CN104513353A - 与有机硅粘接的组合物 - Google Patents

与有机硅粘接的组合物 Download PDF

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CN104513353A
CN104513353A CN201410792960.6A CN201410792960A CN104513353A CN 104513353 A CN104513353 A CN 104513353A CN 201410792960 A CN201410792960 A CN 201410792960A CN 104513353 A CN104513353 A CN 104513353A
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周中涛
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JIANGMEN ABQ ELECTRONIC MATERIAL CO Ltd
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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Abstract

本发明公开了一种与有机硅粘接的组合物，包括聚氨酯、溶剂和颜料，其特征在于，所述聚氨酯含有多元醇单元，所述多元醇单元具有含链烯基的二有机聚硅氧烷结构；其中，所述聚氨酯由以下组分混合反应制成：按摩尔比计算，含链烯基的二有机聚硅氧烷:聚酯二醇:扩链剂:有机聚异氰酸酯=(0.001~0.018):1:(0~2.11):3.11；其中，所述多元醇单元的平均分子量为2000-4000。本发明的组合物与有机硅的粘接强度为超过50N/2.5cm。

Description

与有机硅粘接的组合物
技术领域
本发明涉及与有机硅粘接的组合物。
背景技术
聚氨酯是一种多功能的聚合材料，加工性能良好，然而，其热稳定性、表面性能、耐老化性、耐污染性较差。而有机硅树脂具有低温柔顺性好、表面张力低、生物相容性好等优点，也存在力学强度低、附着力较差等缺点。
由聚氨酯得到的层的表面活性不充分，因此，在层叠有机硅时，需要在层的表面上预先实施表面活性化处理，包括有底涂处理、电晕放电处理、等离子体处理、臭氧处理、火焰处理等，但任何一种方法均具有导致生产率降低及作业效率降低的问题。
发明内容
本发明的一个目的是提供一种能直接与有机硅粘接的组合物，包括聚氨酯、溶剂和颜料，其特征在于，所述聚氨酯含有多元醇单元，所述多元醇单元具有含链烯基的二有机聚硅氧烷结构；其中，所述聚氨酯由以下组分混合反应制成：含链烯基的二有机聚硅氧烷:聚酯二醇:扩链剂:有机聚异氰酸酯=(0.001~0.018):1:2.11:3.11；其中，所述多元醇单元的平均分子量为2000-4000。
上述含链烯基的聚有机硅氧烷多元醇的平均分子量优选在2000-4000的范围内，更优选在2500-4000的范围内，进一步优选在3000-4000的范围内。使用具有上述平均分子量范围的多元醇时，可以得到非粘合性、熔融成形性、熔融粘接性、耐磨性、拉伸断裂强度等力学特性、柔软性、弯曲性、低残余应变性优异的聚氨酯。
本发明的聚氨酯的多元醇结构中，所述含链烯基的二有机聚硅氧烷的分子链末端为羟基，所述羟基与所述有机硅中的硅原子键合，从而实现聚氨酯与有机硅的有效直接联接。
在本发明的一些实施例中，所述含链烯基的二有机聚硅氧烷包括聚甲基乙烯基硅氧烷、聚甲基烯丙基硅氧烷、聚甲基己烯基硅氧烷、二甲基硅氧烷-甲基乙烯基硅氧烷共聚物、二甲基硅氧烷-甲基烯丙基硅氧烷共聚物、二甲基硅氧烷-甲基己烯基硅氧烷共聚物中的一种或多种混合。
在本发明的一些实施例中，还可包括聚酯二醇来形成多元醇结构，所述聚酯二醇包括2-甲基-1,4-丁二醇、3-甲基-1,5-戊二醇、2-甲基-1,8-辛二醇、2,7-二甲基-1,8-辛二醇、2-甲基-1,9-壬二醇、2,8-二甲基-1,9-壬二醇中的一种或多种混合。以上的多元醇结构在分子链两末端具有与硅原子键合的羟基或与硅原子键合的甲醇基，这样，含链烯基二有机聚硅氧烷分子链的两末端被羟基封端。
在本发明的一些实施例中，所述有机聚异氰酸酯包括4，4’-二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或两种。
在本发明的一些实施例中，所述扩链剂包括乙二醇、丙二醇、1，4-丁二醇、1，6-己二醇中的一种或多种。优选1，4-丁二醇。
本发明的有益效果：
本发明的组合物可以有效地与有机硅直接粘结，即使不进行表面活性化处理，也能制造出粘接性优异的覆膜。
利用本发明的组合物得到的印刷物与有机硅的粘接性优异，同时，相对于聚酯、尼龙、聚丙烯等膜也显示优异的粘接性。另外，得到的印刷物的耐煮性、耐热性、表面强度、非粘合性、耐油性优异。
具体实施方式
实施例1-3以及比较例的配方列表
实施例1-3以及比较例的性能比较
将实施例1-3和比较例的组合物涂布在市面上购买的两种不同的有机硅表面，在100℃的热风干燥机中放置30分钟。在干燥的组合物涂布面上贴付胶带（Mchiban株式会社制，布胶带LS No. 101)，对剥下该胶带时的阻力值（粘接强度），使用株式会社岛津制作所制 "Autograph测定装置IS-500D”，在室温下、拉伸速度50mm/分钟的条件下进行测定，作为粘接性的指标。
在实验中，组合物的固化覆膜和有机硅层的界面牢固地粘接，在剥离试验中有机硅层被破坏，而且剥下时的粘接强度为超过50N/2.5cm。

Claims (6)

1.一种与有机硅粘接的组合物，包括聚氨酯、溶剂和颜料，其特征在于，所述聚氨酯含有多元醇单元，所述多元醇单元具有含链烯基的二有机聚硅氧烷结构；其中，所述聚氨酯由以下组分混合反应制成：按摩尔比计算，含链烯基的二有机聚硅氧烷:聚酯二醇:扩链剂:有机聚异氰酸酯=(0.001~0.018):1:(0~2.11):3.11；其中，所述多元醇单元的平均分子量为2000-4000。
2.根据权利要求1所述的组合物，其特征在于，所述含链烯基的二有机聚硅氧烷的分子链末端为羟基，所述羟基与所述有机硅中的硅原子键合。
3.根据权利要求1所述的组合物，其特征在于，所述含链烯基的二有机聚硅氧烷包括聚甲基乙烯基硅氧烷、聚甲基烯丙基硅氧烷、聚甲基己烯基硅氧烷、二甲基硅氧烷-甲基乙烯基硅氧烷共聚物、二甲基硅氧烷-甲基烯丙基硅氧烷共聚物、二甲基硅氧烷-甲基己烯基硅氧烷共聚物中的一种或多种混合。
4.根据权利要求1所述的组合物，其特征在于，所述聚酯二醇包括2-甲基-1,4-丁二醇、3-甲基-1,5-戊二醇、2-甲基-1,8-辛二醇、2,7-二甲基-1,8-辛二醇、2-甲基-1,9-壬二醇、2,8-二甲基-1,9-壬二醇中的一种或多种混合。
5.根据权利要求1所述的组合物，其特征在于，所述有机聚异氰酸酯包括4，4’-二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或两种。
6.根据权利要求1所述的组合物，其特征在于，所述扩链剂包括乙二醇、丙二醇、1，4-丁二醇、1，6-己二醇中的一种或多种。
CN201410792960.6A 2014-12-20 2014-12-20 与有机硅粘接的组合物 Pending CN104513353A (zh)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199346A (zh) * 2011-03-28 2011-09-28 刘春博 可钻滤砂管用聚硅氧烷改性聚氨酯及其制备方法与应用
CN102414240A (zh) * 2009-04-30 2012-04-11 道康宁东丽株式会社 聚氨酯及其制造方法、母料、油墨用粘合剂、油墨组合物、成形用热塑性聚合物组合物、成形体、复合成形体及其制造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102414240A (zh) * 2009-04-30 2012-04-11 道康宁东丽株式会社 聚氨酯及其制造方法、母料、油墨用粘合剂、油墨组合物、成形用热塑性聚合物组合物、成形体、复合成形体及其制造方法
CN102199346A (zh) * 2011-03-28 2011-09-28 刘春博 可钻滤砂管用聚硅氧烷改性聚氨酯及其制备方法与应用

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