CN113518794A - 加成固化性有机硅胶粘剂组合物 - Google Patents
加成固化性有机硅胶粘剂组合物 Download PDFInfo
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- CN113518794A CN113518794A CN201980093362.0A CN201980093362A CN113518794A CN 113518794 A CN113518794 A CN 113518794A CN 201980093362 A CN201980093362 A CN 201980093362A CN 113518794 A CN113518794 A CN 113518794A
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
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Abstract
本文中显示和描述了包括粘附促进剂的固化性有机硅胶粘剂组合物。所述粘附促进剂为含有基于芳族的骨架的硅氢化物材料,其与另一粘附促进剂一起提供可在相对低的温度下和在较短时间内固化并且提供良好的对塑料和金属的粘附的有机硅材料。
Description
技术领域
本发明涉及固化性有机硅胶粘剂组合物以及这样的固化性有机硅组合物在各种表面上的用途和应用,这样的组合物包括粘附促进剂。具体地,本发明涉及包括粘附促进剂的低温和快速固化性有机硅胶粘剂组合物以及这样的固化性有机硅组合物对于不同类型表面的应用。
背景技术
塑料正代替常规材料来用于下一代轻质、高效混合动力模块、逆变器、传感器、和电子控制单元(ECU)和传输控制单元(TCU)系统的开发。用于例如汽车工业中的胶粘剂必须适合于有助于设计灵活性和在恶劣操作条件下的长期可靠性。常规有机硅组合物通常在较低温度下对于塑料材料不是完全胶粘性的。然而,塑料材料在较高加工温度(例如,约150℃)下易于变形。因此,可能需要在升高的温度(例如,大于120℃)下固化的胶粘剂组合物对于某些应用可能不是特别有用的并且限制了它们在多种工业中的使用。近来的为了改善有机硅对塑料的结合(粘合)的尝试已经包括将基于异氰酸酯的添加剂与含有芳族基团的硅氢化物材料一道使用(参见例如EP 2305765)。在例如美国专利No.8,937,123和8,916,646、以及日本公布2014-205800和2013-241522中描述了其它尝试。然而,所提出的这些解决方案仍然需要在超过100℃的温度下加热。
发明内容
以下呈现了本公开内容的概述以提供一些方面的基本理解。该概述既不意图确认关键或者关键性要素,也不意图定义实施方式或权利要求的任何限制。此外,该概述可提供可在本公开内容的其它方面中更详细地描述的一些方面的简化综述。
提供如下的加成固化性有机硅胶粘剂组合物:其已经被发现对于包括塑料基底和金属基底两者在内的多种多样的基底呈现出良好的粘附,并且容许所述组合物在相对低的温度(例如,约100℃或更低)下和以较短的时间(例如,约30-60min)固化。
在一个方面中,提供固化性有机硅组合物,其包括:(a)烯基官能的有机硅;(b)基于有机硅的交联剂;(c)填料;(d)第一粘附促进剂;(e)第二粘附促进剂;(f)任选地,硅烷;(g)抑制剂和(h)催化剂,其中第一粘附促进剂选自式Z1-R1-O-Ar-O-R2-Z2的化合物,其中R1和R2为C1-C30二价烃;C2-C20二价烃;C4-C10二价烃;或C1-C4二价烃;
Z1和Z2独立地为:
其中R3、R4、R5、R6、R7、R8、R9、和R10独立地选自H、C1-C10烷基、或–OR11,其中R11为C1-C10烷基,并且R3、R4、R5、R6、R7、R8、R9、和/或R10的至少一个为H;
X为1-10;
Y为2-10;和
Ar为芳族基团。
在一种实施方式中,芳族基团Ar可选自C6-C30亚芳基基团、或式-Ar1-X-Ar2-的基团,其中Ar1和Ar2独立地选自单环二价芳基基团并且X为桥连基团。
在一种实施方式中,Ar1和Ar2独立地选自C6-C30亚芳基基团,X选自连接Ar1和Ar2的键、C1-C30二价烃基团、C5-C30二价环状烃基团、-O-、-S-、-S(O)-、-S(O)2-、或-C(O)-。
在一种实施方式中,Ar1-X-Ar2为下式的基团:
其中X选自连接Ar1和Ar2的键、C1-C30二价烃基团、C5-C30二价环状烃基团、-O-、-S-、-S(O)-、-S(O)2-、或-C(O)-;R12和R13彼此或在它们所连接至的环内相同或不同并且选自氢、C1-C10烷基、C1-C10烷氧基、C2-C8烯基、C2-C8烯氧基、C3-C8环烷基、C3-C8环烷氧基、C6-C10芳基、C6-C10芳氧基、C7-C10芳烷氧基、C7-C12烷基芳基、或C7-C12烷基芳氧基,并且t和w为0-4,其中当t或w小于4时,未指定的一个或多个化合价被氢占据。
在一种实施方式中,-Ar1-X-Ar2具有下式:
其中X如上所述,并且R14、R15、R16、R17、R18、R19、R20、和R21独立地选自氢、C1-C10烷基、C3-C8环烷基、或C6-C10芳基。
在一种实施方式中,X为–C(R22)2-,其中R22独立地选自氢、C1-C10烷基、C3-C8环烷基、或C6-C10芳基。
在一种实施方式中,Z1和Z2为:
在任意前述实施方式的固化性有机硅组合物的一种实施方式中,所述化合物的O-Ar-O具有下式:
在任意前述实施方式的固化性有机硅组合物的一种实施方式中,第一粘附促进剂以基于所述组合物的总重量的约0.1重量%-约5重量%的量存在。
在任意前述实施方式的固化性有机硅组合物的一种实施方式中,第二粘附促进剂选自一种或多种具有式R47-SiR48 r(OR49)3-r的化合物,其中R47为氢或氢化物(氢基,hydride)官能团;R48独立地选自C1-C10烃基团;各R49独立地选自C1-C10烃;并且r为0、1、或2。
在一种实施方式中,R47为下式的含有环状的氢化(氢基,hydrido)硅氧烷的基团:
其中R51、R52、或R53独立地选自H、C1-C10烷基、或–OR54,其中R54为C1-C10烷基,并且R51、R52、和R53的至少一个为H;和
R50为具有键合至硅原子的侧链的有机基硅基团并且由下式表示:
Q1-C(O)-O-Q2
其中:
Q1表示在所述硅原子和酯键之间形成具有两个或更多个碳原子的碳链的线型或支化的亚烷基基团,和
Q2表示在氧原子和侧链:SiR48 r(OR49)3-r中的硅原子之间形成具有三个或更多个碳原子的碳链的线型或支化的亚烷基基团。
在一种实施方式中,r为0,并且R49为C1-C10烷基基团。
在任意前述实施方式的固化性有机硅组合物的一种实施方式中,第二粘附促进剂以基于所述组合物的总重量的约0.1重量%-约10重量%的量存在。
在任意前述实施方式的固化性有机硅组合物的一种实施方式中,所述组合物包括第二粘附促进剂(i)和(ii),其中:
第二粘附促进剂(i)选自一种或多种具有式R47-SiR48 r(OR49)3-r的化合物,其中R47为氢或氢化物官能团;R48独立地选自C1-C10烃基团;各R49独立地选自C1-C10烃;并且r为0;和
第二粘附促进剂(ii)选自下式的化合物
R47-SiR48 r(OR49)3-r,其中R48独立地选自C1-C10烃基团;各R49独立地选自C1-C10烃;并且r为0、1、或2,并且R47为下式的含有环状的氢化硅氧烷的基团:
其中R51、R52、和R53独立地选自H、C1-C10烷基、或–OR54,其中R54为C1-C10烷基,并且R51、R52、和R53的至少一个和的至少一个为H;并且R50为C1-C30烃;C6-C30芳基基团;烷基丙烯酸酯基团;烷基羧酸酯基团;或酯基团。
在一种实施方式中,第二粘附促进剂(i)以约0.5重量%-约3重量%的量存在,并且第二粘附促进剂(ii)以约0.1重量%-约8重量%的量存在。
在任意前述实施方式的固化性有机硅组合物的一种实施方式中,所述烯基有机硅选自下式的化合物:
M1 aM2 bD1 cD2 dT1 eT2 fQg,其中:
M1=R23R24R25SiO1/2
M2=R26R27R28SiO1/2
D1=R29R30SiO2/2
D2=R31R32SiO2/2
T1=R33SiO3/2
T2=R34SiO3/2
Q=SiO4/2
其中R23、R24、R25、R27、R28、R29、R30、R32、和R33独立地选自C1-C30烃、C6-C30芳族基团、或C1-C30烷氧基基团;
R26、R31、和R34独立地选自C1-C30烃、C6-C30芳族基团、C1-C30烷氧基基团、或C2-C30烯基基团,条件是R26、R31、和/或R34的一个或多个选自C2-C30烯基基团;
下标a、b、c、d、e、f、g为零或正数,其遵从以下限制:2<a+b+c+d+e+f+g<2000,b+d+f>0。
在一种实施方式中,所述烯基有机硅包括选自如下的烯基有机硅的混合物:(i)具有式M2D1 cM2的第一烯基官能的有机硅,其中c为约5-约1000;和(ii)具有式M2D1 c’M2的第二烯基官能的有机硅,其中c’为约1000-约1500。
在一种实施方式中,所述烯基有机硅为包括多个Q g单元和一个或多个M2单元的支化的聚有机基硅氧烷。
在任意前述实施方式的固化性有机硅组合物的一种实施方式中,所述有机硅氢化物交联剂选自下式的化合物:
M3 hM4 iD3 jD4 kT3 mT4 nQo,其中:
M3=R35R36R37SiO1/2
M4=R38R39R40SiO1/2
D3=R41R42SiO2/2
D4=R43R44SiO2/2
T3=R45SiO3/2
T4=R46SiO3/2
Q=SiO4/2
其中R35、R36、R37、R41、R42、R45、和独立地选自C1-C30烃、C6-C30芳族基团、或C1-C30烷氧基基团;
R38、R39、R40、R43、R44、和R46独立地选自氢、C1-C30烃、C6-C30芳族基团、C1-C30烷氧基基团、或C2-C30烯基基团,条件是R38、R39、R40、R43、R44、和/或R46的一个或多个为氢;
下标a、b、c、d、e、f、g为零或正数,其遵从以下限制:1<h+i+j+k+m+n+o<100,i+k+n>0。
在另一方面中,提供由任意前述实施方式的组合物形成的固化的有机硅材料。
在又一方面中,提供在基底上形成胶粘剂涂层的方法,其包括:将任意前述实施方式的固化性组合物施加至基底的表面,和将所述组合物在约50℃-约110℃的温度下加热。
在一种实施方式中,所述方法包括将所述组合物在约60℃-约100℃的温度下加热。
在任意前述实施方式的方法的一种实施方式中,将所述组合物固化10分钟-约3小时的时期。
在任意前述实施方式的方法的一种实施方式中,所述基底选自塑料材料、金属、金属合金、金属化塑料、和/或经涂布或上漆的金属。
以下描述和附图公开了多种说明性方面。一些改进和新型方面可被明确地确认,而其它可从所述描述和附图明晰。
具体实施方式
现在将介绍示例性实施方式,其实例示于附图中。应理解,可利用其它实施方式并且可进行结构和功能变化。此外,各种实施方式的特征可被组合或改变。因此,以下描述仅是作为举例说明而呈现的并且决不应限制可对所举例说明的实施方式进行的各种替代和改动。在本公开内容中,众多具体细节提供主题公开内容的透彻理解。应理解,本公开内容的方面可用未必包括本文中描述的所有方面的其它实施方式等实践。
如本文中使用的,措辞“实例”和“示例性(的)”意指例子、或举例说明。措辞“实例”或“示例性(的)”不表示关键或优选的方面或实施方式。措辞“或”意图是包容性的而不是排他性的,除非上下文另有说明。作为一个实例,短语“A采用B或C”包括任何包容性排列(例如,A采用B;A采用C;或A采用B和C)。作为另一件事,冠词“一个(种)(a,an)”通常意图意指“一个(种)或多个(种)”,除非上下文另有说明。
提供包括基于硅的粘附促进剂的加成固化性有机硅胶粘剂组合物。所述基于硅的粘附促进剂具有芳族骨架与连接至该芳族骨架的含硅基团以及至少一个键合至硅原子的氢。所述基于有机硅的粘附促进剂可衍生自二羟基芳族化合物。本基于有机硅的粘附促进剂起到改善基于硅氧烷的固化性组合物对基底例如由塑料表面形成或者具有塑料表面的那些的粘附的作用。当与其它粘附促进剂一道使用时,本基于有机硅的粘附促进剂可提供如下的固化性有机硅组合物:虽然在低温(约100℃或更低)下和以较短的时间(30-60min)固化,但是其在金属例如铝以及不同类型的塑料表面(例如,PBT和PPS)上呈现出良好的粘附。
在一个方面中,提供适合于充当固化性组合物中的粘附促进剂的基于有机硅的材料。所述基于有机硅的材料为芳族硅氢化物型材料。所述基于有机硅的粘附促进剂含有芳族基团并且衍生自二羟基芳族化合物。在一种实施方式中,所述基于有机硅的粘附促进剂为下式的化合物:
Z1-R1-O-Ar-O-R2-Z2
其中R1和R2为C1-C30二价烃;C2-C20二价烃;C4-C10二价烃;或C1-C4二价烃;
Z1和Z2独立地为:
其中R3、R4、R5、R6、R7、R8、R9、和R10独立地选自H、C1-C10烷基、或–OR11,其中R11为C1-C10烷基,并且R3、R4、R5、R6、R7、R8、R9、和/或R10的至少一个为H;
X为1-10;
Y为2-10;和
Ar为芳族基团。
芳族基团Ar可选自C6-C30亚芳基基团、或式-Ar1-X-Ar2-的基团,其中Ar1和Ar2独立地选自单环二价芳基基团并且X为桥连基团。Ar1和Ar2可独立地选自C6-C30亚芳基基团。X可为连接Ar1和Ar2的键、C1-C30二价烃基团、C5-C30二价环状烃基团、-O-、-S-、-S(O)-、-S(O)2-、-C(O)-。合适的桥连基团X的非限制性实例包括亚甲基、环己基-亚甲基、2-[2.2.1]-双环庚叉基、乙叉基、异丙叉基、新戊叉基、环己叉基、环十五烷叉基、环十二烷叉基、和金刚烷叉基。
在一种实施方式中,Ar1-X-Ar2为下式的基团:
其中X如上所述,R12和R13彼此或在它们所连接至的环内相同或不同并且选自氢、C1-C10烷基、C1-C10烷氧基、C2-C8烯基、C2-C8烯氧基、C3-C8环烷基、C3-C8环烷氧基、C6-C10芳基、C6-C10芳氧基、C7-C10芳烷氧基、C7-C12烷基芳基、或C7-C12烷基芳氧基,并且t和w为0-4,其中当t或w小于4时,未指定的一个或多个化合价被氢占据。
在一种实施方式中,-Ar1-X-Ar2具有下式:
其中X如上所述,并且R14、R15、R16、R17、R18、R19、R20、和R21独立地选自氢、C1-C10烷基、C3-C8环烷基、或C6-C10芳基。在一种实施方式中,X为–C(R22)2-,其中R22独立地选自氢、C1-C10烷基、C3-C8环烷基、或C6-C10芳基。在一种实施方式中,所述化合物的-O-Ar-O-部分具有下式:
所述基于有机硅的粘附促进剂可衍生自二羟基芳族化合物。所述二羟基芳族化合物可具有式HO-Ar-OH,其中Ar如上所述。为了简洁起见,未重现Ar基团的定义。适合于形成所述粘附促进剂的二羟基芳族化合物的一些说明性、非限制性实例包括,但不限于,以下:4,4′-二羟基联苯,1,6-二羟基萘,2,6-二羟基萘,双(4-羟基苯基)甲烷,双(4-羟基苯基)二苯基甲烷,双(4-羟基苯基)-1-萘基甲烷,1,2-双(4-羟基苯基)乙烷,1,1-双(4-羟基苯基)-1-苯基乙烷,2-(4-羟基苯基)-2-(3-羟基苯基)丙烷,双(4-羟基苯基)苯基甲烷,2,2-双(4-羟基-3-溴苯基)丙烷,1,1-双(羟基苯基)环戊烷,1,1-双(4-羟基苯基)环己烷,1,1-双(4-羟基-3-甲基苯基)环己烷,1,1-双(4-羟基苯基)异丁烯,1,1-双(4-羟基苯基)环十二烷,反式-2,3-双(4-羟基苯基)-2-丁烯,2,2-双(4-羟基苯基)金刚烷,(α,α′-双(4-羟基苯基)甲苯,双(4-羟基苯基)乙腈,2,2-双(3-甲基-4-羟基苯基)丙烷,2,2-双(3-乙基-4-羟基苯基)丙烷,2,2-双(3-正丙基-4-羟基苯基)丙烷,2,2-双(3-异丙基-4-羟基苯基)丙烷,2,2-双(3-仲丁基-4-羟基苯基)丙烷,2,2-双(3-叔丁基-4-羟基苯基)丙烷,2,2-双(3-环己基-4-羟基苯基)丙烷,2,2-双(3-烯丙基-4-羟基苯基)丙烷,2,2-双(3-甲氧基-4-羟基苯基)丙烷,2,2-双(4-羟基苯基)六氟丙烷,1,1-二氯-2,2-双(4-羟基苯基)乙烯,1,1-二溴-2,2-双(4-羟基苯基)乙烯,1,1-二氯-2,2-双(5-苯氧基-4-羟基苯基)乙烯,4,4′-二羟基二苯甲酮,3,3-双(4-羟基苯基)-2-丁酮,1,6-双(4-羟基苯基)-1,6-己二酮,乙二醇双(4-羟基苯基)醚,双(4-羟基苯基)醚,双(4-羟基苯基)硫醚,双(4-羟基苯基)亚砜,双(4-羟基苯基)砜,9,9-双(4-羟基苯基)氟,2,7-二羟基芘,6,6′-二羟基-3,3,3′,3′-四甲基螺(双)茚满(“螺二茚满双酚”),3,3-双(4-羟基苯基)苯酞,2,6-二羟基二苯并-对-二英,2,6-二羟基噻蒽,2,7-二羟基酚黄素,2,7-二羟基-9,10-二甲基吩嗪,3,6-二羟基二苯并呋喃,3,6-二羟基二苯并噻吩,和2,7-二羟基咔唑等,间苯二酚,取代的间苯二酚化合物例如5-甲基间苯二酚、5-乙基间苯二酚、5-丙基间苯二酚、5-丁基间苯二酚、5-叔丁基间苯二酚、5-苯基间苯二酚、5-枯基间苯二酚、2,4,5,6-四氟间苯二酚、2,4,5,6-四溴间苯二酚等;邻苯二酚;对苯二酚;取代的对苯二酚例如2-甲基对苯二酚、2-乙基对苯二酚、2-丙基对苯二酚、2-丁基对苯二酚、2-叔丁基对苯二酚、2-苯基对苯二酚、2-枯基对苯二酚、2,3,5,6-四甲基对苯二酚、2,3,5,6-四叔丁基对苯二酚、2,3,5,6-四氟对苯二酚、2,3,5,6-四溴对苯二酚,以及包括前述二羟基芳族化合物的至少一种的组合。
本基于有机硅的粘附促进剂可通过任何合适的方法形成。在多种实施方式中,所述基于有机硅的粘附促进剂通过如下形成:使二羟基芳族化合物(HO-Ar-OH)与卤代烯烃反应成具有式R1’-O-Ar-O-R2’的式的化合物,其中R1’和R2’各自为烯基末端烃;然后使该化合物与氢化硅氧烷经由硅氢化型反应而反应。可使用任何合适的硅氢化催化剂(例如,基于铂的催化剂如Karstedt或Ashby催化剂、或其它)来促进该含有烯基的化合物与氢化硅氧烷的反应。
本基于有机硅的粘附促进剂适合用于多种多样的应用中。在一个方面中,本基于有机硅的粘附促进剂已经被发现在固化性有机硅组合物中特别有用并且特别是,已经被发现可用于提供低温固化性有机硅组合物。已经发现本基于有机硅的粘附促进剂的使用在相对低的温度(例如,100℃或更低)下提供对包括金属和不同类型塑料两者在内的多种多样的表面良好的粘附。
在一个方面中,提供固化性有机硅组合物,其包括:(a)烯基官能的有机硅;(b)基于有机硅的交联剂;(c)填料;(d)选自本基于有机硅的粘附促进剂的第一粘附促进剂;(e)第二粘附促进剂;(f)任选地,硅烷;(g)抑制剂和(h)催化剂。已经发现本基于有机硅的粘附促进剂与第二粘附促进剂的组合提供良好的对宽范围表面的粘附和在相对低的温度下固化。
所述烯基官能的有机硅可为具有一个或多个键合至硅原子的烯基基团的有机基聚硅氧烷。在一种实施方式中,所述组合物包括具有至少两个键合至硅原子的烯基基团的有机基聚硅氧烷。所述组合物可包括两种或更多种不同的烯基官能的有机硅化合物的混合物。
在一种实施方式中,所述组合物包括下式的烯基官能的有机硅化合物:
M1 aM2 bD1 cD2 dT1 eT2 fQg
其中:
M1=R23R24R25SiO1/2
M2=R26R27R28SiO1/2
D1=R29R30SiO2/2
D2=R31R32SiO2/2
T1=R33SiO3/2
T2=R34SiO3/2
Q=SiO4/2
其中R23、R24、R25、R27、R28、R29、R30、R32、和R33独立地选自C1-C30烃、C6-C30芳族基团、或C1-C30烷氧基基团;
R26、R31、和R34独立地选自C1-C30烃、C6-C30芳族基团、C1-C30烷氧基基团、或C2-C30烯基基团,条件是R26、R31、和/或R34的一个或多个选自C2-C30烯基基团;
下标a、b、c、d、e、f、g为零或正数,其遵从以下限制:2<a+b+c+d+e+f+g<2000,b+d+f>0。
在一种实施方式中,所述烯基官能的有机硅包括两个或更多个烯基官能团(即,b+d+f>2)。在一种实施方式中,所述烯基官能的有机硅具有式M2D1 cM2。
进一步地,将领会,所述组合物可包括两种或更多种烯基官能的有机硅的混合物。当使用多种烯基官能的有机硅时,所述烯基官能的有机硅可为不同类型(例如,就M、D、T、和Q单元而言具有不同的总体构成)、或者不同尺寸(例如,具有类似的M、D、T、Q结构,但是就具体单元的数量而言不同)。在一种实施方式中,所述组合物包括具有式M2D1 cM2的第一烯基官能的有机硅,其中c为约5-约1000;和具有式M2D1 c’M2的第二烯基官能的有机硅,其中c’为约1000-约1500。
在一种实施方式中,所述烯基官能的有机硅为含有一个或多个键合至硅原子的烯基基团的支化的、笼状的低聚硅氧烷。所述支化的烯基官能的有机硅包括Q单元(SiO4/2单元)、M单元(R3SiO1/2单元),并且任选地进一步包括D单元(R2SiO单元)和/或T单元(R3SiO3/2单元)(其中R各自独立地为未取代或取代的单价脂族基团或脂环族基团),其中每个分子的R的至少三个优选为烯基基团。将领会,这样的支化的、笼状的硅氧烷被由式M1 aM2 bD1 cD2 dT1 eT2 fQg所描述的烯基官能的硅氧烷化合物所涵盖。
所述烯基官能的有机硅(或者两种或更多种烯基官能的有机硅的混合物)以如下量存在:约40-约75重量%;约45-约65重量%;或约52-约58重量%,基于所述组合物的总重量。
所述组合物包括有机基氢聚硅氧烷。所述有机基氢聚硅氧烷可选自下式的化合物:
M3 hM4 iD3 jD4 kT3 mT4 nQo
其中:
M3=R35R36R37SiO1/2
M4=R38R39R40SiO1/2
D3=R41R42SiO2/2
D4=R43R44SiO2/2
T3=R45SiO3/2
T4=R46SiO3/2
Q=SiO4/2
其中R35、R36、R37、R41、R42、R45、和独立地选自C1-C30烃、C6-C30芳族基团、或C1-C30烷氧基基团;
R38、R39、R40、R43、R44、和R46独立地选自氢、C1-C30烃、C6-C30芳族基团、C1-C30烷氧基基团、或C2-C30烯基基团,条件是R38、R39、R40、R43、R44、和/或R46的一个或多个为氢;
下标a、b、c、d、e、f、g为零或正数,其遵从以下限制:1<h+i+j+k+m+n+o<100,i+k+n>0。
所述氢化物(氢基)官能的有机硅交联剂(或者两种或更多种烯基官能的有机硅的混合物)以如下量存在:约0.01-约20重量%;约0.1-约5重量%;或约0.1-约2重量%,基于所述组合物的总重量。
可用于本发明中的填料(c)为选自如下那些的填料或填料混合物:其现在被知晓或者稍后被发现可用于有机硅组合物中,条件是它们未显著地损耗涂层的半透明性,即,涂覆的基底在其涂层的施加之后保持其原始外观。
合适填料(c)的实例包括,但不限于,用化合物例如硬脂酸盐或酯或硬脂酸处理的磨细、沉淀和胶体碳酸钙;增强用二氧化硅例如热解二氧化硅、沉淀二氧化硅、硅胶以及经疏水化的二氧化硅和硅胶;经破碎和磨细的石英、氧化铝、氢氧化铝、氢氧化钛、硅藻土、铁氧化物、炭黑、石墨或粘土例如高岭土、膨润土、或蒙脱土。
在一种实施方式中,填料(c)为二氧化硅填料,例如用D4和六甲基二硅氮烷或其组合处理的二氧化硅填料。可用于本发明中的填料的量通常为约1重量%-约50重量%、更优选约5重量%-约30重量%、和最优选约8重量%-约20重量%,基于所述固化性有机硅组合物的总重量。
所述固化性组合物包括选自如之前在本文中描述的基于芳族有机硅的粘附促进剂的第一粘附促进剂(d)。为了简洁起见,未重现所述基于芳族有机硅的粘附促进剂的细节。所述基于芳族有机硅的粘附促进剂可以如下量提供:约0.1%-约5%;约0.5%-约3%;或约0.5%-约2%重量,基于所述组合物的总重量。
所述固化性组合物任选地包括选自氢化物(氢基)官能的烷氧基硅烷的第二粘附促进剂。在一种实施方式中,所述氢化物官能的烷氧基硅烷选自下式的化合物:
R47-SiR48 r(OR49)3-r
其中R47为氢或氢化物官能团;
R48独立地选自C1-C10烃基团;各R49独立地选自C1-C10烃;并且r=0、1、或2。
取代基R48和R49基团的实例包括,但不限于,烷基基团例如甲基、乙基、正丙基、异丙基、正丁基、叔丁基、戊基、己基、辛基、和癸基;烯基基团例如2-丙烯基、己烯基、和辛烯基;芳烷基基团例如苄基和苯乙基;芳基基团例如苯基、甲苯基、和二甲苯基。
氢化(烃氧基)硅烷的具体实例包括三烷氧基硅烷、三烯氧基硅烷、和三芳氧基硅烷。三烷氧基硅烷的实例包括三甲氧基硅烷、三乙氧基硅烷、三正丙氧基硅烷、三异丙氧基硅烷、三丁氧基硅烷、三异丙烯氧基硅烷、和三苯氧基硅烷。二烷氧基硅烷、二烯氧基硅烷、和二芳氧基硅烷的实例包括甲基二甲氧基硅烷、甲基二乙氧基硅烷、甲基二正丙氧基硅烷、甲基二异丙烯氧基硅烷、甲基二苯氧基硅烷、乙基二甲氧基硅烷、乙基二乙氧基硅烷、正丙基二甲氧基硅烷、正丙基二乙氧基硅烷、3,3,3-三氟丙基二甲氧基硅烷、3,3,3-三氟丙基二乙氧基硅烷、正己基二甲氧基硅烷、正己基二乙氧基硅烷、正辛基二甲氧基硅烷、正辛基二乙氧基硅烷、苄基二甲氧基硅烷、苄基二乙氧基硅烷、苯乙基二甲氧基硅烷、苯乙基二乙氧基硅烷、苯基二甲氧基硅烷、和苯基二乙氧基硅烷。单烷氧基硅烷、单烯氧基硅烷、和单芳氧基硅烷的实例包括二甲基甲氧基硅烷、二甲基乙氧基硅烷、二甲基-正丙氧基硅烷、二甲基异丙烯氧基硅烷、二甲基苯氧基硅烷、二乙基甲氧基硅烷、甲基乙基乙氧基硅烷、正丙基(甲基)甲氧基硅烷、正丙基(甲基)乙氧基硅烷、3,3,3-三氟丙基(甲基)甲氧基硅烷、双(3,3,3-三氟丙基)乙氧基硅烷、正己基(甲基)甲氧基硅烷、二(正己基)乙氧基硅烷、正辛基(甲基)甲氧基硅烷、二(正辛基)乙氧基硅烷、苄基(甲基)甲氧基硅烷、苯乙基(甲基)甲氧基硅烷、和甲基苯基甲氧基硅烷。具有混合的烷氧基基团、烯氧基基团、芳烷基氧基基团、和芳氧基基团的氢化(烃氧基)硅烷的实例包括二乙氧基丙烯氧基硅烷、二甲氧基苯氧基硅烷、二苯氧基丙烯氧基硅烷、和甲基甲氧基苯乙氧基硅烷。
在多种实施方式中,R47为下式的含有环状的氢化硅氧烷的基团:
其中R51、R52、和R53独立地选自H、C1-C10烷基、或–OR54,其中R54为C1-C10烷基,并且R51、R52、和R53的至少一个为H;并且R50为C1-C30烃;C6-C30芳基基团;烷基丙烯酸酯基团;烷基羧酸酯基团;或酯基团。在一种实施方式中,式R47-SiR48 r(OR49)3-r的氢基官能的烷氧基硅烷,R47为环状的氢化硅氧烷,R50为C1-C30烃;C6-C30芳基基团;烷基丙烯酸酯基团;烷基羧酸酯基团;或酯基团,并且r为0,使得所述化合物包括三烷氧基甲硅烷基基团。在一种实施方式中,R50为具有键合至硅原子的侧链的有机基硅基团并且由下式表示
Q1-C(O)-O-Q2
其中:
Q1表示在该硅原子和酯键之间形成具有两个或更多个碳原子、在多种实施方式中2-20个碳原子、4-15个碳原子、或6-10个碳原子的碳链的线型或支化的亚烷基基团,
Q2表示在氧原子和侧链:SiR48 r(OR49)3-r中的硅原子之间形成具有三个或更多个碳原子、在多种实施方式中2-20个碳原子、4-15个碳原子、或6-10个碳原子的碳链的线型或支化的亚烷基基团。
针对无机基底的各种有机基官能的硅烷和硅氧烷粘附促进剂可用于所述组合物中作为第二粘附促进剂。合适的硅烷包括,但不限于,环氧基硅烷、异氰脲酸酯硅烷、酰亚氨基硅烷、酐硅烷、羧酸酯官能化的硅氧烷等。也可使用多种类型的粘附促进剂的组合。这样的组分典型地抑制经由金属催化的硅氢化的固化。合适的粘附促进剂包括,但不限于各种氨基硅烷材料例如A-1120硅烷、Silquest A-1110硅烷、Silquest A-2120硅烷、和Silquest A-1170硅烷;环氧基硅烷例如Silquest A-187硅烷;异氰脲酸酯硅烷例如Silquest A-597硅烷;和巯基硅烷例如Silquest A-189硅烷、Silquest A-1891硅烷、Silquest A-599硅烷,其可得自Momentive Performance Materials。
第二粘附促进剂可以如下量存在:约0.1%-约10%;约0.2%-约5%;或约0.5%-约3%重量,基于所述组合物的总重量。在采用第二粘附促进剂的实施方式中,第一粘附促进剂对第二粘附促进剂的比率可为约3:5;约3:1;或约1:1。
所述固化性组合物任选地进一步包括烷氧基硅烷(f)。烷氧基硅烷(f)为下式的化合物:
R55-SiR56 n(OR57)3-n
其中R55、R56、和R57独立地选自C1-C30烃、和/或C6-C30芳族基团,并且R55选自C1-C30烃、C6-30芳族基团、C1-C30烷氧基基团、或C2-C20不饱和烃。
合适烷氧基硅烷(f)的实例包括,但不限于,四甲氧基硅烷、四乙氧基硅烷、四正丙氧基硅烷、甲氧基三乙氧基硅烷、二甲氧基二乙氧基硅烷、三甲氧基-正丙氧基硅烷、双(2-乙基己氧基)二乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、戊基三乙氧基硅烷、三乙氧基硅烷、甲基三乙酰氧基硅烷、苯基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、烯丙基三甲氧基硅烷、烯丙基三乙氧基硅烷、γ-氨基丙基三甲氧基硅烷、γ-氨基丙基三乙氧基硅烷、β-氨基乙基三甲氧基硅烷、β-氨基乙基三乙氧基硅烷、N-β-氨基乙基氨基丙基三甲氧基硅烷、γ-异氰酸基丙基三乙氧基硅烷、巯基丙基三甲氧基硅烷、巯基乙基三甲氧基硅烷、巯基丙基三乙氧基硅烷、缩水甘油氧基丙基三甲氧基硅烷、缩水甘油氧基丙基三乙氧基硅烷、4,5-环氧基环己基乙基三甲氧基硅烷、脲基丙基三甲氧基硅烷、脲基丙基三乙氧基硅烷、氯丙基三甲氧基硅烷、氯丙基三乙氧基硅烷、氰基丙基三甲氧基硅烷等。
将领会,可采用两种或更多种不同的烷氧基硅烷作为烷氧基硅烷(f)。当存在时,所述烷氧基硅烷可以如下量存在:约0.1%-约5%;约0.1%-约3%;或约0.1%-约2.5%重量,基于所述组合物的总重量。
所述固化性组合物任选地包括聚合抑制剂(阻聚剂)(g)。所述聚合抑制剂没有特别限制并且可视具体目的或预期用途的需要而选择。合适抑制剂的实例包括,但不限于,烯属不饱和酰胺,芳族不饱和酰胺,炔属化合物,烯属不饱和异氰酸酯,烯烃硅氧烷,不饱和酸的不饱和烃二酯、不饱和烃单酯,共轭或孤立烯-炔,氢过氧化物,酮,亚砜,胺,膦,亚磷酸酯或盐,亚硝酸酯或盐,二氮杂环丙烷等。对于所述组合物而言特别合适的抑制剂为炔醇和马来酸酯或盐。合适的聚合抑制剂的实例包括,但不限于,马来酸二烯丙酯、对苯二酚、对甲氧基苯酚、叔丁基邻苯二酚、吩噻嗪等。.
用于所述组合物中的抑制剂(g)的量不是关键的并且可为在室温下将阻止以上反应,而在适度升高的温度即75-100℃的温度下不阻碍所述反应的任何量。组分(g)的范围可为0-约10%重量、约0.001-2%重量、甚至约0.12-约1重量。此处与说明书和权利要求中的其它地方一样,数值范围可组合以形成新的和替代的范围。
硅氢化催化剂(h)可包括贵金属催化剂例如,但不限于,使用钌、铑、钯、锇、铱、和铂的那些,以及这些金属的络合物。用于本发明中的合适的硅氢化催化剂的实例包括,但不限于:Ashby催化剂;Lamoreax催化剂;Karstedt催化剂;Modic催化剂;和Jeram催化剂以及其两种或更多种的组合。
在一种实施方式中,所述组合物可不含任何抑制剂组分(g)和Pt催化剂(h)。
所述固化性组合物还可包括其它添加剂(i)。其它添加剂可包括,但不限于,抗氧化剂、填料、颜料、染料、填料处理剂、增塑剂、间隔剂、增量剂、杀生物剂、稳定剂、阻燃剂、表面改性剂、抗老化添加剂、流变添加剂、腐蚀抑制剂、表面活性剂或其组合。
所述固化性组合物还可包括抗氧化剂化合物。合适类别的抗氧化剂化合物的实例包括,但不限于,受阻胺和/或受阻酚化合物。
受阻胺抗氧化剂化合物的实例包括,但不限于受阻胺系列抗氧化剂(N,N′,N″,N′″-四(4,6-双(丁基-(N-甲基)-2,2,6,6-四甲基哌啶-4-基)氨基)-三嗪-2-基)-4,7-二氮杂癸烷-1,10-二胺,二丁基胺-1,3,5-三嗪-N,N′-双(2,2,6,6-四甲基-4-哌啶基-1,6-六亚甲基二胺-N-(2,2,6,6-四甲基-4-哌啶基)丁基胺的缩聚产物,聚[{6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亚氨基}六亚甲基{(2,2,6,6-四甲基-4-哌啶基)亚氨基}],琥珀酸二甲酯和4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物,[癸二酸双(2,2,6,6-四甲基-1(辛基氧基)-4-哌啶基)酯、1,1-二甲基乙基氢过氧化物和辛烷的反应产物](70%)-聚丙烯(30%),丙二酸双(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]丁酯,甲基1,2,2,6,6-五甲基-4-哌啶基癸二酸酯,癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯,癸二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯,1-[2-[3-(3,5-二叔丁基-4-羟基苯基)丙酰氧基]乙基]-4-[3-(3,5-二叔丁基-4-羟基苯基)丙酰氧基]-2,2,6,6-四甲基哌啶,4-苯甲酰氧基-2,2,6,6-四甲基哌啶,8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮等)。
在一种实施方式中,所述抗氧化剂化合物为受阻酚类化合物。所述受阻酚可视具体目的或预期应用的需要而选择。合适受阻酚的实例包括,但不限于,单酚例如2,6-二叔丁基-对-甲酚、2-叔丁基-4-甲氧基苯酚、3-叔丁基-4-甲氧基苯酚、和2,6-叔丁基-4-乙基苯酚,双酚例如2,2′-亚甲基-双(4-甲基-6-叔丁基苯酚)、4,4′-硫代双(3-甲基-6-叔丁基苯酚)、和4,4′-丁叉基-双(3-甲基-6-叔丁基苯酚);和聚合物型酚例如1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷,1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯,四[亚甲基-3-(3′,5′-二叔丁基-4′-羟基苯基)丙酸酯]甲烷,双[3,3′-双(4′-羟基-3-叔丁基苯基)丁酸二醇酯,和生育酚(维生素E),季戊四醇-四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯],硫代二甘醇-双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯],十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯),N,N′-己烷-1,6-二基双[3-(3,5-二叔丁基-4-羟基苯基丙酰胺),苯丙酸3,5-双(1,1-二甲基乙基)-4-羟基C7-C9侧链烷基酯,2,4-二甲基-6-(1-甲基十五烷基)苯酚,二乙基[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]膦酸酯,3,3′,3″,5,5′,5″-己烷-叔丁基-4-a,a′,a″-(-2,4,6-甲苯基)三-对-甲酚(3,3′,3″,5,5′,5″-六叔丁基-4-a,a′,a″-(-2,4,6-甲苯基)三-对-甲酚),双[[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]膦酸]二乙酯钙,4,6-双(辛硫基甲基)-邻-甲酚,亚乙基双(氧基亚乙基)双[3-(5-叔丁基-4-羟基-间-甲苯基)丙酸酯],六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯],1,3,5-三(3,5-二叔丁基-4-羟基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮,N-苯基苯胺和2,4,4-三甲基戊烯的反应产物,2,6-二叔丁基-4-(4,6-双(辛硫基)-1,3,5-三嗪-2-基氨基)苯酚等)。
IRGANOX 1330为可从BASF商购获得的空间受阻(位阻)酚类抗氧化剂(“3,3′,3′,5,5′,5′-六叔丁基-a,a′,a′-(-2,4,6-三基)三-对-甲酚”)。Irganox 1010为可从BASF商购获得的空间受阻酚类抗氧化剂(“季戊四醇四(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)”),或者1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯可作为ETHANOXTM330(Albemarle Corporation)商购获得,季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯](Irganox 1010)、三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯(Irganox 3114)、三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯作为Irganox 3114可商购获得。
所述固化性组合物可任选地包括光稳定剂。所述光稳定剂没有特别限制并且可视具体应用或预期用途的需要而选择。对于光稳定剂而言合适材料的实例包括,但不限于,2,4-二叔丁基-6-(5-氯苯并三唑-2-基)苯酚,2-(2H-苯并三唑-2-基)-4,6-二叔戊基苯酚,2-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚,3-(3-(21-1-苯并三唑-2-基)-5-叔丁基-4-羟基苯基)丙酸甲酯/聚乙二醇300的反应产物,2-(2H-苯并三唑-2-基)-6-(直链和支链十二烷基)-4-甲基苯酚,2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]-苯酚,辛苯酮,2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯,tinuvin 622LD,Tinuvin144,CHIMASSORB 119FL,MARK LA-57、LA-62、LA-67、LA-63,SANDOL LS-765、LS-292、LS-2626、LS-1114、LS-744等。
所述固化性组合物可通过如下而固化:提供各组分的混合物并且将该混合物暴露于足够的温度达足够的时间以使所述组合物固化。各组分可单独地或者作为两个或更多个材料包添加,其中料包包括最终组合物所需要的组分的两种或更多种。在一种实施方式中,所述粘附促进剂作为包括如下的料包添加:(i)作为第一粘附促进剂的基于芳族的有机硅化合物,和(ii)第二粘附促进剂。在一种实施方式中,可将所述组合物在如下温度下加热:150℃以下;125℃以下;110℃以下;100℃以下;或90℃以下。在一种实施方式中,可将所述组合物在如下温度下加热:约75℃-约120℃;约85℃-约110℃;或约90℃-约100℃。固化可在暴露于升高的温度下达如下时间而完成:约10分钟-约3小时;15分钟-约1.5小时;或约30分钟-约1小时。
所述组合物可用于多种多样的应用中。在多种实施方式中,可将所述组合物固化并且用作用于密封的材料,用作胶粘剂;用作卫生间中的涂层(涂料);用作不同材料之间的接缝密封,例如,陶瓷或矿物表面和热塑性塑料之间的密封剂;用作纸离型物(paperrelease);用作浸渍材料;挡风雨条(weather strip)涂层、离型涂层、胶粘剂、粘附罩面(finishes)、防漏(堵漏,leak tight)产品,勾缝(pointing)产品,泡沫体等。作为实例,可将所述组合物固化并且用作用于建筑用途、绝缘玻璃的通用和工业密封剂、灌封料、填缝材料(caulk)、或者胶粘剂,其中将玻璃板固定和密封在金属框架中;用于金属板、车身、运载工具、电子设备等的填缝材料、胶粘剂。
进一步地,所述组合物可用于多种多样的基底上并且提供优异的胶粘剂性质。合适基底的实例包括,聚合物型基底,其可包括,但不限于,有机聚合物型材料例如选自如下的热塑性塑料树脂:丙烯腈-丁二烯-苯乙烯(ABS)树脂、聚碳酸酯(PC)树脂、聚氨酯(PU)树脂、苯乙烯树脂、聚乙烯(PE)树脂、聚丙烯(PP)树脂、丙烯酸类树脂、聚对苯二甲酸乙二醇酯(PET)树脂、聚对苯二甲酸丁二醇酯(PBT)树脂、聚苯醚(PPO)树脂、聚苯硫醚(PPS)树脂、聚砜树脂、尼龙(PA)树脂、芳族聚酰胺(芳族PA)树脂、聚酰亚胺(PI)树脂、和液晶树脂。所述组合物还可用于粘附至金属基底,包括铝、铁、镍、不锈钢、金属合金和电镀金属。
以下实施例旨在说明本技术的方面和实施方式。所有的份数和百分比以重量计并且所有的温度以摄氏度计,除非另有明确说明。将在本申请中提及的所有专利、其它出版物以及美国专利申请完全引入本文作为参考。
实施例
根据表1和2中列出的实施例制备组合物。所述组合物通过如下制备:将粘附促进剂(一种或多种)添加至组合物并且混合以分散到组合物中。氢化物烷氧基硅烷粘附促进剂硅烷A为被归入R47-SiR48 r(OR49)3-r的硅烷,其中R47为如本说明书中描述的具有连接至其的基团Q1-C(O)-O-Q2的环状的氢化硅氧烷。将所述组合物施加至在具有145mm2 x 0.15mm深尺寸的Teflon沟槽内的铝基底、聚苯硫醚(PPS)基底、或聚对苯二甲酸丁二醇酯(PBT)基底的表面。将所述基底置于烘箱中并且在90-100℃下固化30-60min。使用INSTRON 3365拉伸强度测试仪、测试方法ASTM D 3163测量经固化的材料的搭接剪切强度。
表1
表2
实施例6-9和11可视作对比例。如表中所示,与使用单独的其它粘附促进剂相比,本粘附促进剂提供良好的粘附。(参见表2。)另外,将本粘附促进剂与第二粘附促进剂一道使用还提供在更宽的基底谱范围内改善的粘附。
以上已经描述的内容包括本说明书的实例。当然,不可能为了描述本说明书的目的而描述组分或方法的每一个可想到的组合,但是本领域普通技术人员可认识到,本说明书的许多其它组合和排列是可能的。因此,本说明书意图涵盖落在所附权利要求的精神和范围内的所有此类改变、改动和变型。此外,就术语“包括”用于详细的描述或权利要求中而言,此类术语意图以与术语“包含”类似的方式而为包容性的,如同“包含”当在权利要求中作为过渡词使用时解释的那样。
前面的描述确定含有芳族的有机硅化合物和包括这样的化合物的固化性组合物的多种非限制性实施方式。本领域技术人员和可实施和利用本发明的人们可想到多种改动。所公开的实施方式仅用于说明目的并且不意图限制本发明的范围或者权利要求中阐述的主题。
Claims (24)
1.固化性有机硅组合物,其包括:(a)烯基官能的有机硅;(b)基于有机硅的交联剂;(c)填料;(d)第一粘附促进剂;(e)第二粘附促进剂;(f)任选地,硅烷;(g)抑制剂和(h)催化剂,其中第一粘附促进剂选自式Z1-R1-O-Ar-O-R2-Z2的化合物,其中R1和R2为C1-C30二价烃;C2-C20二价烃;C4-C10二价烃;或C1-C4二价烃;
Z1和Z2独立地为:
其中R3、R4、R5、R6、R7、R8、R9、和R10独立地选自H、C1-C10烷基、或–OR11,其中R11为C1-C10烷基,并且R3、R4、R5、R6、R7、R8、R9、和/或R10的至少一个为H;
X为1-10;
Y为2-10;和
Ar为芳族基团。
2.如权利要求1所述的固化性有机硅组合物,其中芳族基团Ar可选自C6-C30亚芳基基团、或式-Ar1-X-Ar2-的基团,其中Ar1和Ar2独立地选自单环二价芳基基团并且X为桥连基团。
3.如权利要求2所述的固化性有机硅组合物,其中Ar1和Ar2独立地选自C6-C30亚芳基基团,X选自连接Ar1和Ar2的键、C1-C30二价烃基团、C5-C30二价环状烃基团、-O-、-S-、-S(O)-、-S(O)2-、或-C(O)-。
6.如权利要求5所述的固化性有机硅组合物,其中X为–C(R22)2-,其中R22独立地选自氢、C1-C10烷基、C3-C8环烷基、或C6-C10芳基。
9.如权利要求1-8任一项所述的固化性有机硅组合物,其中第一粘附促进剂以基于所述组合物的总重量的约0.1重量%-约5重量%的量存在。
10.如权利要求1-9任一项所述的固化性组合物,其中第二粘附促进剂选自一种或多种具有式R47-SiR48 r(OR49)3-r的化合物,其中R47为氢或氢化物官能团;R48独立地选自C1-C10烃基团;各R49独立地选自C1-C10烃;并且r为0、1、或2。
12.如权利要求11所述的固化性组合物,其中r为0,并且R49为C1-C10烷基基团。
13.如权利要求1-12任一项所述的固化性组合物,其中第二粘附促进剂以基于所述组合物的总重量的约0.1重量%-约10重量%的量存在。
14.如权利要求1-14任一项所述的固化性组合物,其包括第二粘附促进剂(i)和(ii),其中:
第二粘附促进剂(i)选自一种或多种具有式R47-SiR48 r(OR49)3-r的化合物,其中R47为氢或氢化物官能团;R48独立地选自C1-C10烃基团;各R49独立地选自C1-C10烃;并且r为0;和
第二粘附促进剂(ii)选自式R47-SiR48 r(OR49)3-r的化合物,其中R48独立地选自C1-C10烃基团;各R49独立地选自C1-C10烃;并且r为0、1、或2,且R47为下式的含有环状的氢化硅氧烷的基团:
其中R51、R52、和R53独立地选自H、C1-C10烷基、或–OR54,其中R54为C1-C10烷基,并且R51、R52、和R53的至少一个和的至少一个为H;并且R50为C1-C30烃;C6-C30芳基基团;烷基丙烯酸酯基团;烷基羧酸酯基团;或酯基团。
15.如权利要求14所述的固化性有机硅组合物,其中第二粘附促进剂(i)以约0.5重量%-约3重量%的量存在,和第二粘附促进剂(ii)以约0.1重量%-约8重量%的量存在。
16.如权利要求1-15任一项所述的固化性有机硅组合物,其中所述烯基有机硅选自式M1 aM2 bD1 cD2 dT1 eT2 fQg的化合物
其中:
M1=R23R24R25SiO1/2
M2=R26R27R28SiO1/2
D1=R29R30SiO2/2
D2=R31R32SiO2/2
T1=R33SiO3/2
T2=R34SiO3/2
Q=SiO4/2
其中R23、R24、R25、R27、R28、R29、R30、R32、和R33独立地选自C1-C30烃、C6-C30芳族基团、或C1-C30烷氧基基团;
R26、R31、和R34独立地选自C1-C30烃、C6-C30芳族基团、C1-C30烷氧基基团、或C2-C30烯基基团,条件是R26、R31、和/或R34的一个或多个选自C2-C30烯基基团;
下标a、b、c、d、e、f、g为零或正数,其遵从以下限制:2<a+b+c+d+e+f+g<2000,b+d+f>0。
17.如权利要求16所述的固化性有机硅组合物,其中所述烯基有机硅包括选自如下的烯基有机硅的混合物:(i)具有式M2D1 cM2的第一烯基官能的有机硅,其中c为约5-约1000;和(ii)具有式M2D1 c’M2的第二烯基官能的有机硅,其中c’为约1000-约1500。
18.如权利要求1-17任一项所述的固化性组合物,其中所述烯基有机硅为包括多个Qg单元和一个或多个M2单元的支化的聚有机基硅氧烷。
19.如权利要求1-18任一项所述的固化性有机硅组合物,其中所述有机硅氢化物交联剂选自下式的化合物:
M3 hM4 iD3 jD4 kT3 mT4 nQo
其中:
M3=R35R36R37SiO1/2
M4=R38R39R40SiO1/2
D3=R41R42SiO2/2
D4=R43R44SiO2/2
T3=R45SiO3/2
T4=R46SiO3/2
Q=SiO4/2
其中R35、R36、R37、R41、R42、R45、和独立地选自C1-C30烃、C6-C30芳族基团、或C1-C30烷氧基基团;
R38、R39、R40、R43、R44、和R46独立地选自氢、C1-C30烃、C6-C30芳族基团、C1-C30烷氧基基团、或C2-C30烯基基团,条件是R38、R39、R40、R43、R44、和/或R46的一个或多个为氢;
下标a、b、c、d、e、f、g为零或正数,其遵从以下限制:1<h+i+j+k+m+n+o<100,i+k+n>0。
20.由如权利要求1-19任一项所述的组合物形成的固化的有机硅材料。
21.在基底上形成胶粘剂涂层的方法,其包括:
将如权利要求1-19任一项所述的固化性组合物施加至基底的表面,和将所述组合物在约50℃-约110℃的温度下加热。
22.如权利要求21所述的方法,其包括将所述组合物在约60℃-约100℃的温度下加热。
23.如权利要求21或22所述的方法,其中将所述组合物固化10分钟-约3小时的时期。
24.如权利要求21-24任一项所述的方法,其中所述基底选自塑料材料、金属、金属合金、金属化塑料、和/或经涂布或上漆的金属。
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EP1172413A2 (en) * | 2000-07-11 | 2002-01-16 | Shin-Etsu Chemical Co., Ltd. | Silicone rubber adhesive composition and integrally molded article thereof |
EP1172414A2 (en) * | 2000-07-11 | 2002-01-16 | Shin-Etsu Chemical Co., Ltd. | Silicone rubber adhesive composition and integrally molded article thereof |
JP2010196011A (ja) * | 2009-02-27 | 2010-09-09 | Shin-Etsu Chemical Co Ltd | 付加硬化型自己接着性シリコーンゴム組成物 |
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EP1172413A2 (en) * | 2000-07-11 | 2002-01-16 | Shin-Etsu Chemical Co., Ltd. | Silicone rubber adhesive composition and integrally molded article thereof |
EP1172414A2 (en) * | 2000-07-11 | 2002-01-16 | Shin-Etsu Chemical Co., Ltd. | Silicone rubber adhesive composition and integrally molded article thereof |
JP2010196011A (ja) * | 2009-02-27 | 2010-09-09 | Shin-Etsu Chemical Co Ltd | 付加硬化型自己接着性シリコーンゴム組成物 |
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