CN1073498C - 模塑方法及脱模剂用稀释剂 - Google Patents

模塑方法及脱模剂用稀释剂 Download PDF

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CN1073498C
CN1073498C CN95193032A CN95193032A CN1073498C CN 1073498 C CN1073498 C CN 1073498C CN 95193032 A CN95193032 A CN 95193032A CN 95193032 A CN95193032 A CN 95193032A CN 1073498 C CN1073498 C CN 1073498C
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diluent
releasing agent
surfactant
metal pattern
water
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CN1147788A (zh
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山名雅之
阿贺司
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • Mechanical Engineering (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
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Abstract

本发明提供将脱模剂用水稀释用于模塑时，用含表面活性剂的水溶液形成的稀释剂将上述脱模剂稀释后再加以使用的模塑方法。本发明提供的模塑方法可总是有再现性地得到对金属模的良好湿润性、干燥性和脱模性。

Description

模塑方法及脱模剂用稀释剂
产业上利用的范围
本发明涉及在用金属模将树脂、橡胶等模塑中使用水系脱模剂的模塑方法，以及用于此模塑方法的脱模剂用稀释剂。
现有技术
为了得到树脂、橡胶等模塑品，通常，先在金属模中涂布脱模剂，将模塑用组合物加到金属模中，使该模塑用组合物转变成固体模塑品，然后将固体模塑品从金属模上分离下来。
在这样的模塑中使用的脱模剂，有蜡系、硅氧烷系、含氟化合物系等各种类型，使用时，以在有机溶剂或水中分散或溶解的形式使用。
有机溶剂系的脱模剂因基于有机溶剂的特性，对金属模的湿润性和干燥性良好，因而一般易于使用。
然而，鉴于最近的地球环境和工作环境，例如三氯二氟乙烷(氟冷113)的破坏臭氧层、含氯溶剂的毒性、石油系溶剂的可燃性、毒性等问题，对水系脱模剂的需求变得十分强烈。
另一方面，水系脱模剂通常在使用时当场用水稀释成适当的浓度加以使用。
然而，因为水比有机溶剂蒸发潜热大、干燥性差，当金属模温度在100℃以下时，以往通常用有机溶剂系的脱模剂。而且，与有机溶剂系脱模剂相比，稀释时可见明显的脱模性降低倾向。
关于这些，已知有使用以表面活性剂及水稀释脱模剂的水系脱模剂的模塑方法(特公昭59-32513号、特公平1-26601号)。这种情况与单用水稀释的情况相比，改善了干燥性、脱模性，也可使用于100℃以下的低温模塑。
这种稀释的水系脱模剂中含表面活性剂，因此对金属模的湿润性提高，脱模剂不呈水滴状，因此成为均匀的薄膜状，干燥性提高。而且，与此同时，脱模性、金属模污染也得到改善。
但是，一般说来，通常将蜡、硅氧烷油、硅氧烷树脂或含全氟烷基的化合物用表面活性剂乳化后用作脱模剂。
从而，因稀释前脱模剂中含表面活性剂，一般认为单用水稀释的情况都是相同的，但在实际模塑过程中，因各种模塑材料或金属模形状不同，与之相应地，即使用同样的脱模剂，最适稀释倍数一般也是不同的。因此，对金属模的湿润性随此稀释倍数而大幅度地变动。如特公昭59-32513号、特公平1-26601号所揭示的那样，这在以表面活性剂和水稀释脱模剂而加以使用的方法中也是如此。
发明的目的
本发明的目的是提供可经常地再现性良好地得到对金属模有良好的湿润性、干燥性和脱模性的模塑方法，以及用于该模塑方法的脱模剂用稀释剂。发明的构成
即，本发明涉及在以水稀释而成的脱模剂用于模塑时，预先配制含0.01-1.0重量％表面活性剂的水溶液形成的稀释剂，用此稀释剂水溶液稀释上述脱模剂而加以使用的模塑方法，及在此模塑方法实施中使用的、由含0.01-1重量％表面活性剂的水溶液形成的脱模用稀释剂。
按照本发明的模塑方法和稀释剂，因为在稀释剂中含表面活性剂，因此对金属模的湿润性提高，又因脱模剂不呈水滴状，故形成均匀的薄膜状态，干燥性提高，同时，脱模性、金属模污染也可改善。
此外，在稀释剂中可预先包含最适浓度的表面活性剂，因此其稀释倍数(稀释浓度)通常可被设定在所要求的值，对金属模的湿润性就不变。因此，可按模塑材料或金属模形式的不同而自由选择最适稀释倍数，可使上述湿润性、干燥性、脱模性经常再现性良好地提高。
本发明中，稀释的脱模剂无特别限制，可列举以下蜡系、硅氧烷系、含氟化合物系等。
蜡系，可有如下例子：动物性蜡、植物性蜡、矿物性蜡、合成蜡(脂肪酸酯蜡、脂肪酸酰胺蜡、聚乙烯蜡、微晶蜡、石蜡等)等。
硅氧烷系可列举二甲基硅氧烷油、甲基苯基硅氧烷油、氨基烷基改性二有机硅氧烷、硅氧烷树脂等为例。
含氟化合物系可列举含有全氟烷基或全氟链烯基的化合物，如含有全氟烷基或全氟链烯基的磷酸或基盐、含有全氟烷基或全氟链烯基的羧酸或基盐、含有全氟烷基或全氟链烯基的磺酸或基盐、含有全氟烷基或全氟链烯基的丙烯酰基系聚合物等为例。
这些脱模剂通常以用表面活性剂在成乳化剂或分散剂的形式使用。所用的表面活性剂可以是通常的阴离子型、阳离子型、非离子型和两性表面活性剂，例示于下：
阴离子型表面活性剂：高级脂肪酸碱盐、烷基硫酸盐、烷基磺酸盐、烷基芳基磺酸盐、磷酸烷基酯、含氟羧酸、含氟磺酸等。
阳离子型表面活性剂：高级胺卤酸盐、卤化烷基吡啶、季铵盐、聚氧乙烯烷基胺等。
非离子型表面活性剂：聚氧乙烯烷基醚、聚氧乙烯烷基酯、脱水山梨醇烷基酯、糖酯等。
两性表面活性剂：包含甜菜碱、咪唑啉等。有仲胺、叔胺和季铵盐等。作为阴离子基，羧酸、硫酸酯、磺酸、磷酸酯等是有用的。
用于本发明的稀释剂的表面活性剂，阴离子型、阳离子型、非离子型、两性均可使用，但是，阴离子型、阳离子型、两性等离子型表面活性剂若与异种离子混合，可有凝聚发生。例如，在脱模剂的乳化剂中使用阴离子型表面活性剂时，若在稀释剂中使用阳离子型表面活性剂，乳化状态变得不稳定，不能很好地涂布。
然而，在用非离子型表面活性剂时，无此影响，在任何情况下均能很好地使用，因此，非离子型表面活性剂较佳。
非离子型表面活性剂中，在不降低脱模性这点上，以通式
Figure C9519303200051
(R为C8H17-或C9H19-等CmH2m+1(m为5-20的整数)表示的脂肪族烃基，n为2-100的整数)表示的化合物为佳。它们也可一种或二种以上混合使用。
表面活性剂有市售，在本发明中，不是单用水，而是用含表面活性剂的水溶液(稀释剂)将脱模剂进行稀释后再使用。稀释剂中表面活性剂浓度为0.01-1.0重量％，较好为0.1-1.0重量％。此浓度若大于1重量％，脱模性易降低；而小于0.01重量％，则对金属模的湿润性易降低。
脱模剂的稀释倍数以2-100倍为好。此时，脱模剂在稀释成0.01-1重量％，更好为0.1-1重量％浓度后使用时特别有用。
在本发明中，稀释剂中也可合用防蚀剂，例如，亚硝酸钠等具有还原性的防蚀剂，表面活性剂类的防蚀剂均可使用，具体地可以是三洋化成(株)制的Sanhibitor。产业上利用的可能性
按本发明的模塑方法，将脱模剂用水稀释用于模塑时，因用含表面活性剂的水溶液将上述脱模剂稀释后使用，在稀释剂中含表面活性剂，故对金属模的湿润性提高，又因脱模剂不呈水滴状，故成为均匀的薄膜状，干燥性很高，同时，脱模性，金属模污染性也可改善。
此外，在稀释剂中可预先包含最适浓度的表面活性剂，因此其稀释倍数(稀释浓度)通常可设定在所要求的值，对金属模的湿润性就不变。因此，可按模塑材料或金属模形式的不同而自由选择最适稀释倍数，可使上述湿润性、干燥性、脱模性可总是再现性良好地得到提高。
附图的简单说明
图1是将脱模剂的水分蒸发率(干燥性)与其对照数据作比较所作的图。
实施例
以下以实施例对本发明作更详细的说明，这些实施例不是对本发明的限制。实施例1
在1升的三颈烧瓶中加入497g离子交换过的水，用水浴40℃加热。在烧瓶中加入下述结构式的Nonion HS-210(日本油脂公司制)3g，搅拌30分钟，使其完全溶解。将此作为稀释剂(A)。
Nonion HS-210：
Figure C9519303200061
然后，在100ml烧杯中加入含氟系水基脱模剂Daifree ME-44(含有效成分4重量％、各种表面活性剂0.2-0.5重量％,Daikin工业公司制〕10g，加入稀释剂(A)40g，搅拌，配制成5倍稀释液。
此5倍稀释液对金属模的湿润性、在金属模上的干燥时间、使用金属模时的脱模性表示在下述表1和图1中。
实施例2
用硅氧烷系水基脱模剂SH-7036(含有效成分38重量％、各种表面活性剂3-10重量％,Torey Dowconing Silicone Co.,Ltd．制)代替实施例1的含氟系水基脱模剂Daifree ME-414。在100ml的烧杯中加入1克SH-7036，加入稀释剂(A)46.5克，搅拌，配制成47.5倍稀释液。
实施例3
用蜡系水基脱模剂EMUSTAR0001(含有效成分40重量％、各种表面活性剂0.5-2重量％，日本Seirou公司制)代替实施例1的含氟系水基脱模剂Daifree ME-414。在100ml的烧杯中加入1克EMUSTAR0001，加入稀释剂(A)49克，搅拌，配制成50倍稀释液。实施例4
除了用如下结构式的Nonion HS-206(日本油脂公司制)5克代替实施例1的Nonion HS-210外，按实施例1同样进行配制。
Nonion HS-206：
实施例5
除了用如下结构式的Nonion HS-220(日本油脂公司制)1克代替实施例1的Nonion HS-210外，按实施例1同样进行配制。
Nonion HS-220：
Figure C9519303200072
实施例6
除了用如下结构式的Nonion HS-215(日本油脂公司制)1克代替实施例1的Nonion HS-210外，按实施例1同样进行配制。
Nonion HS-215：
Figure C9519303200073
实施例7
在1升的三颈烧瓶中加入离子交换过的水496克，在水浴中40℃加热。在烧瓶中加入Nonion HS-210(日本油脂公司制)3克和水基防蚀剂SanhibitorNo.52(三洋化成工业公司制)1克，搅拌30分钟，使其完全溶解。将此作为稀释剂(B)。
用稀释剂(B)代替实施例1的稀释剂(A)，将Daifree ME-414稀释5倍。此5倍稀释液对金属模的湿润性、在金属模上的干燥时间、使用金属模时的脱模性列于下面的表1，在金属上的防蚀性列于下面的表2。
在表2中，还列出了实施例1、实施例2、实施例3、比较例1、比较例2、比较例3、比较例4。
实施例8
用2克钼酸钠代替实施例7的1克Sanhibitor No.52，其余进行同样的操作。比较例1
用离子交换过的水代替实施例1的稀释剂(A)，将Daifree ME-414稀释5倍，其余进行同样的操作。比较例2
用离子交换过的水代替实施例2的稀释剂(A)，将SH-7036稀释47.5倍，其余进行同样的操作。比较例3
用离子交换过的水代替实施例3的稀释剂(A)，将EMUSTAR0001稀释50倍，其余进行同样的操作。
实施例9
用代替实施例4的Nonion HS-206，其余进行同样的操作。
实施例10
用
                  [C16H33N(CH3)3]_Cl_代替实施例5的Nonion HS-220，其余进行同样的操作。
实施例11
用
Figure C9519303200082
代替实施例6的Nonion HS-210、HS-215，其余进行同样的操作。比较例4
用DaifreeME-414原液代替实施例1的用稀释剂(A)5倍稀释DaifreeME-414，其余进行同样的操作。实施例12-16、比较例5-10
对于实施例1，将表面活性剂和脱模剂的混合量作各种变化，其余进行同样的操作。
结果分别列于下面的表1、表2、表3和图1。各特性的评价如下。
湿润性：在半硬钢S45C硬质镀铬金属模(56mmΦ×10mm)的内表面涂以一定量的液体时的湿润状态。
评价标准    ○：完全均匀地涂布；
            Δ：有部分未涂布的地方；
            ×：因为液体被排斥，有很多未涂布的地方。
干燥性：在25℃×60％的恒温恒湿室中，将铝制金属模(100mmΦ×10mm)置于红外线水分计上，向金属模上涂布恒量0.4克液体，用所连接的计算机画出重量减少率的经时变化。图1表示一例。此处为了方便，将干燥时间分为三阶段。
评价：干燥时间(分钟)
○：4分钟以下；
Δ：4分钟以上，6分钟以下；
×：6分钟以上。
脱模性：将上述湿润性试验中所用的刷涂了脱模剂的金属模在120℃干燥箱中加热10分钟。在此金属模上流上环氧树脂20克，将夹子靠在上面，在120℃×2小时的条件下硬化。室温下放置2小时后，用拉伸试验机测定脱模力。
环氧树脂组成：
    Epicoat 828(Shell Chemical Co.Ltd．制)    100份
    三亚乙基四胺                                8份
此处为了方便，将脱模力分三级评价。
评价：脱模力(g/cm2)
○：200以下；
Δ：200以上，300以下；
×：300以上。
腐蚀程度：
试验方法
在50cc螺线管中加入20克试样，将两面抛光的SS-400钢材(1.6×20×50mm)斜靠在管中，一半浸入液体，放置在25℃×65％的恒温恒湿室中。
判断标准
按以下标准目测腐蚀程度。
0：无变化；
1：气液界面有一些红锈发生；
2：气液界面外也有红锈发生；
3：引起少量腐蚀；
4：腐蚀严重。
                          表1
稀释剂浓度(重量％)   湿润性   干燥性   脱模性
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       0.60.60.60.990.20.40.60.60.990.20.4 ○○○○○○○○ΔΔΔ ○○○○○○○○ΔΔΔ ○ΔΔ○○○○○ΔΔΔ
比较例1比较例2比较例3        000 ××× ××× Δ××
                            表2
                腐蚀程度
 1日后  2日后  3日后  7日后  14日后
实施例1    1    3    3    4     4
实施例2    1    3    3    4     4
实施例3    1    3    4    4     4
实施例7    0    0    0    0     0
实施例8    0    0    0    0     0
比较例1    1    3    3    4     4
比较例2    1    3    3    4     4
比较例3    1    3    4    4     4
比较例4    0    1    2    3     4
                        表3
    稀释浓度(重量％)  ME-414(4重量％)混合量   HS-210浓度(重量％)    HS-210的混合量   湿润性   干燥性   脱模性
比较例5     8.0    10g   8.0％   40g    ○    ○    ×
比较例6     6.0    10g   6.0％   40g    ○    ○    ×
比较例7     5.0    10g   5.0％   40g    ○    ○    Δ
比较例8     4.0    10g   4.0％   40g    ○    ○    Δ
比较例9     2.0    10g   2.0％   40g    ○    ○    Δ
 实施例12     1.0    10g   1.0％   40g    ○    ○    ○
 实施例13     0.2    10g   0.2％   40g    ○    ○    ○
 实施例14     0.05    10g   0.05％   40g    Δ    Δ    Δ
 实施例15     0.02    10g   0.02％   40g    Δ    Δ    Δ
 实施例16     0.01    10g   0.01％   40g    Δ    Δ    Δ
 比较例10     0.005    10g   0.005％   40g    Δ    ×    Δ
从上面的表1和图1、表3的结果，如实施例1-16(特别是实施例1-8、14-16)所示，按本发明用稀释剂稀释脱模剂后加以使用，可使湿润性、干燥性、脱模性提高。从表2的结果，如实施例7、8所示，添加防蚀剂的效果是明显的。

Claims (4)

1．一种模塑方法，其特征在于：将脱模剂用水稀释用于模塑时，预先配制含0.01-1.0重量％表面活性剂的水溶液形成的稀释剂，用此稀释剂水溶液将上述脱模剂稀释后使用。
2．按权利要求1所述的方法，其中使用非离子型表面活性剂作为表面活性剂。
3．按权利要求2所述的方法，其中非离子型表面活性剂以如下通式表示：
Figure C9519303200021
其中R为CmH2m+1表示的脂肪烃基，m为选自5-20的整数；n为选自2-100的整数。
4．按权利要求1-3之一所述的方法，其中通过调节稀释剂的浓度将脱模剂的稀释倍数设定为2-100倍。
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DE69531347D1 (de) 2003-08-28
WO1995031321A1 (fr) 1995-11-23
KR0174753B1 (ko) 1999-10-01
EP0759348A4 (en) 1997-09-24
DE69531347T2 (de) 2004-04-15
CN1147788A (zh) 1997-04-16
US5853646A (en) 1998-12-29
EP0759348B1 (en) 2003-07-23
EP0759348A1 (en) 1997-02-26
KR970702780A (ko) 1997-06-10
TW326014B (en) 1998-02-01
JPH07304043A (ja) 1995-11-21

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