CN116940612A - 双组分固化型聚氨酯树脂组合物 - Google Patents
双组分固化型聚氨酯树脂组合物 Download PDFInfo
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- CN116940612A CN116940612A CN202280018041.6A CN202280018041A CN116940612A CN 116940612 A CN116940612 A CN 116940612A CN 202280018041 A CN202280018041 A CN 202280018041A CN 116940612 A CN116940612 A CN 116940612A
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- Prior art keywords
- polyol
- component
- polyurethane resin
- resin composition
- mass
- Prior art date
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Classifications
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- 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
- C08G18/76—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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- 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
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明提供一种相溶性、密合性和低介电特性优异的双组分固化型聚氨酯树脂组合物。实施方式涉及的双组分固化型聚氨酯树脂组合物具有:含有多元醇和萜烯树脂的第一成分、和含有多异氰酸酯的第二成分,其中,所述多元醇含有30质量%以上的聚丁二烯多元醇和/或氢化聚丁二烯多元醇,相对于100质量份所述多元醇,所述萜烯树脂的含量为1质量份~60质量份。
Description
技术领域
本发明涉及双组分固化型聚氨酯树脂组合物和使用了该组合物的电气电子部件、以及用于该双组分固化型聚氨酯树脂组合物的多元醇组合物。
背景技术
以往,对于电子电路基板、电子部件来说,为了避免其受到外在因素影响而使用聚氨酯树脂组合物进行密封,并且作为聚氨酯树脂组合物的多元醇,已知使用聚丁二烯多元醇。
例如,专利文献1中公开了一种电绝缘材料,其含有:含羟基的液态二烯系聚合物、多异氰酸酯化合物、多环芳香族烃和石油树脂。专利文献2中公开了一种耐热性防湿绝缘涂料,其通过含有使含羟基的聚丁二烯、含羟基的氢化聚丁二烯以及多异氰酸酯反应而得到的聚合物、增粘剂和溶剂而成。
现有技术文献
专利文献
专利文献1:日本特开昭61-197620号公报
专利文献2:日本特开平8-165454号公报
发明内容
发明欲解决的技术问题
然而,在现有的聚氨酯树脂组合物中,如果是双组分固化型聚氨酯树脂组合物且其具有含有多元醇的第一成分和含有多异氰酸酯的第二成分,则有时在含有多元醇的同时也含有石油树脂等其他成分的第一成分的相容性变差,还有时聚氨酯树脂组合物与基板的密合性不充分。另外,例如在作为对传感器、无线通信部件进行密封的密封材料而使用的情况下,为了抑制对电波的影响,要求聚氨酯树脂组合物为低介电常数。
鉴于以上问题,本发明的实施方式的目的在于提供一种相容性、密合性和低介电特性优异的双组分固化型聚氨酯树脂组合物。
用于解决问题的技术手段
本发明包括以下所示的实施方式。
[1]一种双组分固化型聚氨酯树脂组合物,具有:第一成分,所述第一成分包含多元醇和萜烯树脂;和第二成分,所述第二成分包含多异氰酸酯,其中,所述多元醇含有30质量%以上的聚丁二烯多元醇和/或氢化聚丁二烯多元醇,相对于100质量份所述多元醇,所述萜烯树脂的含量为1质量份~60质量份。
[2]根据[1]所述的双组分固化型聚氨酯树脂组合物,其中,所述萜烯树脂为从由聚萜烯树脂、芳香族改性萜烯树脂和萜烯酚树脂组成的组中选出的至少一种。
[3]根据[1]或[2]所述的双组分固化型聚氨酯树脂组合物,其中,所述多元醇还包含蓖麻油系多元醇。
[4]根据[1]~[3]中任一项所述的双组分固化型聚氨酯树脂组合物,其中,所述双组分固化型聚氨酯树脂组合物为电气电子部件密封用。
[5]一种电气电子部件,使用[1]~[4]中任一项所述的双组分固化型聚氨酯树脂组合物进行树脂密封。
[6]一种多元醇组合物,其中,所述多元醇组合物被用作双组分固化型聚氨酯树脂组合物中的多元醇成分,所述多元醇组合物包含多元醇和萜烯树脂,所述多元醇含有30质量%以上的聚丁二烯多元醇和/或氢化聚丁二烯多元醇,相对于100质量份所述多元醇,所述萜烯树脂的含量为1质量份~60质量份。
发明效果
根据本发明的实施方式,可以提供相容性、密合性和低介电特性优异的双组分固化型聚氨酯树脂组合物。
具体实施方式
本实施方式涉及的双组分固化型聚氨酯树脂组合物具有:第一成分,所述第一成分包含多元醇(A)和萜烯树脂(B);以及第二成分,所述第二成分包含多异氰酸酯(C),其中,所述多元醇(A)含有聚丁二烯多元醇(A1-1)和/或氢化聚丁二烯多元醇(A1-2)。
<第一成分>
[聚丁二烯多元醇(A1-1)和/或氢化聚丁二烯多元醇(A1-2)]
作为第一成分中包含的多元醇(A),可以使用聚丁二烯多元醇(A1-1)和/或氢化聚丁二烯多元醇(A1-2)(以下,有时将两者统称为“PB多元醇(A1)”)。
作为聚丁二烯多元醇(A1-1),优选在分子中具有1,4-键型、1,2-键型或者1,4-键型和1,2-键型混合存在的聚丁二烯结构以及至少2个羟基,更优选在聚丁二烯结构的两末端分别具有羟基。
聚丁二烯多元醇(A1-1)的羟值没有特别限定,例如可以为10~200mgKOH/g,可以为15~150mgKOH/g,可以为20~120mgKOH/g,可以为25~100mgKOH/g,可以为40~90mgKOH/g。本说明书中,羟值按照JIS K1557-1:2007的A法来测定。
氢化聚丁二烯多元醇(A1-2)具有对聚丁二烯多元醇(A1-1)加氢而成的结构,聚丁二烯多元醇中含有的不饱和双键的一部分或全部被氢化。氢化聚丁二烯多元醇(A1-2)的氢化程度没有特别限定,例如碘值可以为50g/100g以下,也可以为30g/100g以下。本说明书中,碘值按照JIS K0070来测定。
氢化聚丁二烯多元醇(A1-2)的羟值没有特别限定,例如可以为10~200mgKOH/g,可以为15~150mgKOH/g,可以为20~120mgKOH/g,可以为25~100mgKOH/g,可以为40~90mgKOH/g。
[蓖麻油系多元醇(A2)]
多元醇(A)中还可以含有蓖麻油系多元醇(A2)。作为蓖麻油系多元醇(A2),可以使用利用蓖麻油、蓖麻油脂肪酸及对它们加氢而成的氢化蓖麻油或氢化蓖麻油脂肪酸而制造出的多元醇。更详细而言,作为蓖麻油系多元醇(A2),例如可以列举:蓖麻油、蓖麻油与其他天然油脂的酯交换物、蓖麻油与多羟基醇的反应产物、蓖麻油脂肪酸与多羟基醇的酯化反应产物、以及对它们加成聚合了环氧烷而得到的多元醇等。
蓖麻油系多元醇(A2)的羟值没有特别限定,例如可以为50~250mgKOH/g,也可以为100~180mgKOH/g。
[多元醇(A)]
多元醇(A)可以仅由PB多元醇(A1)构成,也可以仅由PB多元醇(A1)和蓖麻油系多元醇(A2)构成,还可以在含有PB多元醇(A1)的同时含有其他多元醇(A3),也可以在含有PB多元醇(A1)和蓖麻油系多元醇(A2)的同时含有其他多元醇(A3)。多元醇(A)可以仅由双官能的多元醇构成,也可以含有三官能以上的多元醇,但是在多异氰酸酯(C)仅由双官能的多异氰酸酯构成的情况下,为了使聚氨酯树脂组合物具有热固性,优选含有三官能以上的多元醇。
作为其他多元醇(A3),没有特别限定,是分子内具有多个羟基的化合物,可以列举除PB多元醇(A1)和蓖麻油系多元醇(A2)以外的各种多元醇。具体而言,可以列举:聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、二聚酸多元醇、聚己内酯多元醇、丙烯酸多元醇、聚异戊二烯多元醇、氢化聚异戊二烯多元醇等。作为其他多元醇(A3),还可以是通常作为交联剂而使用的低分子量多元醇,例如可以列举分子量300以下的多羟基醇,具体而言,可以列举:N,N-双(2-羟基丙基)苯胺、对苯二酚-双(β-羟乙基)醚、间苯二酚-双(β-羟乙基)醚等芳香族醇;乙二醇、1,4-丁二醇、辛二醇、三羟甲基丙烷、三异丙醇胺等脂肪族醇。
在多元醇(A)100质量%中,PB多元醇(A1)的含量为30质量%以上,更优选为50质量%以上,进一步优选为60质量%以上。通过使PB多元醇(A1)的含量为30质量%以上,从而能够提高与电子电路基板等的密合性,还能够降低介电常数。PB多元醇(A1)的含量上限没有特别限定,可以为100质量%,可以为95质量%,可以为85质量%,也可以为80质量%。
在多元醇(A)中含有蓖麻油系多元醇(A2)的情况下,多元醇(A)100质量%中,蓖麻油系多元醇(A2)的含量没有特别限定,例如可以为5~70质量%,可以为15~50质量%,也可以为20~40质量%。
[萜烯树脂(B)]
本实施方式中,在第一成分中使用PB多元醇(A1)以及萜烯树脂(B)。萜烯树脂(B)与PB多元醇(A1)的相容性优异,因此能够抑制第一成分的分离、浑浊。另外,通过将PB多元醇(A1)和萜烯树脂(B)并用,从而能够提高与电子电路基板等的密合性,并且能够得到介电常数低的聚氨酯树脂。
萜烯树脂(B)是含有萜烯作为构成单体的聚合物。作为萜烯(也称为萜烯单体),例如可以列举:α-蒎烯、β-蒎烯、柠檬烯(也包括外消旋体的二戊烯)、月桂烯、别罗勒烯、罗勒烯、α-水芹烯、β-水芹烯、α-萜品烯、γ-萜品烯、及桧烯等单萜烯。其中,优选α-蒎烯、β-蒎烯、柠檬烯、α-水芹烯、β-水芹烯、α-萜品烯、及γ-萜品烯等单环式的单萜烯,更优选为从由α-蒎烯、β-蒎烯及柠檬烯组成的组中选出至少一种。
作为萜烯树脂(B),可以列举:聚萜烯树脂(B1),是构成单体仅包括萜烯单体的均聚物或共聚物;芳香族改性萜烯树脂(B2),是萜烯单体与芳香族单体的共聚物;萜烯酚树脂(B3),是萜烯单体与酚系单体的共聚物。它们可以使用任一种,也可并用两种以上。
作为构成芳香族改性萜烯树脂(B2)的芳香族单体,例如可以列举:苯乙烯、α-甲基苯乙烯、4-甲基苯乙烯、2,4-二甲基苯乙烯等。
作为构成萜烯酚树脂(B3)的酚系单体,例如可以列举:苯酚、甲酚、二甲苯酚等。
作为萜烯树脂(B)的优选例,可以列举:聚萜烯树脂(B1),从由α-蒎烯、β-蒎烯和柠檬烯组成的组中选出的至少一种均聚物或共聚物;芳香族改性萜烯树脂(B2),从由α-蒎烯、β-蒎烯和柠檬烯组成的组中选出的至少一种萜烯单体与苯乙烯的共聚物;萜烯酚树脂(B3),从由α-蒎烯、β-蒎烯和柠檬烯组成的组中选出的至少一种萜烯单体与酚的共聚物。
相对于100质量份多元醇(A),萜烯树脂(B)的含量为1质量份~60质量份。通过使萜烯树脂(B)的含量为60质量份以下,从而能够抑制萜烯树脂(B)在聚氨酯树脂固化后渗出。萜烯树脂(B)的含量优选为5质量份以上,更优选为10质量份以上,进一步优选为15质量份以上,另外,优选为50质量份以下,更优选为40质量份以下,进一步优选为30质量份以下。
[其他成分]
在第一成分中,除了上述各成分以外,还可以在不损害本实施方式的目的的范围内,根据需要加入例如催化剂、抗氧化剂、稳泡剂、稀释剂、阻燃剂、紫外线吸收剂、着色剂、填充剂、增塑剂等各种添加剂。
作为催化剂,例如可以使用有机锡催化剂、有机铅催化剂、有机铋催化剂等金属催化剂、胺催化剂等各种氨基甲酸酯聚合催化剂。
<第二成分>
[多异氰酸酯(C)]
作为第二成分中含有的多异氰酸酯(C),没有特别限定,可以使用1分子中具有2个以上异氰酸酯基的各种多异氰酸酯化合物。作为多异氰酸酯(C),例如可以列举:脂肪族多异氰酸酯化合物(C1)、脂环式多异氰酸酯化合物(C2)和芳香族多异氰酸酯化合物(C3)、以及它们的改性体及多核体,可以使用任一种,也可以并用两种以上。
作为脂肪族多异氰酸酯化合物(C1),可以列举:四亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、六亚甲基二异氰酸酯(HDI)、2,2,4-三甲基六亚甲基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、2-甲基戊烷-1,5-二异氰酸酯、3-甲基戊烷-1,5-二异氰酸酯等。
作为脂环式多异氰酸酯化合物(C2),例如可以列举:异佛尔酮二异氰酸酯(IPDI)、氢化苯二亚甲基二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、1,4-环己烷二异氰酸酯、甲基亚环己基二异氰酸酯、1,3-双(异氰酸酯甲基)环己烷等。
作为芳香族多异氰酸酯化合物(C3),例如可以列举:甲苯二异氰酸酯(TDI,例如2,4-TDI、2,6-TDI)、二苯基甲烷二异氰酸酯(MDI,例如2,2’-MDI、2,4’-MDI、4,4’-MDI)、4,4’-二苄基二异氰酸酯、1,5-萘二异氰酸酯、苯二亚甲基二异氰酸酯(XDI)、1,3-苯二异氰酸酯、1,4-苯二异氰酸酯等。
作为这些多异氰酸酯化合物(C1)~(C3)的改性物,例如可以列举:异氰脲酸酯改性体、脲基甲酸酯改性体、缩二脲改性体、加合物改性体、碳二亚胺改性体等。
在一个实施方式中,作为优选的多异氰酸酯(C),例如可以列举:聚合MDI、多异氰酸酯化合物(C1)~(C3)的碳二亚胺改性体(更优选芳香族多异氰酸酯化合物(C3)的碳二亚胺改性体)、多异氰酸酯化合物(C1)~(C3)的异氰脲酸酯改性体(更优选脂肪族多异氰酸酯化合物(C1)的异氰脲酸酯改性体)等,它们可以使用任一种,或2种以上组合使用。更优选使用从由聚合MDI、碳二亚胺改性MDI及异氰脲酸酯改性HDI组成的组中选出的至少一种。
双组分固化型聚氨酯树脂组合物中,多异氰酸酯(C)的含量没有特别限定,例如,相对于100质量份多元醇(A),多异氰酸酯(C)的含量可以为1质量份~70质量份,可以为3质量份~50质量份,可以为5质量份~40质量份。
多异氰酸酯(C)可以仅由双官能的多异氰酸酯构成,也可以包含三官能以上的多异氰酸酯,但在多元醇(A)仅由双官能的多异氰酸酯构成的情况下,为了使聚氨酯树脂组合物具有热固性,优选包含三官能以上的多异氰酸酯。
多异氰酸酯(C)与多元醇(A)之比没有特别限定,例如,多异氰酸酯(C)的摩尔数与多元醇(A)的摩尔数之比即NCO/OH(指数)可以为0.6~1.5,可以为0.7~1.4,可以为0.8~1.3,也可以为0.9~1.2。
[其他成分]
第二成分可以仅由多异氰酸酯(C)构成,另外,除了多异氰酸酯(C)以外,在不损害本实施方式的目的的范围内,还可以根据需要加入例如催化剂、抗氧化剂、稳泡剂、稀释剂、阻燃剂、紫外线吸收剂、着色剂、填充剂、增塑剂等各种添加剂。
<双组分固化型聚氨酯树脂组合物>
本实施方式涉及的双组分固化型聚氨酯树脂组合物通常由作为第一成分的第一液和作为第二成分的第二液构成,但除了第一成分和第二成分以外,还可以具备第三成分作为第三液,该第三成分含有作为任意成分的上述其他成分。
该双组分固化型聚氨酯树脂组合物可以通过分别制备第一成分和第二成分来制造,即,第一成分和第二成分可以分别填充于不同的容器中。分别填充于容器后的第一成分和第二成分可以在使用时通过混合从而使多元醇(A)与多异氰酸酯(C)反应而形成聚氨酯树脂,并固化。此时,也可以通过加热使其固化。实施方式涉及的双组分固化型聚氨酯树脂组合物可以是将第一成分和第二成分混合而得到的组合物,可以是固化前的液态,也可以是正在固化。
<多元醇组合物>
一个实施方式涉及的多元醇组合物被用作双组分固化型聚氨酯树脂组合物的多元醇成分,上述第一成分与此相当。因此,该多元醇组合物含有多元醇(A)和萜烯树脂(B),该多元醇(A)包含30质量%以上的聚丁二烯多元醇和/或氢化聚丁二烯多元醇,相对于100质量份多元醇(A),萜烯树脂(B)的含量为1质量份~60质量份。关于多元醇(A)、萜烯树脂(B)及其他成分的详细情况如上所述,省略说明。
<双组分固化型聚氨酯树脂组合物的用途>
本实施方式涉及的双组分固化型聚氨酯树脂组合物的用途没有特别限定,优选被用于电气电子部件的密封。作为电气电子部件,例如可以列举:变压器线圈、扼流线圈以及电抗器线圈等变压器、设备控制基板、传感器、无线通信部件等。该双组分固化型聚氨酯树脂组合物的低介电特性优异(即,介电常数低),不易受到电波影响,因此为了保护进行无线通信的无线通信部件免受外部环境的影响,优选被用作对该无线通信部件进行树脂密封、即被覆的密封材料,例如,也可以用作将检测到的信息通过无线通信来发送的传感器的密封材料。
使用本实施方式涉及的双组分固化型聚氨酯树脂组合物进行树脂密封而得到的电气电子部件例如可以用于电洗衣机、马桶座、热水器、***、浴池、餐具清洗机、太阳能面板、电动工具、汽车、摩托车等中。
实施例
以下,基于实施例和比较例,对双组分固化型聚氨酯树脂组合物进行详细说明,但本发明不限于此。
以下示出实施例及比较例中使用的原料。
[多元醇(A)]
·聚丁二烯多元醇1:羟值47mgKOH/g、产品名:Poly bd R-45HT、出光兴产株式会社制
·聚丁二烯多元醇2:羟值107mgKOH/g、产品名:Poly bd R-15HT、出光兴产株式会社制
·聚丁二烯多元醇3:羟值49mgKOH/g、产品名:KRASOL LBH-2000、Cray Valley公司制
·氢化聚丁二烯多元醇:羟值49mgKOH/g、产品名:KRASOL H-LBH-2000、CrayValley公司制
·蓖麻油系多元醇:羟值120mgKOH/g、产品名:HS2G-120、丰国制油株式会社制
·聚醚多元醇:羟值160mgKOH/g、产品名:G-1000、第一工业制药株式会社制
[萜烯树脂(B)]
·萜烯树脂1:柠檬烯-苯乙烯共聚物,有效成分50质量%,产品名:YS resin LP,Yasuhara Chemical株式会社制
·萜烯树脂2:蒎烯-二戊烯共聚物,有效成分80质量%,产品名:ダイマロン,Yasuhara Chemical株式会社制
·萜烯树脂3:苯酚-α-蒎烯共聚物,有效成分100质量%,产品名:YS POLYSTERT80,Yasuhara Chemical株式会社制
[比较用树脂]
·石油树脂:东曹株式会社制、产品名:Petrotack
[催化剂]
·锡系催化剂:产品名:Neostan U-810、日东化成株式会社制
[多异氰酸酯(C)]
·多异氰酸酯1:聚合MDI、产品名:Millionate MR-200、东曹株式会社制
·多异氰酸酯2:碳二亚胺改性MDI、产品名:Lupranate MM103、BASF INOACPolyurethan株式会社制
·多异氰酸酯3:异氰脲酸酯改性MDI、产品名:Duranate TPA-100、旭化成株式会社制
[实施例1~14及比较例1~4]
按照下述表1和表2所示的配合(质量份),制备了各实施例和各比较例的双组分固化型聚氨酯树脂组合物。制备时,称量规定量的表1和表2所示的第一成分,一边适当加热溶解一边搅拌混合,混合后,调整为25℃。接着,向该混合物中如表1和表2记载的那样地添加调整至25℃的第二成分(多异氰酸酯(C))并搅拌混合,脱泡。
对于各双组分固化型聚氨酯树脂组合物,测定及评价了相容性、密合性和介电常数。测定及评价方法如下所述。
[相容性]
确认了混合第一成分后的液体的状况,根据下述基准,评价了萜烯树脂或比较用树脂与多元醇(A)的相容性。
A:透明
B:有一些浑浊
C:有浑浊
D:经过30分钟及以后产生分离
E:小于30分钟时发生分离
[密合性]
在市售的FR-4环氧基板上,滴下直径1cm左右的上述脱泡后的双组分固化型聚氨酯树脂组合物,并在80℃下养护16小时(一晚),使其固化。瞄准固化后的聚氨酯树脂与环氧基板上的边界,用切割刀切削树脂,通过目视对残留在基板上的聚氨酯树脂进行了确认。评价时,将内聚破坏设定为聚氨酯树脂部分残留在基板上的状态、将界面剥离设定为聚氨酯树脂从基板上剥离的状态,并且在两种状态混合存在时,根据其面积比例,通过下述基准进行评价。
A:内聚破坏100%
B:内聚破坏为75%以上且小于100%,界面剥离大于0%且为25%以下
C:内聚破坏为50%以上且小于75%,界面剥离大于25%且为50%以下
D:内聚破坏为25%以上且小于50%,界面剥离大于50%且为75%以下
E:内聚破坏小于25%,界面剥离为75%以上
[介电常数]
使上述脱泡后的双组分固化型聚氨酯树脂组合物流入厚度3mm的模具中,在80℃下养护16小时(一晚),制作3mm厚的树脂片。将该树脂片切成50mm×50mm×3mm的片,作为测定用样品。测定使用Agilent Technologies株式会社制的装置(主体的型号:E4980A、名称:Precision LCR Meter。电极部分的型号:16451B、名称:DIELECTRIC TEST FIXTURE)来实施,测定了频率1MHz时的介电常数(相对介电常数)的值。
[表1]
[表2]
结果如表1和表2所示。在使用石油树脂而非萜烯树脂的比较例1中,与聚丁二烯多元醇的相容性差,第一成分分离,因此未实施密合性及介电常数的评价。在未配合树脂的比较例2中,相对于基板的密合性差。在使用蓖麻油系多元醇来代替聚丁二烯多元醇的比较例3中,蓖麻油系多元醇与萜烯树脂的相容性差,第一成分分离,因此未实施密合性及介电常数的评价。另一方面,比较例4中,虽然并用了聚丁二烯多元醇和萜烯树脂,但多元醇中的聚丁二烯多元醇的比例少,密合性差,另外介电常数比比较例2更高。与此相对,若为实施例1~实施例14,则多元醇与萜烯树脂的相容性良好,另外相对于比较例2,在维持低介电特性的同时与基板的密合性优异。
以上,说明了本发明的若干实施方式,但这些实施方式仅作为示例而给出,并非意图限定发明的范围。这些实施方式能够以其他各种方式实施,在不脱离发明的主旨的范围内,能够进行各种省略、替换、变更。这些实施方式及其省略、置换、变更等包含在发明的范围、主旨中,同样也包含在权利要求书所记载的发明及其等同的范围内。
Claims (6)
1.一种双组分固化型聚氨酯树脂组合物,其中,
所述双组分固化型聚氨酯树脂组合物具有:第一成分,所述第一成分包含多元醇和萜烯树脂;和第二成分,所述第二成分包含多异氰酸酯,
所述多元醇含有30质量%以上的聚丁二烯多元醇和/或氢化聚丁二烯多元醇,
相对于100质量份所述多元醇,所述萜烯树脂的含量为1质量份~60质量份。
2.根据权利要求1所述的双组分固化型聚氨酯树脂组合物,其中,
所述萜烯树脂为从由聚萜烯树脂、芳香族改性萜烯树脂和萜烯酚树脂组成的组中选出的至少一种。
3.根据权利要求1或2所述的双组分固化型聚氨酯树脂组合物,其中,
所述多元醇还包含蓖麻油系多元醇。
4.根据权利要求1至3中任一项所述的双组分固化型聚氨酯树脂组合物,其中,
所述双组分固化型聚氨酯树脂组合物用于密封电气电子部件。
5.一种电气电子部件,其中,
使用权利要求1至4中任一项所述的双组分固化型聚氨酯树脂组合物进行树脂密封。
6.一种多元醇组合物,其中,
所述多元醇组合物被用作双组分固化型聚氨酯树脂组合物中的多元醇成分,
所述多元醇组合物包含多元醇和萜烯树脂,
所述多元醇含有30质量%以上的聚丁二烯多元醇和/或氢化聚丁二烯多元醇,
相对于100质量份所述多元醇,所述萜烯树脂的含量为1质量份~60质量份。
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US20240052088A1 (en) | 2024-02-15 |
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