CN1692151A - 用于改善对金属基材的粘合的有羧基苯并三唑的粘合剂 - Google Patents

用于改善对金属基材的粘合的有羧基苯并三唑的粘合剂 Download PDF

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CN1692151A
CN1692151A CNA2003801003064A CN200380100306A CN1692151A CN 1692151 A CN1692151 A CN 1692151A CN A2003801003064 A CNA2003801003064 A CN A2003801003064A CN 200380100306 A CN200380100306 A CN 200380100306A CN 1692151 A CN1692151 A CN 1692151A
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binder composition
resin
carboxyl benzotriazole
resins
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CN1294222C (zh
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T·塔卡诺
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L15/00—Compositions of rubber derivatives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract

一种在金属基材上、尤其在铜基材上使用的粘合剂包含(a)羧基苯并三唑、(b)有反应性双键的环氧树脂、(c)自由基固化树脂、和(d)自由基引发剂。由要素(c)和(d)组成的自由基固化树脂系统中要素(a)和(b)的组合，与含有(c)和(d)而无(a)和(b)的组合物相比，提供了改善的对铜金属的粘合强度。

Description

用于改善对金属基材的粘合的有羧基苯并三唑的粘合剂
                      技术领域
本发明涉及金属基材上使用、尤其半导体封装内铜引线架上使用的粘合剂组合物。
                      背景技术
羧基苯并三唑作为铜金属的一种良好螯合材料是已知的。它不仅作为抗氧剂用于金属基材，而且也作为粘合促进剂用于环氧树脂糊状物。例如，自由基固化性树脂如丙烯酸酯或甲基丙烯酸酯、马来酰亚胺树脂、乙烯基醚树脂和联马来酰亚胺树脂，因其吸湿量低、固化能力、贮存期长，已有人进行了研究并应用于半导体封装中模头附着粘合剂的用途。然而，这些组合物仍不足以提供对铜引线架的良好粘合。
                      发明内容
本发明是一种金属基材上使用，尤其铜基材上使用的粘合剂，包含(a)羧基苯并三唑、(b)一种有反应性双键的环氧树脂、(c)一种自由基固化性树脂、和(d)一种自由基引发剂。由要素(c)和(d)组成的自由基固化性树脂系统中要素(a)和(b)的组合，与含有(c)和(d)而无(a)和(b)的组合物相比，提供了改善的对铜金属的粘合强度。
                      具体实施方式
羧基苯并三唑有如下结构
Figure A20038010030600031
而且可购自Johoku化学公司。当用于本发明的粘合剂组合物中时，羧基苯并三唑将以0.5～15wt％的数量存在。
有反应性双键的适用环氧树脂包括聚合物，例如，可购自Daicel化学工业公司的环氧化聚丁二烯；环脂族环氧化物，例如，可购自Daicel化学工业公司的甲基丙烯酸(3，4-环氧环己基)甲酯，其结构为：
和芳香族环氧经物，例如，有以下结构的那些：
Figure A20038010030600042
将通过环氧树脂和羧基苯并三唑的添加而有益于对金属基材的粘合的自由基固化性树脂包括丙烯酸酯树脂、甲基丙烯酸酯树脂、马来酰亚胺树脂、联马来酰亚胺树脂、乙烯醚树脂、聚丁二烯树脂、和聚酯树酯。适用的引发剂包括购自Crompton公司、KkuzoNoble公司、Kayaku-Akuzo公司的有机过氧化物和偶氮化合物。
                      实施例
制备两种自由基固化性权脂和引发剂配方(RCR)作为对照。这些对照组合物利用有的应性双键的环氧和羧基苯并三唑在不同水平上的组合进行扩充。所有配方都按照以下实验方案进行模头剪切强度测试：
将每种配方分配在Hirai Seimitu Kougyou公司(日本)供应的铜金属引线架上。然后用于在该粘合剂上安放一种300×300×15密耳裸硅模头。所有样本都在一台烘箱中固化，在氮气下使其温度用30分钟时间爬升到175℃并在175℃保持15分钟。然后，将这些样本在240℃热板上放置1分钟、随后在烘箱中于175℃放置4小时，以模拟半导体封装过程。所得到的样本用Dagy公司的一台Model Dagy 2400PC测试模头剪切强度。
这些配方和结果列于以下表中。
                    表1自由基固化性树脂配方(重量份)
RCR A RCR B
丙烯酸聚氨酯 50 马来酰亚胺     45
丙烯酸月桂酯 30 联马来酰亚胺     20
粘合促进剂 1 乙烯基醚     20
自由基引发剂 1 粘合促进剂     1
自由基引发剂     2
合计重量份 82     88
                                 表2与RCR A的最终配方(重量份)和模头剪切强度
配方#  A1  A2  A3  A4  A5  A6  A7  A8  A9  A10
RCR A  82  82  82  82  82  82  82  82  82  82
NMP溶剂  4  4  4  4  4  4  4  4  4  4
CBT*  2  2  1  5  10  2  2  2
环氧树脂  10  10  10  10  10  5  30  50
银填料  350  350  350  350  350  350  350  350  350  350
合计ppw**  98  96  88  86  97  101  106  93  118  138
Wt％CBT**  2.0  0.0  2.3  0.0  1.0  5.0  9.4  2.2  1.7  1.4
Wt％环氧**  10.2  10.4  0.0  0.0  10.3  9.9  9.4  5.4  25.4  36.2
260℃的模头剪切  8.6  0.5  3.0  0.0  8.6  13.6  8.7  8.7  8.0  6.2
*羧基苯并三唑                **不包括银填料
                                    表3与RCR B的最终配方(重量份)和模头剪切强度
 配方#  B1  B2  B3  B4  B5  B6  B7  B8  B9  B10
 RCR B  88  88  88  88  88  88  88  88  88  88
 NMP溶剂  4  4  4  4  4  4  4  4  4  4
 CBT*  2  2  1  5  10  2  2  2
 环氧树脂  10  10  10  10  10  5  30  50
 银填料  350  350  350  350  350  350  350  350  350  350
 合计ppw**  104  102  94  92  103  107  112  99  124  144
 Wt％CBT**  1.9  0.0  2.1  0.0  1.0  4.7  8.9  2.0  1.6  1.4
 Wt％环氧**  9.6  9.8  0.0  0.0  9.7  9.3  8.9  5.1  24.2  34.7
 260℃的模头剪切  14.4  0.6  1.8  0.0  1.8  10.4  8.5  6.9  5.8  6.3
*羧基苯并三唑         **不包括银填料
从以上实施例可以看出，含有至少一个反应性碳-碳双键的环氧树脂与羧基苯三唑的组合改善了自由基固化性树脂对金属基材的粘合。该环氧树脂与羧基苯并三唑的组合将在总粘合剂组合物(不包括填料)的5wt％～40wt％范围内、较好在10wt％～15wt％范围内。羧基苯并三唑与环氧树脂之比将是1∶2～1∶40、较好是1∶2～1∶5。

Claims (8)

1.一种粘合剂组合物，包含：
(a)羧基苯并三唑，
(b)一种有反应性双键的环氧树脂，
(c)一种自由基固化性树脂，和
(d)一种自由基引发剂。
2.按照权利要求1的粘合剂组合物，其中，环氧树脂(b)选自下列组成的一组：环氧化聚丁二烯，甲基丙烯酸(3，4-环氧环己基)甲酯，和有以下结构的环氧
Figure A2003801003060002C1
3.按照权利要求1的粘合剂组合物，其中，该自由基固化性树脂选自下列组成的一组：丙烯酸酯树脂，甲基丙烯酸酯树脂，马来酰亚胺树脂、联马来酰亚胺树脂、乙烯酯树脂、聚丁二烯树脂、和聚酯树脂。
4.按照权利要求1的粘合剂组合物，其中，该自由基固化引发剂选自下列组成的一组：有机过氧化物和偶氮化合物。
5.按照权利要求1、2、3或4中任何一项的粘合剂组合物，其中，羧基苯并三唑与环氧树脂之比是1∶2～1∶40。
6.按照权利要求1、2、3或4中任何一项的粘合剂组合物，其中，羧基苯并三唑与环氧树脂之比是1∶2～1∶5。
7.按照权利要求1、2、3或4中任何一项的粘合剂组合物，其中，羧基苯并三唑与环氧树脂的组合范围是该粘合剂组合物的5wt％～40wt％/
8.按照权利要求1、2、3、或4中任何一项的粘合剂组合物，其中，羧基苯并三唑与环氧树脂的组合范围是该粘合剂组合物的10wt％～15wt％。
CNB2003801003064A 2003-01-02 2003-12-12 用于改善对金属基材的粘合的有羧基苯并三唑的粘合剂 Expired - Lifetime CN1294222C (zh)

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CN111995867A (zh) * 2020-07-28 2020-11-27 江南大学 第三代半导体器件封装用热固性树脂组合物及其制备方法
CN113337204A (zh) * 2020-03-03 2021-09-03 米巴滑动轴承奥地利有限公司 减摩漆

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BR122019017983B1 (pt) 2010-11-16 2021-01-12 Adeka Corporation método de produção de um tecido falso a partir de pelo menos uma olefina

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CN113337204A (zh) * 2020-03-03 2021-09-03 米巴滑动轴承奥地利有限公司 减摩漆
CN113337204B (zh) * 2020-03-03 2022-06-28 米巴滑动轴承奥地利有限公司 减摩漆
CN111995867A (zh) * 2020-07-28 2020-11-27 江南大学 第三代半导体器件封装用热固性树脂组合物及其制备方法
CN111995867B (zh) * 2020-07-28 2021-10-12 江南大学 第三代半导体器件封装用热固性树脂组合物及其制备方法

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EP1578881A1 (en) 2005-09-28
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KR101088350B1 (ko) 2011-11-30
DE60316186T2 (de) 2008-02-21
ATE372368T1 (de) 2007-09-15
DK1578881T3 (da) 2008-01-02
AU2003301044A1 (en) 2004-07-29
US20040132955A1 (en) 2004-07-08
EP1578881B1 (en) 2007-09-05
KR20050084777A (ko) 2005-08-29
WO2004061039A1 (en) 2004-07-22
US6822047B2 (en) 2004-11-23
JP2006512455A (ja) 2006-04-13
HK1082956A1 (en) 2006-06-23

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