是它不得起溶胀剂的作用,也不得充当树脂的增塑剂,因为在这种情况下内润滑剂对树脂的紧密度和机械性能,特别是耐磨性能具有极不利的影响。
因此,在磁性记录媒介与读/写头接触点的温度作用下,以及由此接触而引起的压力作用下,内润滑剂的作用过程是通过磁性层的微孔缓慢地和受控地向表面迁移的。
一般用作内润滑剂的材料是脂肪酸酯、具有分支链或无支链的脂肪酸,或其混合物。
尽管能保证磁性媒介有满意的性能、长的寿命和高的耐磨性能,但是目前在所有柔性的磁性媒介中所采用的这些材料,在长期的使用过程中稳定性变差,而且容易氧化。
众所周知,采用全氟聚醚基的外润滑剂可以得到较好的耐磨和耐久性能,这是由于全氟聚醚基的外润滑剂具有较高的热稳定性和化学稳定性以及较好的润滑性能。
虽然起初采用中性的全氟聚醚类作外润滑剂,但是后来根据美国专利号4,268,556和4,267,238公开的内容,通过把具有极性和反应性的端基引入到全氟聚醚基链中,使外润滑剂的性能得到改善。
一般在技术较先进的磁性媒介(例如计算机用的刚性磁盘)领域中所采用的方法包括这样一个步骤,即在磁性媒介制备之后采用稀溶液浸涂法在其表面涂上一层润滑剂薄膜。
这种用润滑剂进行后处理的方法实际上很复杂,因而使生产成本大大增加,为省去这一后处理步骤,可采用上述类型的内润滑剂。就是将润滑剂直接加入到所采用的树脂组合物中以形成磁性层。这种方法只能用在柔性的磁性记录媒介的场合。
然而,试验过的脂肪酸酯类型的化合物都显示出具有上述的缺点。
因此,越来越有必要获得一种对热和化学试剂稳定的、耐氧化的,并能保证得到性能比用已知氢化内润滑剂所得到的磁性媒介好的磁性媒介,尤其是在长期操作中的使用。
另一方面,由于中性全氟聚醚与用作粘结剂的氢化树脂的可混性很差,并且在这种树脂中的溶解度低,因此它不能用作内润滑剂。
这种低溶解度导致润滑剂向表面快速的和非受控的迁移,接着在表面发生粘附现象,从而形成污点和沉淀物。
此外,具有各种不同功能端基的全氟聚醚基化合物也不能用作内润滑剂,因为它在用作粘结剂的聚合物基体中的溶解度太高,起着增塑剂的作用,会引起磁性层机械性能的显著恶化。
现已意外地发现,采用具有两个极性或非极性氢化端基的、并且在25℃温度下为液体的特殊类型的全氟聚醚化合物作为内润滑剂时,所得到的柔性磁性媒介的性能有很大改善。
因此,本发明的目的是,在柔性磁性记录媒介的涂料树脂组合物中采用内润滑剂,所述润滑剂是在25℃为液体的双官能的全氟聚醚基化合物。这些化合物具有氢化的极性或非极性的端基,具有平均分子量至少为1000的全氟氧化烯链,20℃时在甲乙酮中具有0.05%(重量)~2%(重量)范围的溶解度,包括两个极端值。
本发明另一个目的是上述的含有0.5~3%(重量)的上述内润滑剂的树脂组合物。
长度适当的一系列全氟氧化烯单元连结有极性或非极性的氢化端基时,可以保证它与树脂可部分混溶,这正是为了达到润滑剂向表面恒定地和受控地迁移所必需的。实际上,根据全氟聚醚基化合物在20℃的甲乙酮中的溶解度,就可以确定它的适用性:事实上它的溶解度必须在0.05%~2%(重量)范围之内。
通常使产品有适当溶解度的氢化端基是一些含氧的羟基、酯基、芳香基和杂环基等端基。
具体来说,本发明的润滑剂最好具有选自下列基团的T和T′端基:
b)-CH2O-(CH2CH2O)zH,其中Z是从1至3的整数;
c)
;
d)-COOR,其中R是具有2~12碳原子的烷基;
适用于本发明的全氟聚醚化合物尤其是属于如下类别的那些化合物:
(Ⅰ)TO(CF2CF2O)n(CF2O)m-T′;
(Ⅲ)TO(CH2CF2CF2O)sT′;
(Ⅳ)T(OCF2CF2CH2)tORfO(CH2CF2CF2O)tT′;
(Ⅴ)TO(CF2CF2O)rT′;
其中:T和T′是彼此相同或不相同的氢化端基,例如前面所规定的各种端基;下标n、m、g、h、p、q、s、t、r、u是整数,选择时应使全氟聚醚基链的平均分子量至少为1000,最好为1800到4500,而且在任何情况下,都应使全氟聚醚在25℃时可以为液体;R是氟化亚烷基;全氟氧化烯单元是沿其链按统计学分布的。
在适宜用作本发明内润滑剂的化合物中,比较好的是具有上述两个a)种或b)种端基的(Ⅰ)类全氟氧化烯链的化合物。
用于本发明的全氟聚醚化合物可按下述方法制备:
-根据美国专利号3,242,218介绍的方法制备(Ⅰ)类全氟聚醚化合物;
-根据美国专利号3,665,041介绍的方法制备(Ⅱ)类化合物;
-根据美国专利公开的欧洲专利148,482介绍的方法制备(Ⅲ)类和(Ⅳ)类化合物;
-根据美国专利号4,523,039介绍的方法制备(Ⅴ)类化合物;
-根据欧洲专利公开的欧洲专利148,482介绍的方法制备(Ⅵ)类化合物。
根据美国专利号3,810,874和欧洲专利公开的欧洲专利165,649和165,650介绍的方法可以引进一些适合于本发明的功能端基。
在(Ⅱ)、(Ⅲ)和(Ⅴ)类的情形中,起始的全氟聚醚只有一种功能端基,但采用意大利专利申请号22920A/85介绍的方法,有可能转变成相应的两功能化的产物。
如上所述,内润滑剂的基本特点是它在树脂组合物中具有限定在一个很窄范围内的可利用的临界溶解度。
现已查明,具有这种特性的产品在溶剂中,例如在四氢呋喃(THF)、甲乙酮(MEK)和异丙醇(iPrOH)中,也具有临界溶解度,它被精确地限制在一定的范围内(在20℃时,为0.05%到2%重量)。众所周知,这些被氢化的溶剂通常用于用来形成磁性层的树脂组合物中。
为了说明起见,下文简要地说明本发明的一些全氟聚醚基化合物在上述溶剂中的溶解度。
此外,也给出了有关不适合本发明用途的、以及在下面一些实例中用来作为对比的全氟聚醚基化合物的溶解度数据。
表Ⅰ在20℃时的溶解度(重量%)
材料 四氢呋喃 甲乙酮 异丙醇
A 0.10 0.15 0.15
B 0.12 0.17 0.18
C 0.12 0.14 0.16
D(对比物) 0.02 0.03 0.03
用A、B、C和D表示的材料区别如下:
A:具有两个化学式为-CH2OCH2CH2OH的端基,而且全氟聚醚基链的平均分子量等于2000的(Ⅰ)类全氟聚醚;
B:具有两个化学式为-CH2OCH2CH2OCH2CH2OH的端基,而且全氟聚醚基链的平均分子量等于2000的(Ⅰ)类全氟聚醚;
D:具有两个化学式如下的端基,而且全氟聚醚基链的平均分子量等于2000的(Ⅰ)类全氟聚醚:
本发明的氟化内润滑剂可用在用来形成磁性层的树脂组合物中,其用量按重量计为0.5%到3%。
下面的一些实例仅仅是对本发明的说明而已,并不是对本发明的限制。
实例1
录象磁带的制作
采用下面的组分(重量份)制备以聚氨酯/环氧树脂为基体的录象磁带:
a)颜料(磁性的)
铁酸盐BAYFERROX AC型5127M 76.0
b)树脂
c)交联剂
拜耳(Bayer)公司生产的DES ODUR
,(聚氨基甲酸酯
类整合剂)(异氰酸酯交联剂) 1.02
d)分散剂
e)内润滑剂:
从上述本发明的A、B、C和对比化合物D以及硬脂酸异鲸蜡酯(ICS)(在本技术领域中用作内润滑剂的另一个对比化合物)挑选出来,其用量可在上述规定组合物总重量的1~3%内变化。
涂料可按照已知的方法来制备,先借助于分散剂制备颜料在溶剂(甲乙酮/四氢呋喃=30/70)中的悬浮体;接着添加溶解于类似的溶剂中的树脂、交联剂和本发明的内润滑剂。所制得的涂料含有50%(重量)的溶剂和50%(重量)的上述a)至e)的组分。尔后在微球磨机中进行分散,随后过滤除去未分散的氧化物团粒。
用可逆滚压涂覆技术,将所得到的磁性涂料在宽为6英寸,厚度为50微米的聚对苯二甲酸乙二醇酯的磁带上;然后对磁性层进行颜料的定向和砑光。
将如此得到的磁带切割成0.5英寸宽,并且缠成标准的录象盒式磁带VHS。
实例2
“静止画面寿命”试验
用按照实例1方法制作的磁带记录彩条信号,而且在复制该信号的同时,使磁带保持在静止画面的操作状态,在这期间,磁带处于静止状态,而安装在支承磁头的转动磁鼓上的一些磁头在同样的轨迹上继续滑动。
这种试验的寿命表明该磁性涂料的耐磨性能,因此,润滑剂的存在及其效力对耐磨性能有很大的影响。
表2列出了一些试验结果。
表2
内润滑剂 静止画面寿命
(%重量) (分钟)
A(1%) 85
A(3%) 90
C(1%) 75
ICS(1%) 55
ICS(3%) 50
实例3
按照美国材料试验协会标准D1894-73和德国工业标准53375,对根据实例1方法制备的录象磁带进行磨擦系数试验。
所使用的装置由形成该运动副(即一对运动元件)的两种材料之一的一个平台组成,在本试验中用的是铬板;另一个运动副元件由载荷滑板组成,磁带就绷紧地覆盖在载荷滑板上。
在表3中列出了静磨擦和动磨擦系数。
表3
内润滑剂 静磨擦系数 动磨擦系数
(%重量)
A(1%) 0.45 0.42
A(2%) 0.45 0.44
B(1%) 0.32 0.28
C(1%) 0.50 0.48
D(1%) 0.65 0.61
ICS(1%) 0.70 0.68
ICS(3%) 0.80 0.79
实例4
按照Fulmer实验室研究出的方法,对根据实例1方法制备的磁带进行磨损试验。
在本试验中,磨损传感器由一个小的陶瓷圆柱体组成,在该陶瓷圆柱体上沉积了一层薄薄的金属层,由在其上面滑动的磁带研磨这一层薄薄的金属层。
上述的磨损引起薄膜传感器电阻的变化,由此产生一种信号,将其作为时间的函数进行适当的处理和计算,从而可以测定磁带的磨损值。这个数值可用来确定由于磁带在磁头上的滑动而引起磁头的磨损程度。
在表4中用任选单位表示试验结果(每单位磁带长度引起的传感器电阻的变化值,特别是400英尺长的磁带10次试验的平均值)。
表4
内润滑剂 磨损性
(%重量)
A(1%) 84
A(3%) 90
D(1%) 130
ICS(1%) 156
ICS(3%) 321
无内润滑剂 438
Claims (8)
1、内润滑剂在用于柔性型磁性记录媒介的涂料树脂组合物中的应用,上述的润滑剂是在25℃为液体的、双功能的全氟聚醚基化合物,这类化合物具有极性或非极性的氢化端基,具有平均分子量至少为1000的全氟氧化烯链,20℃时在甲乙酮中具有0.05%至2%(重量)范围的溶解度,包括两个极端值。
2、根据权利要求1的用途,其中全氟聚醚基链的分子量范围是1,800至4,500。
4、根据权利要求3的用途,其中端基T和T′是含氧的羟基、酯基、芳香基、杂环基等端基。
6、根据权利要求3的用途,其中双功能全氟聚醚基化合物具有(Ⅰ)类分子式,其中T和T′属于-CH2O(CH2CH2O)zOH类,其中Z等于1或2。
8、按重量计含有0.5%至3%的、由权利要求1所定义的内润滑剂的树脂组合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT19910A/86 | 1986-03-27 | ||
IT19910/86A IT1188635B (it) | 1986-03-27 | 1986-03-27 | Lubrificanti per fluoropolieterei interni per mezzi magnetici di registrazione |
Publications (2)
Publication Number | Publication Date |
---|---|
CN87102398A true CN87102398A (zh) | 1987-10-07 |
CN1007940B CN1007940B (zh) | 1990-05-09 |
Family
ID=11162260
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN87102398A Expired CN1007940B (zh) | 1986-03-27 | 1987-03-27 | 用于磁性记录媒介的全氟聚醚基内润滑剂 |
Country Status (13)
Country | Link |
---|---|
US (1) | US5382614A (zh) |
EP (1) | EP0239123B1 (zh) |
JP (1) | JP2589080B2 (zh) |
KR (1) | KR960000823B1 (zh) |
CN (1) | CN1007940B (zh) |
AT (1) | ATE89428T1 (zh) |
AU (1) | AU601174B2 (zh) |
CA (1) | CA1284989C (zh) |
CS (1) | CS266341B2 (zh) |
DE (1) | DE3785784T2 (zh) |
IL (1) | IL81965A0 (zh) |
IT (1) | IT1188635B (zh) |
ZA (1) | ZA872071B (zh) |
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CN107201262A (zh) * | 2016-11-23 | 2017-09-26 | 阜宁协鑫光伏科技有限公司 | 一种减少金刚线切割断线的切割液 |
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-
1986
- 1986-03-27 IT IT19910/86A patent/IT1188635B/it active
-
1987
- 1987-03-20 ZA ZA872071A patent/ZA872071B/xx unknown
- 1987-03-23 JP JP62065920A patent/JP2589080B2/ja not_active Expired - Lifetime
- 1987-03-23 IL IL81965A patent/IL81965A0/xx not_active IP Right Cessation
- 1987-03-23 AU AU70537/87A patent/AU601174B2/en not_active Ceased
- 1987-03-26 CA CA000533109A patent/CA1284989C/en not_active Expired - Lifetime
- 1987-03-27 DE DE8787104587T patent/DE3785784T2/de not_active Expired - Fee Related
- 1987-03-27 AT AT87104587T patent/ATE89428T1/de not_active IP Right Cessation
- 1987-03-27 CN CN87102398A patent/CN1007940B/zh not_active Expired
- 1987-03-27 EP EP87104587A patent/EP0239123B1/en not_active Expired - Lifetime
- 1987-03-27 KR KR1019870002871A patent/KR960000823B1/ko not_active IP Right Cessation
- 1987-03-27 CS CS872125A patent/CS266341B2/cs unknown
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1993
- 1993-09-17 US US08/130,144 patent/US5382614A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107201262A (zh) * | 2016-11-23 | 2017-09-26 | 阜宁协鑫光伏科技有限公司 | 一种减少金刚线切割断线的切割液 |
Also Published As
Publication number | Publication date |
---|---|
IT8619910A0 (it) | 1986-03-27 |
IL81965A0 (en) | 1987-10-20 |
ZA872071B (en) | 1987-09-14 |
DE3785784D1 (de) | 1993-06-17 |
US5382614A (en) | 1995-01-17 |
IT1188635B (it) | 1988-01-20 |
CA1284989C (en) | 1991-06-18 |
KR870009342A (ko) | 1987-10-26 |
AU7053787A (en) | 1987-10-01 |
DE3785784T2 (de) | 1993-09-16 |
EP0239123A2 (en) | 1987-09-30 |
JPS62270019A (ja) | 1987-11-24 |
AU601174B2 (en) | 1990-09-06 |
EP0239123B1 (en) | 1993-05-12 |
CS266341B2 (en) | 1989-12-13 |
KR960000823B1 (ko) | 1996-01-13 |
ATE89428T1 (de) | 1993-05-15 |
EP0239123A3 (en) | 1990-12-19 |
JP2589080B2 (ja) | 1997-03-12 |
IT8619910A1 (it) | 1987-09-27 |
CS212587A2 (en) | 1989-02-10 |
CN1007940B (zh) | 1990-05-09 |
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