JP4879616B2 - Curing catalyst for curable silicone resin and curable silicone resin composition - Google Patents
Curing catalyst for curable silicone resin and curable silicone resin composition Download PDFInfo
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- JP4879616B2 JP4879616B2 JP2006068551A JP2006068551A JP4879616B2 JP 4879616 B2 JP4879616 B2 JP 4879616B2 JP 2006068551 A JP2006068551 A JP 2006068551A JP 2006068551 A JP2006068551 A JP 2006068551A JP 4879616 B2 JP4879616 B2 JP 4879616B2
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- 229920002050 silicone resin Polymers 0.000 title claims description 90
- 239000003054 catalyst Substances 0.000 title claims description 71
- 239000011342 resin composition Substances 0.000 title claims description 25
- -1 nitrogen-containing compound Chemical class 0.000 claims description 58
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910015900 BF3 Inorganic materials 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 30
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical group C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- FZBFHIZXBALZCU-UHFFFAOYSA-N 1-(2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-10-yl)propan-2-ol Chemical compound CC(O)CC1CCCCN2CCCN=C12 FZBFHIZXBALZCU-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 0 *C(CC1C2=NCCCN2CCCC1)O* Chemical compound *C(CC1C2=NCCCN2CCCC1)O* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- AOBOMOUUYYHMOX-UHFFFAOYSA-N diethylboron Chemical compound CC[B]CC AOBOMOUUYYHMOX-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Description
本発明は、硬化性シリコーン系樹脂の硬化触媒に関し、特に湿気硬化型の硬化性シリコーン系樹脂を速く硬化させ、なおかつ、触媒のブリードアウトを抑えた硬化触媒に関するものである。また、この硬化触媒と硬化性シリコーン系樹脂とを含有する硬化性シリコーン系樹脂組成物に関し、特に、この硬化触媒と、湿気硬化型の硬化性シリコーン系樹脂とを含有する湿気硬化性シリコーン系樹脂組成物に関するものである。 The present invention relates to a curing catalyst for a curable silicone resin, and more particularly to a curing catalyst that cures a moisture-curable curable silicone resin quickly and suppresses bleed out of the catalyst. The present invention also relates to a curable silicone resin composition containing this curing catalyst and a curable silicone resin, and in particular, a moisture curable silicone resin containing this curing catalyst and a moisture curable silicone resin. It relates to a composition.
従来、分子内に加水分解性珪素基を有する湿気硬化型の硬化性シリコーン系樹脂の硬化触媒として、ジブチル錫ジラウレート、ジブチル錫ジアセテート、ジオクチル錫ジラウレート等の有機錫化合物が使用されている。この有機錫化合物は、硬化性シリコーン系樹脂を速やかに硬化させるため、重宝されている。しかしながら、有機錫化合物は重金属である錫を含有しているため、近年、人体に対する危険性・有害性が指摘されている。 Conventionally, organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and dioctyltin dilaurate have been used as curing catalysts for moisture-curable curable silicone resins having hydrolyzable silicon groups in the molecule. This organotin compound is useful because it quickly cures the curable silicone resin. However, since organic tin compounds contain tin, which is a heavy metal, in recent years, danger and harm to human bodies have been pointed out.
また、そのような重金属以外の硬化触媒として、アミン化合物等の塩基化合物が使用されることがある。しかしながら、そのような塩基化合物は一般的に触媒活性が低く、助触媒程度の役割しかなかった。そこで本発明者等は、鋭意研究の結果、際だった触媒活性を有するアミン化合物を見出した（特許文献１及び特許文献２）。 In addition, a base compound such as an amine compound may be used as a curing catalyst other than such heavy metals. However, such a basic compound generally has a low catalytic activity and only plays a role of a promoter. Accordingly, the present inventors have found an amine compound having outstanding catalytic activity as a result of intensive studies (Patent Document 1 and Patent Document 2).
しかしながら、特許文献１及び特許文献２で記載されている含窒素化合物を用いた場合、硬化後に含窒素化合物がブリードアウト（硬化物中に分散していた添加剤等が硬化物表面に浮き出てきてくる現象）してくることがあった。接着剤等の硬化物表面が露出しない用途では問題はないものの、シーリング材や塗料等の硬化物表面が露出する用途においては、含窒素化合物がブリードアウトすると、場合によっては黄変あるいは着塵等により意匠性が低下することがあり、問題となっていた。 However, when the nitrogen-containing compound described in Patent Document 1 and Patent Document 2 is used, the nitrogen-containing compound bleeds out after curing (additives and the like dispersed in the cured product are raised on the surface of the cured product). (Phenomenon to come)). In applications where the surface of the cured product such as adhesive is not exposed, there is no problem, but in applications where the surface of the cured product such as a sealant or paint is exposed, yellowing or dusting may occur if the nitrogen-containing compound bleeds out. As a result, the designability may deteriorate, which is a problem.
本発明者等は、鋭意研究の結果、特定の構造を持つ含窒素化合物が、硬化性シリコーン系樹脂の硬化触媒として有効で、なおかつ、ブリードアウトが低減されることを見出し、本発明を完成させるに至った。
すなわち、第一の発明は、分子内に下記一般式（１）で表される加水分解性珪素基を含有する硬化性シリコーン系樹脂を硬化させるための硬化触媒であって、下記一般式（２）及び／又は一般式（４）で表される含窒素化合物であることを特徴とする硬化性シリコーン系樹脂の硬化触媒に関するものである。また、当該硬化性シリコーン系樹脂とこの当該含窒素化合物とを含有する硬化性シリコーン系樹脂組成物に関するものである。
一般式（１）：
一般式（２）：
一般式（４）：
As a result of intensive studies, the present inventors have found that a nitrogen-containing compound having a specific structure is effective as a curing catalyst for a curable silicone resin and further reduces bleed-out, thereby completing the present invention. It came to.
That is, the first invention is a curing catalyst for curing a curable silicone-based resin containing a hydrolyzable silicon group represented by the following general formula (1) in the molecule. And / or a nitrogen-containing compound represented by the general formula (4) . The present invention also relates to a curable silicone resin composition containing the said curable silicone resin and the said nitrogen-containing compound.
General formula (1):
General formula (2):
General formula (4):
また、第二の発明は、分子内に下記一般式（１）で表される加水分解性珪素基を含有する硬化性シリコーン系樹脂を硬化させるための硬化触媒であって、三フッ化ホウ素と下記一般式（２）、一般式（３）及び／又は一般式（４）で表される含窒素化合物との錯体よりなることを特徴とする硬化性シリコーン系樹脂の硬化触媒に関するものである。また、当該硬化性シリコーン系樹脂とこの当該錯体とを含有する硬化性シリコーン系樹脂組成物に関するものである。
一般式（１）：
一般式（２）：
一般式（３）：
一般式（４）：
The second invention is a curing catalyst for curing a curable silicone resin containing a hydrolyzable silicon group represented by the following general formula (1) in the molecule, and boron trifluoride and The present invention relates to a curing catalyst for a curable silicone resin, characterized by comprising a complex with a nitrogen-containing compound represented by the following general formula (2) , general formula (3) and / or general formula (4) . The present invention also relates to a curable silicone resin composition containing the curable silicone resin and the complex.
General formula (1):
General formula (2):
General formula (3):
General formula (4):
本発明に係る硬化触媒は、分子内に上記一般式（１）で表される加水分解性珪素基を含有する硬化性シリコーン系樹脂の硬化速度を速めるという効果を奏する。また、本発明に係る硬化触媒は、硬化後にもブリードアウトが起こりにくく、意匠性が求められる用途に好適である。 The curing catalyst according to the present invention has an effect of increasing the curing rate of the curable silicone resin containing a hydrolyzable silicon group represented by the general formula (1) in the molecule. In addition, the curing catalyst according to the present invention is suitable for applications in which bleed-out hardly occurs even after curing and design properties are required.
（硬化性シリコーン系樹脂について）
本発明でいう硬化性シリコーン系樹脂は、分子内に一般式（１）で表される加水分解性珪素基を持つものである。加水分解性珪素基は、珪素原子に加水分解性基が１〜３個結合すると共に、炭化水素基が２〜０個結合しているものである。そして、この珪素原子には、主鎖が結合している。ここで、加水分解性基としては、ヒドロキシル基や、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等のアルコキシル基が、一般的に用いられる。その他、ハロゲン基やメルカプト基等の従来公知の加水分解性基も用いることができる。炭化水素基としては、メチル基やエチル基等のアルキル基が一般的に用いられる。また、アルキル基等の炭化水素基には、ヒドロキシアルキル基等の置換基を有していてもよい。主鎖としては、ポリオキシアルキレンやビニル重合体等の硬化性シリコーン系樹脂に一般的に用いられているものが採用される。さらに、シロキサン結合（Ｓｉ−Ｏ−Ｓｉ）よりなる重合体等のシリコーン樹脂に一般に用いられているものも採用される。
(About curable silicone resin)
The curable silicone resin referred to in the present invention has a hydrolyzable silicon group represented by the general formula (1) in the molecule. The hydrolyzable silicon group has 1 to 3 hydrolyzable groups bonded to silicon atoms and 2 to 0 hydrocarbon groups bonded thereto. The main chain is bonded to the silicon atom. Here, as the hydrolyzable group, an alkoxyl group such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group is generally used. In addition, conventionally known hydrolyzable groups such as halogen groups and mercapto groups can also be used. As the hydrocarbon group, an alkyl group such as a methyl group or an ethyl group is generally used. The hydrocarbon group such as an alkyl group may have a substituent such as a hydroxyalkyl group. As the main chain, those generally used for curable silicone resins such as polyoxyalkylene and vinyl polymers are employed. Furthermore, what is generally used for silicone resins, such as a polymer which consists of a siloxane bond (Si-O-Si), is also employ | adopted.
硬化性シリコーン系樹脂は、シリコーン樹脂又は硬化性シリコーン系樹脂として多数販売されている。たとえば、株式会社カネカ製のサイリルシリーズ、カネカＭＳポリマーシリーズ、ＭＡシリーズ、ＳＡシリーズ、ＯＲシリーズ；旭硝子株式会社製のＥＳシリーズ、ＥＳＧＸシリーズ；デグサジャパン株式会社製のベストプラスト２０６；信越化学工業株式会社製のＫＣシリーズ、ＫＲシリーズ、Ｘ−４０シリーズ；東亜合成株式会社製のＸＰＲシリーズ；綜研化学株式会社製のアクトフローシリーズ等が挙げられる。なお、加水分解性基の数が３個の硬化性シリコーン系樹脂は、あまり市販されていないけれども、後述の実施例記載の方法又は公知の特許文献（たとえば、特開２００５−０５４１７４等）に記載の方法で適宜調製することができる。 Many curable silicone resins are sold as silicone resins or curable silicone resins. For example, Kaneka Co., Ltd. Silyl Series, Kaneka MS Polymer Series, MA Series, SA Series, OR Series; Asahi Glass Co., Ltd. ES Series, ESGX Series; Degussa Japan Co., Ltd. Best Plast 206; Shin-Etsu Chemical Co., Ltd. KC series, KR series, X-40 series manufactured by company; XPR series manufactured by Toa Gosei Co., Ltd .; Actflow series manufactured by Soken Chemical Co., Ltd., and the like. In addition, although the curable silicone resin having 3 hydrolyzable groups is not commercially available, it is described in the methods described in Examples below or in known patent documents (for example, JP-A-2005-054174). It can prepare suitably by the method of this.
また、本発明では、分子内に極性基を含有する硬化性シリコーン系樹脂を好適に用いることができる。ここで、極性基とは、ウレタン結合基、チオウレタン結合基、尿素結合基、チオ尿素結合基、置換尿素結合基、置換チオ尿素結合基、アミド結合基、スルフィド結合基、ヒドロキシル基、第一級アミノ基、第二級アミノ基及び第三級アミノ基等の酸素原子、窒素原子、硫黄原子を含有する結合基又は官能基等を指す。このような極性基が硬化性シリコーン系樹脂中に存在すると、硬化触媒のブリードアウトがより低減され、好ましい。また、このような極性基を加水分解性珪素基の近傍に導入すると、硬化性シリコーン系樹脂の硬化がさらに促進され、好ましい。 In the present invention, a curable silicone resin containing a polar group in the molecule can be preferably used. Here, the polar group means a urethane bond group, a thiourethane bond group, a urea bond group, a thiourea bond group, a substituted urea bond group, a substituted thiourea bond group, an amide bond group, a sulfide bond group, a hydroxyl group, a first group A linking group or functional group containing an oxygen atom, a nitrogen atom, or a sulfur atom, such as a secondary amino group, secondary amino group, and tertiary amino group. When such a polar group is present in the curable silicone resin, the bleedout of the curing catalyst is further reduced, which is preferable. Moreover, it is preferable to introduce such a polar group in the vicinity of the hydrolyzable silicon group because the curing of the curable silicone resin is further promoted.
特に、これらの極性基の中では、ウレタン結合基、チオウレタン結合基、尿素結合基、チオ尿素結合基、置換尿素結合基、置換チオ尿素結合基、アミド結合基、第一級アミノ基、第二級アミノ基及び第三級アミノ基等の含窒素極性基を有するものが、ブリードアウトが抑制するかつ硬化をさらに促進せしめるため好ましく、とりわけウレタン結合基（−ＮＨＣＯＯ−）、（置換）尿素結合基（−ＮＨＣＯＮＨ−）は、ブリードアウトを大きく抑制するかつ硬化を顕著に促進せしめるものであり最も好ましい。
ブリードアウトが低減される理由としては、硬化性シリコーン系樹脂中に存在する含窒素極性基と本発明における硬化触媒（すなわち、含窒素化合物あるいはその錯体）の極性基（例えば、水酸基、ウレタン結合基、尿素結合基など）との間に強い相互作用が発生し、硬化性シリコーン系樹脂組成物の硬化後もこれらの化合物が硬化物内部に十分保持され得るためであると考えられる。
また、含窒素極性基を有する硬化性シリコーン系樹脂組成物において顕著に硬化が促進する理由としては、硬化性シリコーン系樹脂の分子内に存在する含窒素極性基が、本発明に係る硬化触媒（すなわち、含窒素化合物あるいはその錯体）に対して、分子的相性の良いドメインとなるからであると考えられる。この結果、本発明に係る錯体が、硬化性シリコーン系樹脂の加水分解性珪素基の近傍に集まって相互作用しやすくなり、加水分解性基の脱離能がさらに高まって、加水分解性珪素基同士のカップリング反応がさらに促進されるためであると考えられるのである。
In particular, among these polar groups, urethane bond groups, thiourethane bond groups, urea bond groups, thiourea bond groups, substituted urea bond groups, substituted thiourea bond groups, amide bond groups, primary amino groups, primary amino groups, Those having a nitrogen-containing polar group such as a secondary amino group and a tertiary amino group are preferred in order to suppress bleed out and further accelerate curing, and in particular, urethane bond groups (—NHCOO—) and (substituted) urea bonds. The group (—NHCONH—) is most preferable because it greatly suppresses bleed-out and significantly accelerates curing.
The reason why the bleed-out is reduced is that the nitrogen-containing polar group present in the curable silicone resin and the polar group (for example, hydroxyl group, urethane bonding group) of the curing catalyst (that is, nitrogen-containing compound or complex thereof) in the present invention. This is considered to be because a strong interaction occurs between the compound and the urea bonding group, and these compounds can be sufficiently retained inside the cured product even after curing of the curable silicone resin composition.
Moreover, as a reason which hardening accelerates | stimulates notably in the curable silicone resin composition which has a nitrogen-containing polar group, the nitrogen-containing polar group which exists in the molecule | numerator of curable silicone resin is the curing catalyst ( That is, it is considered that this is a domain having good molecular compatibility with a nitrogen-containing compound or a complex thereof. As a result, the complex according to the present invention is likely to gather in the vicinity of the hydrolyzable silicon group of the curable silicone-based resin and interact with each other, and the ability to remove the hydrolyzable group is further increased. This is probably because the coupling reaction between the two is further promoted.
分子内に極性基を含有する硬化性シリコーン系樹脂は、従来公知の方法で、主鎖に各極性基を導入すればよい。たとえば、ウレタン結合基は、後述の実施例記載の方法や公知の特許文献（たとえば、特許第３３１７７３５３号公報、特許第３０３００２０号公報、特開２００５−０５４１７４号公報等）に記載の方法により、容易に導入することができる。 The curable silicone resin containing a polar group in the molecule may be introduced by introducing each polar group into the main chain by a conventionally known method. For example, the urethane linking group can be easily formed by a method described in Examples below or a method described in known patent documents (for example, Japanese Patent No. 33177353, Japanese Patent No. 3030020, Japanese Patent Application Laid-Open No. 2005-054174, etc.). Can be introduced.
（硬化触媒である含窒素化合物あるいはその錯体について）
本発明に係る硬化触媒は、上記した硬化性シリコーン系樹脂を速やかに硬化させるものであり、上記一般式（２）、上記一般式（３）若しくは上記一般式（４）で表される含窒素化合物、又は三フッ化ホウ素とこれらの含窒素化合物との錯体である。（なお、以下では「本発明に係る含窒素化合物、又は三フッ化ホウ素とこれらの含窒素化合物との錯体」を総称して、単に「本発明に係る硬化触媒」と記載することがある。）該含窒素化合物は単独でも十分な触媒活性を有しているが、三フッ化ホウ素との錯体とするとなおいっそうの触媒活性が発揮される。一般的に、上記一般式（２）、上記一般式（３）又は上記一般式（４）で表される含窒素化合物は、酸化合物と錯体を形成する。そのような酸化合物としては、カルボン酸等のブレンステッド酸、ハロゲン化ホウ素等のルイス酸等が挙げられ、これらの錯体は硬化性シリコーン系樹脂の硬化触媒として機能する。なかでも、硬化性シリコーン系樹脂の硬化触媒として使用する場合は、触媒活性が高いことから三フッ化ホウ素、三塩化ホウ素、三臭化ホウ素等のハロゲン化ホウ素が適しており、さらには、原料の入手のしやすさから三フッ化ホウ素が最も適している。
(About nitrogen-containing compounds or their complexes as curing catalysts)
The curing catalyst according to the present invention rapidly cures the above-described curable silicone resin, and the nitrogen-containing compound represented by the above general formula (2), the above general formula (3), or the above general formula (4). It is a compound or a complex of boron trifluoride and these nitrogen-containing compounds. (Hereinafter, the “nitrogen-containing compound according to the present invention or a complex of boron trifluoride with these nitrogen-containing compounds” may be collectively referred to simply as “the curing catalyst according to the present invention”. The nitrogen-containing compound alone has sufficient catalytic activity, but when it is complexed with boron trifluoride, further catalytic activity is exhibited. Generally, the nitrogen-containing compound represented by the general formula (2), the general formula (3), or the general formula (4) forms a complex with an acid compound. Examples of such acid compounds include Bronsted acids such as carboxylic acids, Lewis acids such as boron halides, etc., and these complexes function as curing catalysts for curable silicone resins. Of these, boron halides such as boron trifluoride, boron trichloride, and boron tribromide are suitable for use as a curing catalyst for curable silicone resins because of their high catalytic activity. Boron trifluoride is most suitable because of its availability.
また、本発明に係る硬化触媒は、上記一般式（３）で表されるように、分子内にウレタン結合基を有しているものが好ましい。ウレタン結合基を含有していることにより、硬化性シリコーン系樹脂中のシリル基あるいは極性基と強く相互作用し、その結果、ブリードアウトがいっそう抑制されるためである。また、本発明に係る硬化触媒は、上記一般式（４）で表されるように、分子内に加水分解性珪素基を含有しているものが好ましい。加水分解性珪素基を含有していることにより、硬化過程で硬化性シリコーン系樹脂と硬化触媒（すなわち、含窒素化合物あるいはその錯体）が結合し、その結果、硬化物構造中に化学的結合によりこれらの含窒素化合物あるいはその錯体が取り込まれ、ブリードアウトがよりいっそう抑制されるためである。 In addition, the curing catalyst according to the present invention preferably has a urethane bond group in the molecule as represented by the general formula (3). This is because by containing the urethane bond group, it strongly interacts with the silyl group or polar group in the curable silicone resin, and as a result, bleed out is further suppressed. The curing catalyst according to the present invention preferably contains a hydrolyzable silicon group in the molecule as represented by the general formula (4). By containing a hydrolyzable silicon group, a curable silicone resin and a curing catalyst (that is, a nitrogen-containing compound or a complex thereof) are bonded in the curing process, and as a result, a chemical bond is formed in the cured product structure. This is because these nitrogen-containing compounds or their complexes are incorporated, and the bleed-out is further suppressed.
本発明に係る硬化触媒としては、上記一般式（２）においてＲ２が水素原子である化合物（Ａ）が市販されている。
また、Ｒ２が有機基である化合物は、上記化合物（Ａ）が有する水酸基と、イソシアネート化合物若しくはイソチオシアネート化合物とを反応させることにより、又は、上記化合物（Ａ）が有する水酸基とエポキシ化合物若しくはエピスルフィド化合物とを反応させることにより、容易に合成することができる。これらの方法のうち、上記化合物（Ａ）が有する水酸基とイソシアネート化合物を反応させる方法により、上記一般式（３）で表される化合物を得ることができる。
さらに、Ｒ２に加水分解性珪素基を導入する方法としては、例えば、上記化合物（Ａ）が有する水酸基とイソシアネートシラン化合物若しくはイソチオシアネートシラン化合物とを反応させることにより、又は、上記化合物（Ａ）が有する水酸基とエポキシシラン化合物若しくはチイランシラン化合物とを反応させることにより、上記一般式（４）で表される化合物を容易に合成することができる。
As the curing catalyst according to the present invention, a compound (A) in which R 2 is a hydrogen atom in the general formula (2) is commercially available.
The compound in which R 2 is an organic group is obtained by reacting the hydroxyl group of the compound (A) with an isocyanate compound or an isothiocyanate compound, or the hydroxyl group of the compound (A) and an epoxy compound or episulfide. It can be easily synthesized by reacting with a compound. Among these methods, the compound represented by the general formula (3) can be obtained by a method in which the hydroxyl group of the compound (A) is reacted with an isocyanate compound.
Furthermore, as a method of introducing a hydrolyzable silicon group into R 2 , for example, by reacting a hydroxyl group of the compound (A) with an isocyanate silane compound or an isothiocyanate silane compound, or the compound (A) The compound represented by the general formula (4) can be easily synthesized by reacting the hydroxyl group possessed by the epoxy silane compound or thiirane silane compound.
また、三フッ化ホウ素と上記一般式（２）で表される含窒素化合物（一般式（３）又は（４）で表される化合物も含む）との錯体は、三フッ化ホウ素に上記一般式（２）で表される含窒素化合物を作用させることで、容易に錯体が形成され、得ることができる。また、三フッ化ホウ素ジエチルエーテル錯体等に、上記一般式（２）で表される含窒素化合物を作用させると、ジエチルエーテル等が脱離することで、容易に錯体が形成され、本発明に係る硬化触媒を得ることができる。三フッ化ホウ素等と特定の含窒素化合物との反応性が悪い場合や、より反応性を高めたい場合は、ヘキサン、トルエン、メチルシクロヘキサン等の反応溶媒中で反応させたり、又は加熱して反応させるのが好ましい。反応終了後においても、未反応物や脱離物（ジエチルエーテル等）が、硬化触媒中に残存していることがあるが、触媒能に悪影響を与えることが少ないので、いっこうに差し支えない。しかし、硬化触媒の純度を高めたいときは、減圧留去等の手段で、未反応物や脱離物を除去すればよい。なお、三フッ化ホウ素等と特定の含窒素化合物との仕込み比は任意であるが、一般的に、三フッ化ホウ素等：特定の含窒素化合物＝１０〜９０：９０〜１０（モル比）であり、３０〜７０：７０〜３０（モル比）が好ましく、特に５０：５０（モル比）が最も好ましい。 In addition, a complex of boron trifluoride and a nitrogen-containing compound represented by the above general formula (2) (including a compound represented by the general formula (3) or (4)) is boron trifluoride. By allowing the nitrogen-containing compound represented by the formula (2) to act, a complex can be easily formed and obtained. Further, when a nitrogen-containing compound represented by the above general formula (2) is allowed to act on boron trifluoride diethyl ether complex or the like, the complex is easily formed by the elimination of diethyl ether or the like. Such a curing catalyst can be obtained. If the reactivity between boron trifluoride or the like and a specific nitrogen-containing compound is poor, or if you want to increase the reactivity further, react in a reaction solvent such as hexane, toluene, or methylcyclohexane, or react by heating. It is preferable to do so. Even after the completion of the reaction, unreacted substances and desorbed substances (diethyl ether, etc.) may remain in the curing catalyst, but there is little adverse effect on the catalytic performance, so there is no problem. However, when it is desired to increase the purity of the curing catalyst, unreacted substances and desorbed substances may be removed by means such as distillation under reduced pressure. The charging ratio of boron trifluoride and the like to the specific nitrogen-containing compound is arbitrary, but generally boron trifluoride etc .: specific nitrogen-containing compound = 10 to 90:90 to 10 (molar ratio) 30 to 70:70 to 30 (molar ratio) is preferable, and 50:50 (molar ratio) is most preferable.
（硬化性シリコーン系樹脂組成物について）
本発明に係る硬化性シリコーン系樹脂組成物は、上記した硬化性シリコーン系樹脂と、上記した含窒素化合物（硬化触媒）とが配合されてなるものであり、含窒素化合物の配合量によって、その硬化速度を調整することができる。すなわち、含窒素化合物の配合量を多くすればするほど、硬化性シリコーン系樹脂の硬化速度を速めることができる。一般的に、硬化性シリコーン系樹脂１００質量部に対し、含窒素化合物の配合量は０．１〜１０質量部程度が好ましく、特に０．５〜５質量部程度が好ましい。また、硬化触媒が三フッ化ホウ素と含窒素化合物との錯体である場合、硬化性シリコーン系樹脂１００質量部に対し、含窒素化合物の配合量は０．００１〜１０質量部程度が好ましく、特に０．０１〜５質量部程度が好ましい。また、硬化性シリコーン系樹脂が３官能であるときは、本来的に硬化速度が速いので、含窒素化合物の量は少なくてもよい。１〜２官能であるときは、本来的に硬化速度が遅いので、含窒素化合物の量を多くするのが好ましい。
(About curable silicone resin composition)
The curable silicone resin composition according to the present invention is formed by blending the above curable silicone resin and the above nitrogen-containing compound (curing catalyst), and depending on the amount of the nitrogen-containing compound, The curing rate can be adjusted. That is, the curing rate of the curable silicone resin can be increased as the amount of the nitrogen-containing compound is increased. Generally, the blending amount of the nitrogen-containing compound is preferably about 0.1 to 10 parts by weight, particularly preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of the curable silicone resin. Further, when the curing catalyst is a complex of boron trifluoride and a nitrogen-containing compound, the amount of the nitrogen-containing compound is preferably about 0.001 to 10 parts by mass with respect to 100 parts by mass of the curable silicone resin. About 0.01-5 mass parts is preferable. In addition, when the curable silicone resin is trifunctional, the curing rate is inherently high, so the amount of the nitrogen-containing compound may be small. When it is 1-2 functional, the curing rate is inherently slow, so it is preferable to increase the amount of the nitrogen-containing compound.
本発明に係る硬化性シリコーン系樹脂組成物中には、硬化性シリコーン系樹脂と硬化触媒以外に、従来公知の任意の化合物乃至物質を配合することができる。たとえば、本発明で用いる硬化性シリコーン系樹脂以外の各種の樹脂、本発明に係る硬化触媒以外の錫系又はアミン系等の硬化触媒、γ−アミノプロピルトリメトキシシラン等のシランカップリング剤、親水性又は疎水性シリカ系粉体等の充填剤、フェノール樹脂等の粘着付与剤、無水シリカ等の揺変剤、酸化カルシウム等の脱水剤、希釈剤、可塑剤、難燃剤、オリゴマー、老化防止剤、紫外線吸収剤、顔料、チタネートカップリング剤、アルミニウムカップリング剤、乾性油等を配合することができる。 In the curable silicone resin composition according to the present invention, any conventionally known compound or substance can be blended in addition to the curable silicone resin and the curing catalyst. For example, various resins other than the curable silicone resin used in the present invention, a tin-based or amine-based curing catalyst other than the curing catalyst according to the present invention, a silane coupling agent such as γ-aminopropyltrimethoxysilane, hydrophilic Fillers such as hydrophilic or hydrophobic silica powders, tackifiers such as phenolic resins, thixotropic agents such as anhydrous silica, dehydrating agents such as calcium oxide, diluents, plasticizers, flame retardants, oligomers, anti-aging agents UV absorbers, pigments, titanate coupling agents, aluminum coupling agents, drying oils and the like can be blended.
本発明に係る硬化性シリコーン系樹脂組成物は、水分の存在下で、加水分解性基同士が縮重合することによって硬化するものである。したがって、１液型として使用される場合は、保管乃至搬送中は、空気（空気中の水分）と接触しないよう、気密に密封した状態で取り扱われる。そして、使用時には開封して任意の箇所に適用すれば、空気中の水分と接触して硬化性シリコーン系樹脂が硬化するのである。
あるいは、本発明に係る硬化性シリコーン系樹脂組成物は、２液型としても使用することができる。この場合には、本発明に係る硬化触媒は触媒活性が高いため、混合中に硬化しないような工夫が必要である。
The curable silicone resin composition according to the present invention is cured by condensation polymerization of hydrolyzable groups in the presence of moisture. Therefore, when used as a one-pack type, it is handled in an airtightly sealed state so as not to come into contact with air (water in the air) during storage or transportation. And if it opens and uses it in arbitrary places at the time of use, it will contact with the water | moisture content in air and a curable silicone resin will harden | cure.
Alternatively, the curable silicone resin composition according to the present invention can be used as a two-component type. In this case, since the curing catalyst according to the present invention has high catalytic activity, it is necessary to devise such that it does not cure during mixing.
本発明に係る硬化性シリコーン系樹脂組成物は、従来の硬化性シリコーン系樹脂が適用されていた全ての用途に用いることができる。たとえば、接着剤、シーラント、塗料、コーティング材、目止め材、注型材、被覆材等として用いることができる。 The curable silicone resin composition according to the present invention can be used for all applications to which a conventional curable silicone resin has been applied. For example, it can be used as an adhesive, sealant, paint, coating material, sealing material, casting material, coating material, and the like.
以下、本発明を実施例に基づいて詳細に説明するが、本発明は実施例に限定されるものではない。また、以下では「１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン構造」を「ＤＢＵ構造」と略記することがある。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example. Hereinafter, “1,8-diazabicyclo [5.4.0] undec-7-ene structure” may be abbreviated as “DBU structure”.
（硬化触媒の調製）
（１）硬化触媒Ｃ−１
市販の６−（２−ヒドロキシプロピル）−１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（サンアプロ株式会社製、分子内にＤＢＵ構造及び水酸基を有する化合物（一般式（２）において、Ｒ２が水素原子であり、Ｒ３がメチル基である化合物））を準備した。
(Preparation of curing catalyst)
(1) Curing catalyst C-1
Commercially available 6- (2-hydroxypropyl) -1,8-diazabicyclo [5.4.0] undec-7-ene (manufactured by San Apro Co., Ltd., a compound having a DBU structure and a hydroxyl group in the molecule (general formula (2) In the above, a compound in which R 2 is a hydrogen atom and R 3 is a methyl group)) was prepared.
（２）硬化触媒Ｃ−２
反応容器内で、６−（２−ヒドロキシプロピル）−１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（４．２ｇ、２０ｍｍｏｌ）をジエチルエーテル（１０ｍｌ）に溶解させ窒素雰囲気下で撹拌しながら、３−イソシアネートプロピルトリエトキシシラン（５．０ｇ、２０ｍｍｏｌ）を加え、室温で１時間反応させた。その後、ジエチルエーテルを減圧留去し、分子内にＤＢＵ構造、ウレタン結合基及びトリエトキシシリル基を有する硬化触媒Ｃ−２（黄色液体）を得た。
(2) Curing catalyst C-2
In a reaction vessel, 6- (2-hydroxypropyl) -1,8-diazabicyclo [5.4.0] undec-7-ene (4.2 g, 20 mmol) was dissolved in diethyl ether (10 ml) under a nitrogen atmosphere. 3-Isocyanatopropyltriethoxysilane (5.0 g, 20 mmol) was added with stirring at rt and allowed to react for 1 hour at room temperature. Then, diethyl ether was distilled off under reduced pressure to obtain a curing catalyst C-2 (yellow liquid) having a DBU structure, a urethane bond group and a triethoxysilyl group in the molecule.
（３）硬化触媒Ｃ−３
反応容器内で、６−（２−ヒドロキシプロピル）−１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（４．２ｇ、２０ｍｍｏｌ）をジエチルエーテル（２０ｍｌ）に溶解させ窒素雰囲気下で撹拌しながら、三フッ化ホウ素ジエチルエーテル錯体（２．８ｇ、２０ｍｍｏｌ）を加え、室温で１時間反応させた。その後、ジエチルエーテル及び未反応物を減圧留去し、分子内にＤＢＵ構造及び水酸基を有する含窒素化合物と三フッ化ホウ素との錯体である硬化触媒Ｃ−３（淡黄色固体）を得た。
(3) Curing catalyst C-3
In a reaction vessel, 6- (2-hydroxypropyl) -1,8-diazabicyclo [5.4.0] undec-7-ene (4.2 g, 20 mmol) was dissolved in diethyl ether (20 ml) under a nitrogen atmosphere. And stirring, boron trifluoride diethyl ether complex (2.8 g, 20 mmol) was added and allowed to react at room temperature for 1 hour. Thereafter, diethyl ether and unreacted substances were distilled off under reduced pressure to obtain a curing catalyst C-3 (light yellow solid) which is a complex of a nitrogen-containing compound having a DBU structure and a hydroxyl group in the molecule and boron trifluoride.
（４）硬化触媒Ｃ−４
反応容器内で、６−（２−ヒドロキシプロピル）−１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（４．２ｇ、２０ｍｍｏｌ）をジエチルエーテル（４０ｍｌ）に溶解させ窒素雰囲気下で撹拌しながら、オクタデシルイソシアネート（６．０ｇ、２０ｍｍｏｌ）を加え、室温で１時間反応させることで、分子内にＤＢＵ構造及びウレタン結合基を有する化合物ＰＣ−４を得た。
別の反応容器内で、化合物ＰＣ−４（２．５ｇ、５．０ｍｍｏｌ）をジエチルエーテル（１０ｍｌ）及びトルエン（１０ｍｌ）の混合溶媒に溶解させ窒素雰囲気下で撹拌しながら、三フッ化ホウ素ジエチルエーテル錯体（０．７ｇ、５．０ｍｍｏｌ）を加え、室温で１時間反応させた。その後、ジエチルエーテル、トルエン及び未反応物を減圧留去し、分子内にＤＢＵ構造及びウレタン結合基を有する含窒素化合物と三フッ化ホウ素との錯体である硬化触媒Ｃ−４（橙白色固体）を得た。
(4) Curing catalyst C-4
In a reaction vessel, 6- (2-hydroxypropyl) -1,8-diazabicyclo [5.4.0] undec-7-ene (4.2 g, 20 mmol) was dissolved in diethyl ether (40 ml) under a nitrogen atmosphere. While stirring at 0, octadecyl isocyanate (6.0 g, 20 mmol) was added and reacted at room temperature for 1 hour to obtain Compound PC-4 having a DBU structure and a urethane bond group in the molecule.
In a separate reaction vessel, compound PC-4 (2.5 g, 5.0 mmol) was dissolved in a mixed solvent of diethyl ether (10 ml) and toluene (10 ml) and stirred under a nitrogen atmosphere while diethyl boron trifluoride. Ether complex (0.7 g, 5.0 mmol) was added and reacted at room temperature for 1 hour. Thereafter, diethyl ether, toluene and unreacted substances are distilled off under reduced pressure, and a curing catalyst C-4 (orange white solid) which is a complex of a nitrogen-containing compound having a DBU structure and a urethane bonding group in the molecule and boron trifluoride. Got.
（５）硬化触媒Ｃ−５
反応容器内で、３−アミノプロピルトリメトキシシラン（１７９．３ｇ、１．０ｍｍｏｌ）を窒素雰囲気下で撹拌しながら、アクリル酸イソステアリル（新中村化学工業株式会社製、３２４．５ｇ、１．０ｍｍｏｌ）を１時間かけて滴下し、さらに５０℃で７日間反応させることで、分子内にトリメトキシシリル基及び第２級アミノ基を有する化合物ＳＣ−５を得た。
別の反応容器内で、６−（２−ヒドロキシプロピル）−１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（４．２ｇ、２０ｍｍｏｌ）をジエチルエーテル（４０ｍｌ）に溶解させ窒素雰囲気下で撹拌しながら、イソホロンジイソシアネート（４．５ｇ、２０ｍｍｏｌ）を加え、室温で１時間反応させることで、分子内にＤＢＵ構造、ウレタン結合基及びイソシアネート基を有する化合物を得た。さらに、化合物ＳＣ−５（５０３．８ｇ、１．０ｍｍｏｌ）を添加し、室温で１時間反応させた。その後、ジエチルエーテルを減圧留去し、分子内にＤＢＵ構造、ウレタン結合基、ウレア結合基及びトリメトキシシリル基を有する化合物ＰＣ−５（黄白色固体）を得た。
別の反応容器内で、化合物ＰＣ−５（４．７ｇ、５．０ｍｍｏｌ）をジエチルエーテル（１０ｍｌ）に溶解させ窒素雰囲気下で撹拌しながら、三フッ化ホウ素ジエチルエーテル錯体（０．７ｇ、５．０ｍｍｏｌ）を加え、室温で１時間反応させた。その後、ジエチルエーテル及び未反応物を減圧留去し、分子内にＤＢＵ構造、ウレタン結合基、ウレア結合基及びトリメトキシシリル基を有する含窒素化合物と三フッ化ホウ素との錯体である硬化触媒Ｃ−５（黄白色固体）を得た。
(5) Curing catalyst C-5
While stirring 3-aminopropyltrimethoxysilane (179.3 g, 1.0 mmol) in a nitrogen atmosphere in a reaction vessel, isostearyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., 324.5 g, 1.0 mmol) ) Was added dropwise over 1 hour and further reacted at 50 ° C. for 7 days to obtain Compound SC-5 having a trimethoxysilyl group and a secondary amino group in the molecule.
In a separate reaction vessel, 6- (2-hydroxypropyl) -1,8-diazabicyclo [5.4.0] undec-7-ene (4.2 g, 20 mmol) was dissolved in diethyl ether (40 ml) and nitrogen was added. While stirring under an atmosphere, isophorone diisocyanate (4.5 g, 20 mmol) was added and reacted at room temperature for 1 hour to obtain a compound having a DBU structure, a urethane bond group and an isocyanate group in the molecule. Further, Compound SC-5 (503.8 g, 1.0 mmol) was added and reacted at room temperature for 1 hour. Thereafter, diethyl ether was distilled off under reduced pressure to obtain a compound PC-5 (yellowish white solid) having a DBU structure, a urethane bond group, a urea bond group and a trimethoxysilyl group in the molecule.
In a separate reaction vessel, compound PC-5 (4.7 g, 5.0 mmol) was dissolved in diethyl ether (10 ml) and stirred in a nitrogen atmosphere while stirring with boron trifluoride diethyl ether complex (0.7 g, 5 mmol). 0.0 mmol) was added and allowed to react at room temperature for 1 hour. Thereafter, diethyl ether and unreacted substances are distilled off under reduced pressure, and a curing catalyst C which is a complex of boron trifluoride with a nitrogen-containing compound having a DBU structure, a urethane bond group, a urea bond group and a trimethoxysilyl group in the molecule. -5 (yellowish white solid) was obtained.
（４）硬化触媒Ｄ−１
市販のジオクチルスズジバーサテートを準備した。
(4) Curing catalyst D-1
A commercially available dioctyltin diversate was prepared.
（８）硬化触媒Ｄ−２
市販の１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（サンアプロ株式会社製）を準備した。
(8) Curing catalyst D-2
Commercially available 1,8-diazabicyclo [5.4.0] undec-7-ene (manufactured by San Apro Co., Ltd.) was prepared.
（９）硬化触媒Ｄ−３
反応容器内で、１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（３．０ｇ、２０ｍｍｏｌ）をジエチルエーテル（１０ｍｌ）に溶解させ窒素雰囲気下で撹拌しながら、三フッ化ホウ素ジエチルエーテル錯体（２．８ｇ、２０ｍｍｏｌ）を加え、室温で１時間反応させた。その後、ジエチルエーテル及び未反応物を減圧留去し、橙色固体の硬化触媒Ｄ−２を得た。
(9) Curing catalyst D-3
In a reaction vessel, boron trifluoride was dissolved in 1,8-diazabicyclo [5.4.0] undec-7-ene (3.0 g, 20 mmol) in diethyl ether (10 ml) and stirred under a nitrogen atmosphere. Diethyl ether complex (2.8 g, 20 mmol) was added and reacted at room temperature for 1 hour. Thereafter, diethyl ether and unreacted substances were distilled off under reduced pressure to obtain an orange solid curing catalyst D-2.
なお、符合Ｃで示した硬化触媒は、本発明の例に係る硬化触媒であり、符合Ｄで示した硬化触媒は、本発明の例以外の硬化触媒である。 The curing catalyst indicated by reference numeral C is a curing catalyst according to an example of the present invention, and the curing catalyst indicated by reference numeral D is a curing catalyst other than the example of the present invention.
（硬化性シリコーン系樹脂の調製）
（１）硬化性シリコーン系樹脂Ｂ−１
反応容器内で、「ＰＭＬＳ４０１２」（旭硝子ウレタン株式会社製、ポリオキシプロピレンポリオール、数平均分子量１０，０００、１０００ｇ）、３−イソシアネートプロピルトリエトキシシラン（５１．９ｇ）及びジオクチルスズジバーサテート（５０ｍｇ）を仕込み、窒素雰囲気下にて撹拌混合しながら、８０℃で３時間反応させて、分子内にトリエトキシシリル基を有する硬化性ポリオキシアルキレン樹脂Ｂ−１を得た。２３℃における硬化性樹脂Ｂ−１の粘度は、１３，０００ｍＰａ・ｓ（ＢＨ型粘度計、Ｎｏ．７ローター、１０回転）であった。
(Preparation of curable silicone resin)
(1) Curable silicone resin B-1
In the reaction vessel, “PMLS4012” (manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000, 1000 g), 3-isocyanatopropyltriethoxysilane (51.9 g) and dioctyltin diversate (50 mg) The mixture was reacted at 80 ° C. for 3 hours with stirring and mixing under a nitrogen atmosphere to obtain a curable polyoxyalkylene resin B-1 having a triethoxysilyl group in the molecule. The viscosity of curable resin B-1 at 23 ° C. was 13,000 mPa · s (BH viscometer, No. 7 rotor, 10 revolutions).
（２）硬化性シリコーン系樹脂Ｂ−２
反応容器内で、３−アミノプロピルメチルジメトキシシラン（１６３．３ｇ、１．０ｍｍｏｌ）を窒素雰囲気下８０℃で撹拌しながら、アクリル酸ラウリル（２４０．４ｇ、１．０ｍｍｏｌ）を１時間かけて滴下し、さらに５０℃で７日間反応させることで、分子内にメチルジメトキシシリル基及び第２級アミノ基を有する反応物ＳＥ−１を得た。別の反応容器内で、「ＰＭＬＳ４０１２」（旭硝子ウレタン株式会社製、ポリオキシプロピレンポリオール、数平均分子量１０，０００、１０００ｇ）、イソホロンジイソシアネート（４７．５ｇ）及びジオクチルスズジバーサテート（５０ｍｇ）を仕込み、窒素雰囲気下にて撹拌混合しながら、８０℃で３時間反応させて、分子内にイソシアネート基を有するポリオキシアルキレン樹脂を得た。その後、反応物ＳＥ−１（９０．７ｇ）を添加し、窒素雰囲気下にて撹拌混合しながら、８０℃で１時間反応させることで、分子内にメチルジメトキシシリル基を有する硬化性ポリオキシアルキレン樹脂Ｂ−２を得た。２３℃における硬化性樹脂Ｂ−２の粘度は、６０，０００ｍＰａ・ｓ（ＢＨ型粘度計、Ｎｏ．７ローター、１０回転）であった。
(2) Curable silicone resin B-2
In a reaction vessel, lauryl acrylate (240.4 g, 1.0 mmol) was added dropwise over 1 hour while stirring 3-aminopropylmethyldimethoxysilane (163.3 g, 1.0 mmol) at 80 ° C. in a nitrogen atmosphere. The reaction product SE-1 having a methyldimethoxysilyl group and a secondary amino group in the molecule was obtained by further reacting at 50 ° C. for 7 days. In a separate reaction vessel, “PMLS4012” (manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000, 1000 g), isophorone diisocyanate (47.5 g) and dioctyltin diversate (50 mg) are charged. While stirring and mixing in a nitrogen atmosphere, the mixture was reacted at 80 ° C. for 3 hours to obtain a polyoxyalkylene resin having an isocyanate group in the molecule. Thereafter, the reaction product SE-1 (90.7 g) was added, and the mixture was allowed to react at 80 ° C. for 1 hour while stirring and mixing in a nitrogen atmosphere, thereby curable polyoxyalkylene having a methyldimethoxysilyl group in the molecule. Resin B-2 was obtained. The viscosity of curable resin B-2 at 23 ° C. was 60,000 mPa · s (BH viscometer, No. 7 rotor, 10 revolutions).
（３）硬化性シリコーン系樹脂Ｂ−３
市販の硬化性シリコーン系樹脂「ＥＳ−ＧＸ−３４４０ＳＴ」（旭硝子株式会社、主鎖がポリオキシアルキレンであり加水分解性珪素基がトリメトキシ型の硬化性シリコーン系樹脂）を準備した。
(3) Curable silicone resin B-3
A commercially available curable silicone resin “ES-GX-3440ST” (Asahi Glass Co., Ltd., main chain is polyoxyalkylene and hydrolyzable silicon group is trimethoxy type curable silicone resin) was prepared.
実施例１〜４、比較例１〜４
表１に示した硬化性シリコーン系樹脂と硬化触媒を、表１に示す配合割合（質量部）で手混ぜすることで、８種類の硬化性シリコーン系樹脂組成物を得た。
Examples 1-4, Comparative Examples 1-4
Eight types of curable silicone resin compositions were obtained by manually mixing the curable silicone resin and the curing catalyst shown in Table 1 at the blending ratio (parts by mass) shown in Table 1.
実施例５〜７、比較例５
表１に示した硬化性シリコーン系樹脂と硬化触媒を、表１に示す配合割合（質量部）で反応容器内に投入し、真空ポンプで反応容器内を減圧し、１００ｍｍＨｇまで減圧されたところで弁を閉じた。反応容器内を減圧した状態に保ったまま、１００℃まで昇温し、さらに１００℃で１時間撹拌した後、室温まで冷却し、密閉容器に充填して、４種類の硬化性シリコーン系樹脂組成物を得た。
Examples 5-7, Comparative Example 5
The curable silicone resin and the curing catalyst shown in Table 1 were put into the reaction vessel at the blending ratio (parts by mass) shown in Table 1, the inside of the reaction vessel was depressurized with a vacuum pump, and the valve was depressurized to 100 mmHg. Closed. While maintaining the reduced pressure inside the reaction vessel, the temperature was raised to 100 ° C., and further stirred at 100 ° C. for 1 hour, then cooled to room temperature, filled into a sealed vessel, and four kinds of curable silicone resin compositions I got a thing.
そして、実施例１〜７、比較例１〜５に係る硬化性シリコーン系樹脂組成物の皮張り時間及びブリードアウト現象の有無を、以下の方法で測定した。その結果を表１に示した。 And the presence or absence of the skinning time and bleed-out phenomenon of the curable silicone resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 were measured by the following methods. The results are shown in Table 1.
（皮張り時間）
実施例１〜７、比較例１〜５に係る硬化性シリコーン系樹脂組成物を、２３±２℃で相対湿度３０±５％の雰囲気下で開封して放置し、指触により、表面に張った硬化皮膜が指に転着しなくなるまでの時間を、皮張り時間として測定した。
(Skinning time)
The curable silicone resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 were opened and left in an atmosphere of a relative humidity of 30 ± 5% at 23 ± 2 ° C. and stretched on the surface by finger touch. The time until the cured film did not transfer to the finger was measured as the skinning time.
（ブリードアウト現象の有無）
実施例１〜７、比較例１〜５に係る硬化性シリコーン系樹脂組成物を、２３±２℃で相対湿度３０±５％の雰囲気下で開封して１週間放置した後、硬化物の表面の状態（ブリードアウト現象）を目視で評価した。
(Existence of bleed-out phenomenon)
The curable silicone resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 were opened in an atmosphere of 23 ± 2 ° C. and a relative humidity of 30 ± 5% and left for 1 week, and then the surface of the cured product The state (bleed out phenomenon) was evaluated visually.
「なし」・・・硬化物表面に特に変化は認められなかった。
「あり」・・・硬化後にオイル状の成分で硬化物表面が覆われる、場合によってはさらに表面に白色固体が形成された。
“None”: No change was observed on the surface of the cured product.
“Yes”: The surface of the cured product was covered with an oily component after curing. In some cases, a white solid was further formed on the surface.
表１の結果から明らかなように、本発明の例に係る硬化触媒を用いた場合には、比較的安全なオクチル錫系触媒であるジオクチルスズジバーサテートと比較して、硬化性シリコーン系樹脂を速やかに硬化させることが分かる。
また、官能基がないＤＢＵを使用した場合は、硬化後１〜３日の間にオイル状の成分で表面が覆われ、さらに２〜３日の間に表面が白色固形化した（比較例２〜５）。これは、硬化後に配合したＤＢＵの一部がブリードアウトした後、空気中の二酸化炭素と反応して炭酸塩化したものと推定される。このようなブリードアウト現象は、硬化性シリコーン系樹脂組成物を接着剤、シーリング材、塗料として用いた場合に、その意匠性を損ねるあるいは密着性を低下させるおそれがあるため好まれない現象である。一方、本発明に係る硬化触媒を使用した場合はそのような現象が見られなかった（実施例１〜７）。
以上のことから、本発明に係る硬化触媒は、硬化性シリコーン系樹脂を速やかに硬化させ、なおかつ、ブリードアウトが非常に少ないことが分かる。
As is apparent from the results of Table 1, when the curing catalyst according to the example of the present invention is used, a curable silicone resin is used as compared with dioctyltin diversate, which is a relatively safe octyltin catalyst. It turns out that is hardened rapidly.
Moreover, when DBU without a functional group was used, the surface was covered with an oily component within 1 to 3 days after curing, and the surface was solidified to white during 2 to 3 days (Comparative Example 2). ~ 5). This is presumed that a part of DBU blended after curing bleeds out, and then reacts with carbon dioxide in the air to be carbonated. Such a bleed-out phenomenon is an unfavorable phenomenon when the curable silicone resin composition is used as an adhesive, a sealing material, or a paint because it may impair the design or reduce the adhesion. . On the other hand, when the curing catalyst according to the present invention was used, such a phenomenon was not observed (Examples 1 to 7).
From the above, it can be seen that the curing catalyst according to the present invention quickly cures the curable silicone resin and has very little bleed out.
実施例８
硬化性シリコーン系樹脂Ｂ−１（５００質量部）及びＮＳ４００（日東粉化工業（株）製、重質炭酸カルシウム、２５０質量部）を反応容器内に投入し、真空ポンプで反応容器内を減圧しながら１００℃で１時間撹拌した後、室温まで冷却した。その後、γ−アミノプロピルトリメトキシシラン（２５質量部）及び６−（２−ヒドロキシプロピル）−１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（１．０質量部）を加えた。真空ポンプで反応容器内を減圧し、反応容器内を減圧した状態に保ったまま１０分間撹拌した後、密閉容器に充填して硬化性シリコーン系樹脂組成物を得た。そして、表３に示す木板（厚さ５ｍｍ、幅２５ｍｍ、長さ１００ｍｍ）、ＳＵＳ板（厚さ１．６ｍｍ、幅２５ｍｍ、長さ１００ｍｍ）、ＡＢＳ板（厚さ３ｍｍ、幅２５ｍｍ、長さ１００ｍｍ）を用いて接着強さを測定した。接着強さは、得られた硬化性シリコーン系樹脂組成物（０．１ｇ）を１２．５ｍｍ×２５ｍｍの面積に均一に塗布し、１２．５ｍｍ×２５ｍｍの面積で各被着材同士をはり合わせた。各はり合わせ試験体を２３±２℃相対湿度３０±５％で７日間養生して、引張りせん断接着強さ（Ｎ／ｍｍ２）をＪＩＳ Ｋ ６８５０に準じて測定した。それらの結果を表３に示した。
Example 8
Curable silicone resin B-1 (500 parts by mass) and NS400 (manufactured by Nitto Flour Chemical Co., Ltd., heavy calcium carbonate, 250 parts by mass) are charged into the reaction vessel, and the inside of the reaction vessel is decompressed with a vacuum pump. While stirring at 100 ° C. for 1 hour, the mixture was cooled to room temperature. Thereafter, γ-aminopropyltrimethoxysilane (25 parts by mass) and 6- (2-hydroxypropyl) -1,8-diazabicyclo [5.4.0] undec-7-ene (1.0 parts by mass) were added. It was. The inside of the reaction vessel was depressurized with a vacuum pump, stirred for 10 minutes while keeping the inside of the reaction vessel depressurized, and then filled into a sealed vessel to obtain a curable silicone resin composition. And the wooden board (thickness 5 mm, width 25 mm, length 100 mm) shown in Table 3, SUS board (thickness 1.6 mm, width 25 mm, length 100 mm), ABS board (thickness 3 mm, width 25 mm, length 100 mm) ) Was used to measure the bond strength. The adhesive strength was obtained by uniformly applying the obtained curable silicone resin composition (0.1 g) to an area of 12.5 mm × 25 mm, and bonding the adherends to each other with an area of 12.5 mm × 25 mm. It was. Each bonded specimen was cured for 7 days at 23 ± 2 ° C. and a relative humidity of 30 ± 5%, and the tensile shear bond strength (N / mm 2 ) was measured according to JIS K 6850. The results are shown in Table 3.
参考例１
６−（２−ヒドロキシプロピル）−１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エンをジオクチルスズジバーサテートに置き換えた以外は、実施例８と同様に硬化性シリコーン系樹脂組成物を調製し、引張せん断接着強さを測定した。それらの結果を表３に示した。
Reference example 1
Curable silicone-based resin composition as in Example 8, except that 6- (2-hydroxypropyl) -1,8-diazabicyclo [5.4.0] undec-7-ene was replaced with dioctyltin diversate. Articles were prepared and the tensile shear bond strength was measured. The results are shown in Table 3.
［表３］
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例８ 参考例１
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
木材／木材 １．４５ １．５６
木材／ＳＵＳ １．４６ １．５３
木材／ＡＢＳ １．３６ １．３９
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
[Table 3]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 8 Reference Example 1
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Wood / Wood 1.45 1.56
Wood / SUS 1.46 1.53
Wood / ABS 1.36 1.39
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
表３の結果から明らかなように、本発明の例に係る硬化性シリコーン系樹脂組成物は接着剤として使用する際には、十分な接着強さを発揮することが分かる。 As is apparent from the results in Table 3, it can be seen that the curable silicone resin composition according to the example of the present invention exhibits sufficient adhesive strength when used as an adhesive.
本発明に係る室温硬化性シリコーン系樹脂組成物は、従来の硬化性シリコーン系樹脂が適用されていた全ての用途に用いることができる。例えば、接着剤、シーラント、塗料、コーティング材、目止め材、注型材、被覆材等として用いることができる。
The room temperature curable silicone resin composition according to the present invention can be used for all applications to which conventional curable silicone resins have been applied. For example, it can be used as an adhesive, sealant, paint, coating material, sealing material, casting material, coating material, and the like.
Claims (7)
一般式（１）：
一般式（２）：
General formula (1):
General formula (2):
一般式（１）：
一般式（４）：
General formula (1):
General formula (4):
一般式（１）：
一般式（２）：
General formula (1):
General formula (2):
一般式（１）：
一般式（３）：
General formula (1):
General formula (3):
一般式（１）：
一般式（４）：
General formula (1):
General formula (4):
一般式（１）：
General formula (1):
一般式（１）：
100 parts by mass of a curable silicone resin containing a hydrolyzable silicon group represented by the following general formula (1) in the molecule, and a curing catalyst 0.001 according to any one of claims 3 to 5. A curable silicone resin composition containing 10 parts by mass.
General formula (1):
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