JPH10152561A - Production of polysiloxane, polysiloxane coating and inorganically insulated wire having the same coating - Google Patents
Production of polysiloxane, polysiloxane coating and inorganically insulated wire having the same coatingInfo
- Publication number
- JPH10152561A JPH10152561A JP8314654A JP31465496A JPH10152561A JP H10152561 A JPH10152561 A JP H10152561A JP 8314654 A JP8314654 A JP 8314654A JP 31465496 A JP31465496 A JP 31465496A JP H10152561 A JPH10152561 A JP H10152561A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- coating
- boron compound
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims description 28
- 238000000576 coating method Methods 0.000 title claims description 28
- -1 polysiloxane Polymers 0.000 title abstract description 9
- 229920001296 polysiloxane Polymers 0.000 title abstract description 5
- 238000004519 manufacturing process Methods 0.000 title description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 abstract description 25
- 229920000592 inorganic polymer Polymers 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 14
- 235000010338 boric acid Nutrition 0.000 description 14
- 229960002645 boric acid Drugs 0.000 description 14
- 230000001588 bifunctional effect Effects 0.000 description 13
- 239000004327 boric acid Substances 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 9
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004031 devitrification Methods 0.000 description 4
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- XCLIHDJZGPCUBT-UHFFFAOYSA-N dimethylsilanediol Chemical compound C[Si](C)(O)O XCLIHDJZGPCUBT-UHFFFAOYSA-N 0.000 description 1
- SLAYMDSSGGBWQB-UHFFFAOYSA-N diphenyl(dipropoxy)silane Chemical compound C=1C=CC=CC=1[Si](OCCC)(OCCC)C1=CC=CC=C1 SLAYMDSSGGBWQB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- MLSKXPOBNQFGHW-UHFFFAOYSA-N methoxy(dioxido)borane Chemical compound COB([O-])[O-] MLSKXPOBNQFGHW-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Insulated Conductors (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、ポリボロシロキサンの
製造方法に関し、より詳細には、高い可撓性を有し、比
較的低い温度での焼成により、べたつきを示さず、加熱
減量が少なく、高い耐熱性を有する無機ポリマーを形成
することができるポリボロシロキサンの製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyborosiloxane, and more particularly, to a method having a high flexibility and a non-sticky property by firing at a relatively low temperature. And a method for producing a polyborosiloxane capable of forming an inorganic polymer having high heat resistance.
【0002】[0002]
【従来の技術】ポリボロシロキサンはホウ素を介してシ
ロキサン結合が連結された構造を有するポリマーであ
る。ポリボロシロキサンは、焼成することにより耐熱性
に優れた無機ポリマーを形成できることが知られてお
り、耐熱性を要する電線の絶縁被膜等に使用されてい
る。2. Description of the Related Art Polyborosiloxane is a polymer having a structure in which siloxane bonds are linked via boron. It is known that polyborosiloxane can form an inorganic polymer having excellent heat resistance by firing, and is used for an insulating coating of an electric wire requiring heat resistance.
【0003】ポリボロシロキサンにおいては、ホウ素が
三配位構造をとり、ある程度の三次元網目構造が形成さ
れるため、加熱時のシロキサンの環化脱落が防がれ、二
官能アルコキシシランから形成されたポリシロキサン等
よりも高い耐熱性が得られる。また、シロキサン化合物
を、それと縮合するホウ素化合物自体を触媒として縮合
させることにより製造できるので、後に触媒を除去する
必要がなく、この点でも別途触媒を添加して縮合される
ポリシロキサン等よりも優れている。[0003] In polyborosiloxane, boron has a three-coordinate structure and a certain degree of three-dimensional network structure is formed. Therefore, cyclization of the siloxane during heating is prevented from falling off, and the boron is formed from a bifunctional alkoxysilane. Higher heat resistance than polysiloxane or the like. In addition, since the siloxane compound can be produced by condensing the boron compound itself that condenses with the catalyst as a catalyst, there is no need to remove the catalyst later. ing.
【0004】このようにポリボロシロキサンは種々の特
性において優れているので、特に高い耐熱性が要求され
る絶縁被膜として有用であることが期待されるが、さら
に取り扱いや製造上の利点を有していることが望まれ
る。例えば、形成される無機ポリマーの高い耐熱性に加
え、焼成前に十分な可撓性を有していれば被膜形成後取
り扱いやすく、また加工することも可能である。また、
形成される無機ポリマーの耐熱性等の観点から焼成時の
加熱減量が少ないことが好ましく、耐久性の観点から耐
湿性に優れていることが好ましい。さらには、低い温度
で焼成しても低分子量成分が残ることがなくべたつきの
ない無機絶縁被膜が得られれば、製造上有利である。Since polyborosiloxane is excellent in various properties as described above, it is expected to be particularly useful as an insulating coating requiring high heat resistance, but has further advantages in handling and manufacturing. Is desired. For example, in addition to the high heat resistance of the formed inorganic polymer, if it has sufficient flexibility before firing, it is easy to handle after forming the film and can be processed. Also,
From the viewpoint of the heat resistance and the like of the formed inorganic polymer, it is preferable that the heating loss during firing is small, and it is preferable that the inorganic polymer has excellent moisture resistance from the viewpoint of durability. Furthermore, if an inorganic insulating film having no low molecular weight components and no stickiness even when calcined at a low temperature is obtained, it is advantageous in production.
【0005】しかし、例えばポリジメチルボロシロキサ
ンは可撓性には優れるものの、200℃程度の低温での
焼成ではべたつきが残り、メチル基が300℃以下の温
度でも脱落するため、より高い耐熱性が要求される用途
には十分であるとはいえない。またホウ素の加水分解の
ため耐湿性にも劣る。さらにポリジフェニルボロシロキ
サンでは低温焼成におけるべたつき、耐熱性、耐湿性等
は改善されるが、可撓性が劣る。[0005] However, for example, polydimethylborosiloxane is excellent in flexibility, but remains sticky when calcined at a low temperature of about 200 ° C, and has a higher heat resistance because methyl groups are dropped off even at a temperature of 300 ° C or less. It is not enough for the required use. Further, it has poor moisture resistance due to hydrolysis of boron. Further, polydiphenylborosiloxane improves tackiness, heat resistance, moisture resistance, and the like at low temperature firing, but is inferior in flexibility.
【0006】また、ポリジフェニルボロシロキサンをシ
リコーンオイルを用いて縮合させることも知られている
が、このようにして得られる重合体では、耐熱性、耐湿
性、可撓性は改善されるが、低温での焼成ではシリコー
ンオイルが残存してべたつくので高温で焼成することが
必要である。It is also known that polydiphenylborosiloxane is condensed using silicone oil. The polymer obtained in this way has improved heat resistance, moisture resistance and flexibility. Since firing at a low temperature causes the silicone oil to remain and become sticky, firing at a high temperature is necessary.
【0007】さらに、三官能のシロキサン等のケイ素成
分を用い、三次元網目構造を形成することも知られてい
るが、三官能のケイ素成分だけでは可撓性が得られず、
また二官能のケイ素成分を併用しても、単純に二官能と
三官能のケイ素成分をホウ素化合物と一括して反応させ
るだけでは三官能性のケイ素成分の反応性が高いために
構造が不均一で部分的に可撓性が劣る等、十分な性質の
ものが得られなかった。Further, it is known that a three-dimensional network structure is formed by using a silicon component such as a trifunctional siloxane, but flexibility cannot be obtained by using only a trifunctional silicon component.
Even when a bifunctional silicon component is used in combination, simply reacting the bifunctional and trifunctional silicon components together with the boron compound at the same time results in a non-uniform structure due to the high reactivity of the trifunctional silicon component. In this case, a material having sufficient properties such as partially inferior flexibility could not be obtained.
【0008】[0008]
【発明が解決しようとする課題】そこで本発明は、高い
可撓性を有し、比較的低い温度での焼成でもべたつきを
示さず、加熱減量が少なく、高い耐熱性と耐湿性を有す
る無機ポリマーを形成することができるポリボロシロキ
サンの製造方法を提供することを目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention is directed to an inorganic polymer which has high flexibility, does not show stickiness even when fired at a relatively low temperature, has a small loss on heating, and has high heat resistance and moisture resistance. It is an object of the present invention to provide a method for producing a polyborosiloxane capable of forming a polyborosiloxane.
【0009】[0009]
【課題を解決するための手段】本発明者らの研究の結
果、二官能と三官能のケイ素化合物とホウ素化合物とを
使用してポリボロシロキサンを製造する場合、先ず、二
官能のケイ素化合物をホウ素化合物と反応させ、そして
得られた化合物をさらに三官能のケイ素化合物及びホウ
素化合物と反応させることにより、上記のような所望の
特性を満足するポリボロシロキサンが得られることを見
出した。As a result of the study of the present inventors, when producing a polyborosiloxane using a bifunctional and trifunctional silicon compound and a boron compound, first, the bifunctional silicon compound is It has been found that a polyborosiloxane satisfying the above-mentioned desired properties can be obtained by reacting with a boron compound and further reacting the obtained compound with a trifunctional silicon compound and a boron compound.
【0010】従って本発明は、下記式(a)Accordingly, the present invention provides the following formula (a)
【0011】[0011]
【化4】 (式中、Rはアルキル基、アルケニル基またはアリール
基を表し、Xはアルコキシ基、ヒドロキシル基またはハ
ロゲン原子を表す)の化合物をホウ素化合物と反応さ
せ、得られた生成物をさらに、下記式(b)Embedded image (Wherein R represents an alkyl group, an alkenyl group or an aryl group, and X represents an alkoxy group, a hydroxyl group or a halogen atom), and the resulting product is further reacted with a boron compound according to the following formula ( b)
【0012】[0012]
【化5】 (式中、R及びXは上記と同じ意味を表す)の化合物及
びホウ素化合物と反応させることを含む、ポリボロシロ
キサンの製造方法を提供するものである。Embedded image (Wherein, R and X have the same meanings as described above) and a boron compound.
【0013】上記本発明の方法の好ましい態様において
は、式(a) の化合物とホウ素化合物とが、下記式(c)In a preferred embodiment of the method of the present invention, the compound of the formula (a) and the boron compound are represented by the following formula (c)
【0014】[0014]
【化6】 (式中、Rは上記と同じ意味を表す)で表される単位が
平均で2〜10個含まれる縮合化合物に変換されるまで
式(a) の化合物とホウ素化合物との反応を行う。上記の
本発明の方法においては、液体状態の式(a) の化合物と
ホウ素化合物との反応物に液体状態の式(b) の化合物を
加えることが好ましい。Embedded image (Wherein R represents the same meaning as described above). The compound of the formula (a) is reacted with the boron compound until the unit is converted into a condensed compound containing 2 to 10 units on average. In the above method of the present invention, it is preferable to add the compound of the formula (b) in the liquid state to the reaction product of the compound of the formula (a) in the liquid state and the boron compound.
【0015】また本発明は、上記の方法により製造され
たポリボロシロキサンを含む塗料を塗布し焼成すること
により得られる塗膜、及びそのような塗膜を絶縁被覆と
して有する無機絶縁電線も提供する。The present invention also provides a coating film obtained by applying and baking a coating containing polyborosiloxane produced by the above method, and an inorganic insulated wire having such a coating film as an insulating coating. .
【0016】[0016]
【発明の実施の形態】以下、本発明につき詳述する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
【0017】本発明のポリボロシロキサンの製造方法に
使用される式(a) の化合物は、従来からポリシロキサ
ン、ポリボロシロキサン等の製造に用いられていたもの
と同様の二官能ケイ素化合物である。The compound of the formula (a) used in the method for producing a polyborosiloxane of the present invention is the same bifunctional silicon compound as that conventionally used for producing polysiloxane, polyborosiloxane and the like. .
【0018】式(a) 中のRは、アルキル基、アルケニル
基またはアリール基であり、好ましくは炭素数1〜1
0、より好ましくは炭素数1〜5、特に好ましくは炭素
数1〜3のアルキル基、好ましくは炭素数2〜10、よ
り好ましくは炭素数2〜5、特に好ましくは炭素数2〜
3のアルケニル基、または好ましくは炭素数6〜18、
より好ましくは炭素数6〜12のアリール基である。R
の好ましい例としては、限定するものではないが、メチ
ル基、エチル基、プロピル基、ブチル基、ビニル基、フ
ェニル基等が挙げられる。R in the formula (a) is an alkyl group, an alkenyl group or an aryl group, preferably having 1 to 1 carbon atoms.
0, more preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, particularly preferably 2 to 2 carbon atoms.
3 alkenyl groups, or preferably 6 to 18 carbon atoms,
More preferably, it is an aryl group having 6 to 12 carbon atoms. R
Preferred examples include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, a phenyl group and the like.
【0019】式(a) 中のXは官能基であり、アルコキシ
基、ヒドロキシル基、またはハロゲン原子である。Xと
して使用されるアルコキシ基は、好ましくは炭素数1〜
10、より好ましくは炭素数1〜4のアルコキシ基であ
り、後の反応時にアルコールとして除去できるメトキシ
基、エトキシ基、プロポキシ基、ブトキシ基等が好まし
い。ハロゲン原子は、フッ素原子、塩素原子、臭素原
子、ヨウ素原子から選択され、好ましくは塩素である。X in the formula (a) is a functional group, which is an alkoxy group, a hydroxyl group, or a halogen atom. The alkoxy group used as X preferably has 1 to 1 carbon atoms.
10, more preferably an alkoxy group having 1 to 4 carbon atoms, preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., which can be removed as an alcohol in a subsequent reaction. The halogen atom is selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and is preferably chlorine.
【0020】式(a) 中のR及びXはそれぞれ独立して上
記の基等を表し、式(a) の化合物においてR及びXはそ
れぞれにおいて互いに異なってもよく同一であってもよ
いが、式(a) の化合物は好ましくはそれぞれ同一のR並
びにXを有する。R and X in the formula (a) each independently represent the above-mentioned groups and the like. In the compound of the formula (a), R and X may be different from each other or the same, The compounds of formula (a) preferably each have the same R and X.
【0021】式(a) の化合物は、官能基のXを2個有す
る限り、数個、例えば2〜5個程度、ホウ素化合物と反
応させる前に縮合していても本発明の効果を得るのに差
し支えない。また式(a) の化合物は1種でまたは2種以
上組み合わせて使用することができる。As long as the compound of the formula (a) has two functional groups X, even if it is condensed before reacting with several, for example, about 2 to 5 boron compounds, the effects of the present invention can be obtained. No problem. The compounds of the formula (a) can be used alone or in combination of two or more.
【0022】式(a) の化合物の好ましい例としては、例
えば、ジメチルジヒドロキシシラン、ジフェニルジヒド
ロキシシラン、ジメチルジエトキシシラン、ジメチルジ
メトキシシラン、ジメチルジプロポキシシラン、ジフェ
ニルジメトキシシラン、ジフェニルジメトキシシラン、
ジフェニルジプロポキシシラン、及びこれらの脱水縮合
物等が挙げられる。Preferred examples of the compound of the formula (a) include, for example, dimethyldihydroxysilane, diphenyldihydroxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethyldipropoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane,
Examples include diphenyldipropoxysilane and dehydration condensates thereof.
【0023】本発明のポリボロシロキサンの製造方法に
使用される式(b) の化合物は、公知の三官能ケイ素化合
物である。The compound of the formula (b) used in the method for producing a polyborosiloxane of the present invention is a known trifunctional silicon compound.
【0024】式(b) 中のR及びXは式(a) におけるもの
と同じ意味を有し、Xはそれぞれ独立して上記の基等を
表し、式(b) の化合物においてXは互いに異なってもよ
く同一であってもよいが、式(b) の化合物は好ましくは
同一のXを有する。In the formula (b), R and X have the same meanings as in the formula (a), X each independently represents the above-mentioned groups and the like, and X in the compound of the formula (b) is different from each other. Or the same, but the compounds of formula (b) preferably have the same X.
【0025】また式(b) の化合物も、ホウ素化合物と反
応させる前に数個、例えば2〜5個程度縮合していても
よい。式(b) の化合物も1種でまたは2種以上組み合わ
せて使用することができる。The compound of the formula (b) may have been condensed several times, for example, about 2 to 5 before reacting with the boron compound. The compounds of the formula (b) can also be used alone or in combination of two or more.
【0026】式(b) の化合物の好ましい例としては、例
えば、メチルトリクロロシラン、フェニルトリクロロシ
ラン、フェニルトリメトキシシラン、フェニルトリエト
キシシラン、メチルトリメトキシシラン、メチルトリエ
トキキシシラン等が挙げられる。Preferred examples of the compound of the formula (b) include, for example, methyltrichlorosilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and the like.
【0027】上記の式(a) の化合物及び式(b) の化合物
の基Rの種類により、得られるポリボロシロキサンの特
性が変化する。例えば、Rとしてアルキル基が含まれる
量が多い程、可撓性は高くなるが、耐熱性は低くなる。
一方、Rとしてフェニル基等のアリール基が含まれる量
が多い程、可撓性は低くなるが、耐熱性は高くなる。例
えば、同一の化合物中に異なるRを有する式(a) の化合
物または式(b) の化合物を使用するか、あるいは2種以
上のそれぞれの化合物を使用して、得られる重合体がR
としてアルキル基とアリール基を含むものとする場合、
アルキル基とアリール基の量はモル比で20:1〜1:
1の範囲にあることが好ましい。The properties of the resulting polyborosiloxane vary depending on the type of the group R of the compound of the formula (a) and the compound of the formula (b). For example, the larger the amount of the alkyl group as R, the higher the flexibility but the lower the heat resistance.
On the other hand, the larger the amount of an aryl group such as a phenyl group as R, the lower the flexibility but the higher the heat resistance. For example, using a compound of the formula (a) or a compound of the formula (b) having different R in the same compound, or using two or more kinds of the respective compounds, the polymer obtained is
When an alkyl group and an aryl group are included as
The molar ratio of the alkyl group and the aryl group is from 20: 1 to 1:
It is preferably in the range of 1.
【0028】本発明の方法に使用されるホウ素化合物
は、従来ポリボロシロキサンを製造するのに使用されて
いたものでよく、例えば、オルトホウ酸、メタホウ酸、
無水ホウ酸のようなホウ酸、ホウ砂等のホウ酸金属塩、
ホウ酸メチルのようなホウ酸エステル、トリメトキシボ
ロンのようなホウ酸アルコキシド、塩化ホウ素のような
ハロゲン化ホウ素等を使用することができる。The boron compound used in the method of the present invention may be any of those conventionally used to produce polyborosiloxanes, for example, orthoboric acid, metaboric acid,
Boric acid such as boric anhydride, metal borate salts such as borax,
Boric acid esters such as methyl borate, boric acid alkoxides such as trimethoxyboron, and boron halides such as boron chloride can be used.
【0029】本発明の方法においては、先ず上記式(a)
の化合物とホウ素化合物を反応させる。これらの化合物
を、例えば不活性ガス気流中、例えば50〜150 ℃の温度
範囲で還流させることにより縮重合反応を行うことがで
きる。In the method of the present invention, first, the above formula (a)
Is reacted with a boron compound. The condensation polymerization reaction can be carried out by refluxing these compounds in an inert gas stream, for example, at a temperature in the range of 50 to 150 ° C.
【0030】この場合、式(a) の化合物(またはそのオ
リゴマー)とホウ素化合物とは、ケイ素とホウ素の原子
比で5:1〜2:1の量で使用し、次の三官能ケイ素化
合物との反応に使用される程度のアルコキシ基等の官能
基が残るようにすることが好ましい。In this case, the compound of the formula (a) (or an oligomer thereof) and the boron compound are used in an amount of 5: 1 to 2: 1 by atomic ratio of silicon to boron, and the following trifunctional silicon compound is used. It is preferable that functional groups such as an alkoxy group remain in such a degree as to be used in the above reaction.
【0031】この最初の二官能性ケイ素化合物とホウ素
化合物との反応の生成物の重合度によって最終的な生成
物の可撓性等の特性が左右されるが、この反応において
は反応時間を選択することにより得られる縮合体の重合
度を調節することができるので、最終的な生成物に所望
の特性を与えるように反応時間を選択すればよい。The degree of polymerization of the product of the reaction between the first bifunctional silicon compound and the boron compound affects the properties such as flexibility of the final product. In this reaction, the reaction time is selected. Thus, the degree of polymerization of the condensate obtained can be adjusted, so that the reaction time may be selected so as to give desired properties to the final product.
【0032】前記のような所望の特性を有するポリボロ
シロキサンを得るためには、式(a)の化合物(またはそ
のオリゴマー)とホウ素化合物との反応において、両者
が、下記式(c)In order to obtain a polyborosiloxane having desired properties as described above, in the reaction of a compound of the formula (a) (or an oligomer thereof) with a boron compound, both react with the following formula (c)
【0033】[0033]
【化7】 (式中、Rは前記のものと同じ意味を有する)で表され
るボロシロキサン単位が平均で2〜10個、特に2〜5
個含まれる縮合化合物に変換されるまで行うことが好ま
しい。このような程度の重合度を得るためには、その他
の反応条件にもよるが、上記のような条件で反応を行っ
た場合、1〜8時間の反応時間を使用すればよい。Embedded image (Wherein R has the same meaning as described above) on average 2 to 10, especially 2 to 5 borosiloxane units
It is preferable to carry out the reaction until it is converted into a condensed compound. In order to obtain such a degree of polymerization, depending on other reaction conditions, when the reaction is carried out under the above conditions, a reaction time of 1 to 8 hours may be used.
【0034】このような二官能ケイ素化合物とホウ素化
合物の縮合体の重合度はゲルパーミエーションクロマト
グラフィー(GPC)により測定することができ、特定
の化合物について特定の反応温度等の反応条件について
所望の重合度が得られる反応時間を測定しておき、その
後は重合度の測定から求められた反応時間を使用すれば
よい。The degree of polymerization of the condensate of such a bifunctional silicon compound and boron compound can be measured by gel permeation chromatography (GPC), and the specific compound has a desired reaction condition such as a specific reaction temperature. The reaction time for obtaining the degree of polymerization may be measured, and then the reaction time determined from the measurement of the degree of polymerization may be used.
【0035】次いで上記で得られた二官能ケイ素化合物
とホウ素化合物の縮合体に、式(b)で表される三官能ケ
イ素化合物とホウ素化合物を反応させる。上記の二官能
ケイ素化合物とホウ素化合物の反応生成物に式(b) で表
される三官能ケイ素化合物とホウ素化合物を加え、上記
の二官能ケイ素化合物との反応と同様の条件で、好まし
くは1時間以上還流させることにより、存在する官能基
を実質的に全て反応させる。そして蒸留操作により副生
物のアルコール等を除去し、さらに好ましくは100〜
300℃以上に昇温して1時間以上熟成させ、未反応の
低分子量成分を反応させる。Next, the condensate of the bifunctional silicon compound and the boron compound obtained above is reacted with the trifunctional silicon compound represented by the formula (b) and the boron compound. A trifunctional silicon compound represented by the formula (b) and a boron compound are added to the above-mentioned reaction product of the bifunctional silicon compound and the boron compound, and under the same conditions as in the reaction with the bifunctional silicon compound, preferably 1 By refluxing for more than an hour, substantially all of the functional groups present are reacted. Then, by-products such as alcohol are removed by a distillation operation, and more preferably 100 to 100%.
The temperature is raised to 300 ° C. or higher and aged for 1 hour or more to react unreacted low molecular weight components.
【0036】使用する三官能ケイ素化合物の量は、最終
的に得られるポリボロシロキサンの可撓性を左右し、二
官能性ケイ素化合物の量が多い程柔軟なポリボロシロキ
サンが得られ、一方、三官能ケイ素化合物の量が多い程
強固なポリボロシロキサンが得られるが、通常は二官能
性ケイ素化合物と三官能ケイ素化合物の比がケイ素の原
子比で2:1〜5:1となるようにすることが好まし
い。The amount of the trifunctional silicon compound used affects the flexibility of the finally obtained polyborosiloxane, and the higher the amount of the bifunctional silicon compound, the more flexible the polyborosiloxane is obtained. As the amount of the trifunctional silicon compound increases, a stronger polyborosiloxane is obtained, but usually, the ratio of the bifunctional silicon compound to the trifunctional silicon compound is set so that the atomic ratio of silicon is 2: 1 to 5: 1. Is preferred.
【0037】三官能ケイ素化合物とともに使用するホウ
素化合物の量は、存在する官能基が十分に反応し、かつ
ホウ素化合物がケイ素化合物の官能基を反応させるのに
必要な量よりも多くならないようにする。例えばホウ素
化合物としてホウ酸を使用した場合、ホウ酸のヒドロキ
シル基の量がケイ素化合物に残る官能基の量を越えない
ようにする。三官能ケイ素化合物とホウ素化合物の比
は、ケイ素とホウ素の原子比で1:0.1〜1:4であ
ることが好ましい。The amount of boron compound used with the trifunctional silicon compound is such that the functional groups present are sufficiently reacted and that the boron compound does not exceed the amount required to react the functional groups of the silicon compound. . For example, when boric acid is used as the boron compound, the amount of hydroxyl groups of boric acid should not exceed the amount of functional groups remaining in the silicon compound. The ratio of the trifunctional silicon compound to the boron compound is preferably from 1: 0.1 to 1: 4 in the atomic ratio of silicon to boron.
【0038】また、上記の式(a) の化合物とホウ素化合
物との反応生成物及び式(b) の化合物でXとしてヒドロ
キシル基を有するものには、常温で固体であるものがあ
る。これらの化合物を加熱する前に固体のまま互いに混
合すると、昇温時に不均一に反応が進行し、結果として
得られる重合体の構造が不均一になる可能性がある。従
って、式(a) の化合物とホウ素化合物との反応生成物が
常温で固体となる場合は、式(a) の化合物とホウ素化合
物との反応後温度を低下させないようにして液体状態に
維持し、さらに式(b) の化合物が常温で固体である場合
はこれを予め加熱して溶融し、液体状態にしてから式
(a) の化合物とホウ素化合物との反応生成物に添加する
ことが好ましい。The reaction product of the compound of the formula (a) with the boron compound and the compound of the formula (b) having a hydroxyl group as X include those which are solid at room temperature. If these compounds are mixed together in a solid state before heating, the reaction proceeds non-uniformly when the temperature is raised, and the structure of the resulting polymer may be non-uniform. Therefore, when the reaction product of the compound of the formula (a) and the boron compound becomes a solid at room temperature, it is maintained in a liquid state without lowering the temperature after the reaction of the compound of the formula (a) and the boron compound. When the compound of the formula (b) is a solid at room temperature, it is heated and melted in advance to obtain a liquid state,
It is preferably added to the reaction product of the compound (a) and the boron compound.
【0039】上記のようにして得られたポリボロシロキ
サンは、エタノール等の溶媒に可溶であり、そのような
溶媒に溶解し、任意に酸化物、炭化物、窒化物等の充填
剤、その他のポリマー等を加えて絶縁被覆塗料とし、こ
れを被膜が所望される表面に塗布し、乾燥及び焼成して
無機絶縁被膜とすることができる。The polyborosiloxane obtained as described above is soluble in a solvent such as ethanol, and is dissolved in such a solvent, and optionally a filler such as an oxide, a carbide, a nitride, or the like. A polymer or the like is added to form an insulating coating, which is applied to the surface where the coating is desired, dried and fired to form an inorganic insulating coating.
【0040】上記のようにして得られた絶縁被覆塗料
を、導電体線材のような基体上に慣用の方法により塗布
し、200〜500℃程度の温度で2〜30分間程度焼
成することにより、耐熱温度400℃以上の耐熱性を有
する優れた絶縁被膜が得られる。特に本発明の方法によ
り製造されたポリボロシロキサンによれば、200℃程
度の低温で焼成してもべたつきのない被膜を形成するこ
とができる。The insulating coating material obtained as described above is applied on a substrate such as a conductor wire by a conventional method, and baked at a temperature of about 200 to 500 ° C. for about 2 to 30 minutes. An excellent insulating coating having a heat resistance of 400 ° C. or higher can be obtained. In particular, according to the polyborosiloxane produced by the method of the present invention, a non-sticky film can be formed even when calcined at a low temperature of about 200 ° C.
【0041】このようにして得られた無機絶縁電線も本
発明に包含されるものである。本発明の無機絶縁電線に
設けられる絶縁被覆の厚さは、電線の用途にもよるが、
一般的には数μm 〜数mm程度である。The inorganic insulated wire thus obtained is also included in the present invention. The thickness of the insulating coating provided on the inorganic insulated wire of the present invention depends on the use of the wire,
Generally, it is about several μm to several mm.
【0042】本発明の方法により製造されたポリボロシ
ロキサンを使用して得られる絶縁被覆塗料は、電線の耐
熱性を有する絶縁被覆を形成するのに特に好適である
が、その他の用途における耐熱性絶縁被覆塗料としても
使用することができ、例えばプレコート(PC)加工板
等の絶縁被覆を形成した後に加工されるようなものにも
好ましく使用できる。The insulating coating obtained by using the polyborosiloxane produced by the method of the present invention is particularly suitable for forming an insulating coating having heat resistance of electric wires, but is suitable for use in other applications. It can also be used as an insulating coating paint, and can be preferably used, for example, on a precoated (PC) processed plate or the like which is processed after forming an insulating coating.
【0043】[0043]
【実施例】以下、実施例により本発明をさらに説明す
る。The present invention will be further described with reference to the following examples.
【0044】実施例1 36.1 g (0.3 モル) のジメチルジメトキシシランと6.18
g (0.1 モル) のホウ酸をフラスコに入れ、窒素気流中
80℃で3時間還流させた。反応物をGPCにより分析し
たところ、ジメチルジメトキシシランが平均でボロシロ
キサン単位を約3個含む縮合体に変換されていた。次い
でこれに13.6 g (0.1 モル) のフェニルトリメトキシシ
ランと6.18 g (0.1 モル) のホウ酸を添加し、さらに3
時間還流させた。その後副生成物を蒸留操作により除去
した後、200℃で3時間加熱撹拌し、ポリボロシロキ
サンを得た。Example 1 36.1 g (0.3 mol) of dimethyldimethoxysilane and 6.18
g (0.1 mol) of boric acid in a flask
Reflux at 80 ° C. for 3 hours. Analysis of the reaction product by GPC indicated that dimethyldimethoxysilane had been converted to a condensate containing on average about 3 borosiloxane units. Next, 13.6 g (0.1 mol) of phenyltrimethoxysilane and 6.18 g (0.1 mol) of boric acid were added thereto, followed by addition of 3%.
Reflux for hours. Thereafter, by-products were removed by a distillation operation, and the mixture was heated and stirred at 200 ° C. for 3 hours to obtain a polyborosiloxane.
【0045】実施例2 実施例1のジメチルジメトキシシランの代わりにその2
量体である1,1,3,3-テトラメチル-1,3-ジメトキシシラ
ンを同モル量使用して同様にポリボロシロキサンを得
た。Example 2 In place of dimethyldimethoxysilane of Example 1,
A polyborosiloxane was similarly obtained by using the same molar amount of 1,1,3,3-tetramethyl-1,3-dimethoxysilane as a monomer.
【0046】1,1,3,3-テトラメチル-1,3-ジメトキシシ
ランとホウ酸との反応後に反応物をGPCにより分析し
たところ、1,1,3,3-テトラメチル-1,3-ジメトキシシラ
ンは平均でボロシロキサン単位を約3個含む縮合体に変
換されていた。After the reaction of 1,1,3,3-tetramethyl-1,3-dimethoxysilane with boric acid, the reaction product was analyzed by GPC, and found to be 1,1,3,3-tetramethyl-1,3 -Dimethoxysilane had been converted to a condensate containing on average about 3 borosiloxane units.
【0047】実施例3 実施例1の0.3 モルのジメチルジメトキシシランの代わ
りに、0.25モルのジメチルジメトキシシランと0.05モル
のジフェニルジメトキシシランを使用して同様にポリボ
ロシロキサンを得た。Example 3 A polyborosiloxane was obtained in the same manner as in Example 1 except that 0.25 mol of dimethyldimethoxysilane and 0.05 mol of diphenyldimethoxysilane were used instead of 0.3 mol of dimethyldimethoxysilane.
【0048】ジメチルジメトキシシラン及びジフェニル
ジメトキシシランとホウ酸との反応後に反応物をGPC
により分析したところ、ジメチルジメトキシシラン及び
ジフェニルジメトキシシランは平均でボロシロキサン単
位を約3個含む縮合体に変換されていた。After the reaction of dimethyldimethoxysilane and diphenyldimethoxysilane with boric acid, the reaction product was subjected to GPC.
As a result, dimethyldimethoxysilane and diphenyldimethoxysilane were converted to a condensate containing on average about 3 borosiloxane units.
【0049】実施例4 24.4 g (0.1 モル) のジフェニルジメトキシシラン、4
3.26 g (0.2モル) のジフェニルジヒドロキシシラン及
び6.18 g (0.1 モル) のホウ酸をフラスコに入れ、窒素
気流下に撹拌しながら110 ℃に加熱して溶融し、この温
度に3時間維持した。その後反応物をGPCにより分析
したところ、ジフェニルジメトキシシラン及びジフェニ
ルジヒドロキシシランが平均でボロシロキサン単位を約
3個含む縮合体に変換されていた。Example 4 24.4 g (0.1 mol) of diphenyldimethoxysilane, 4
3.26 g (0.2 mol) of diphenyldihydroxysilane and 6.18 g (0.1 mol) of boric acid were placed in a flask, heated to 110 ° C. with stirring under a stream of nitrogen, melted and maintained at this temperature for 3 hours. Thereafter, the reaction product was analyzed by GPC, and it was found that diphenyldimethoxysilane and diphenyldihydroxysilane were converted to a condensate containing on average about 3 borosiloxane units.
【0050】次いで上記の反応物を溶融状態に保ったま
まフラスコに6.18 g (0.1 モル) のホウ酸を加え、さら
に24.0 g (0.1 モル) のフェニルトリエトキシシランを
チューブポンプを用いて1.2 g/分(0.005モル/分) の速
度で上記フラスコ内に滴下した。フェニルトリエトキシ
シランの全量を添加した後、反応物を300 ℃に1時間加
熱し、残ったモノマーを反応させ、ポリボロシロキサン
を得た。Then, while the above reaction mixture was kept in a molten state, 6.18 g (0.1 mol) of boric acid was added to the flask, and 24.0 g (0.1 mol) of phenyltriethoxysilane was further added to the flask at 1.2 g / 0.1 g using a tube pump. Minutes (0.005 mol / min). After all of the phenyltriethoxysilane had been added, the reaction was heated to 300 ° C. for 1 hour to allow the remaining monomer to react, yielding a polyborosiloxane.
【0051】比較例1 0.2 モル のジフェニルジメトキシシランと6.18 g (0.
1 モル) のホウ酸をフラスコに入れ、窒素気流中80℃で
3時間還流させた。その後副生成物を蒸留操作により除
去した後、200℃で3時間加熱撹拌し、ポリジフェニ
ルボロシロキサンを得た。Comparative Example 1 0.28 mol of diphenyldimethoxysilane and 6.18 g (0.
(1 mol) of boric acid was placed in a flask and refluxed at 80 ° C. for 3 hours in a nitrogen stream. Thereafter, by-products were removed by a distillation operation, and the mixture was heated and stirred at 200 ° C. for 3 hours to obtain polydiphenylborosiloxane.
【0052】比較例2 0.2 モル のジフェニルジメトキシシランの代わりに0.
2 モルのジメチルジメトキシシランを使用した以外は比
較例1と同様にしてポリジメチルボロシロキサンを得
た。Comparative Example 2 Instead of 0.2 mol of diphenyldimethoxysilane, 0.2
A polydimethylborosiloxane was obtained in the same manner as in Comparative Example 1 except that 2 mol of dimethyldimethoxysilane was used.
【0053】比較例3 432 g (2モル) のジフェニルジヒドロキシシラン、83 g
(1.3 モル) のホウ酸、255 g の10センチストークスの
ジメチルポリシロキサンシリコーンオイルをフラスコに
入れ、窒素雰囲気中で撹拌しながら約6時間で室温から
400 ℃まで徐々に加熱し、さらに400 ℃で1時間加熱撹
拌して縮重合反応を行い、重合体を得た。Comparative Example 3 432 g (2 mol) of diphenyldihydroxysilane, 83 g
(1.3 moles) of boric acid, 255 g of 10 centistokes dimethylpolysiloxane silicone oil in a flask and stir in a nitrogen atmosphere for about 6 hours from room temperature.
The mixture was gradually heated to 400 ° C. and further heated and stirred at 400 ° C. for 1 hour to carry out a polycondensation reaction to obtain a polymer.
【0054】上記の実施例及び比較例で得られた重合体
のそれぞれの10 gを10 ml のエタノールに溶解し、ステ
ンレス基板(SUS430)に焼成後の厚さが10μmとなるよう
に塗布、乾燥し、200 ℃で10分間焼成して絶縁被膜を得
た。10 g of each of the polymers obtained in the above Examples and Comparative Examples was dissolved in 10 ml of ethanol, coated on a stainless steel substrate (SUS430) so that the thickness after firing was 10 μm, and dried. Then, it was baked at 200 ° C. for 10 minutes to obtain an insulating film.
【0055】得られた絶縁被膜について、以下のように
して可撓性、耐熱性、べたつき、耐湿性及び加熱減量を
評価した。The obtained insulating film was evaluated for flexibility, heat resistance, stickiness, moisture resistance and heat loss as follows.
【0056】可撓性 上記で得られた被膜をJIS K5400 の耐屈曲試験で評価し
た。Flexibility The coating obtained above was evaluated by a bending resistance test according to JIS K5400.
【0057】耐熱性 上記で得られた被膜をさらに400 ℃で1時間焼成し、被
膜におけるクラックの発生を目視評価した。クラックが
発生しなかった場合を○、クラックが発生した場合を×
で示す。Heat resistance The coating obtained above was further baked at 400 ° C. for 1 hour, and the occurrence of cracks in the coating was visually evaluated. ○: No crack occurred, ×: Crack occurred
Indicated by
【0058】べたつき上記で得られた被膜に触れること
によりべたつきがないかどうかを調べた。べたつきが感
じられなかった場合を○、べたつきが感じられた場合を
×で示す。The coating obtained above was examined for any stickiness by touching it. The case where stickiness was not felt is indicated by ○, and the case where stickiness was felt is indicated by ×.
【0059】耐湿性 上記で得られた被膜を水中に10分間浸漬し、その後1日
放置した後に外観を目視観察し、失透していないかどう
かを評価した。失透が見られなかった場合を○、失透が
わずかに見られた場合を△、失透が明確に見られた場合
を×で示す。Moisture resistance The coating obtained above was immersed in water for 10 minutes, and then left standing for one day. Then, the appearance was visually observed to evaluate whether or not devitrification had occurred. The case where no devitrification was observed is indicated by ○, the case where devitrification is slightly observed is indicated by Δ, and the case where devitrification is clearly observed is indicated by ×
【0060】加熱減量 10 mg のポリボロシロキサン試料を白金パンに取り、10
℃/分の速度で室温から400 ℃まで昇温し、減少した重
量を当初試料重量に対するパーセントとして表した(熱
重量法)。アルミナ粉末をリファレンスとした。Heat loss 10 mg of a polyborosiloxane sample was placed in a platinum pan,
The temperature was raised from room temperature to 400 ° C. at a rate of ° C./min and the reduced weight was expressed as a percentage of the original sample weight (thermogravimetric method). Alumina powder was used as a reference.
【0061】上記の評価の結果を、重合体の製造に使用
したケイ素化合物及びホウ酸のモル数(シリコーンオイ
ルについてはグラム数)とともに下記表1に示す。The results of the above evaluation are shown in Table 1 below together with the number of moles of silicon compound and boric acid (gram number for silicone oil) used in the production of the polymer.
【0062】[0062]
【表1】 表1に示した結果から明らかなように、本発明の方法に
より製造されたポリボロシロキサンは、可撓性、耐熱
性、耐湿性、低温での焼成後のべたつき、及び加熱減量
のいずれについても、比較例のものと比べて有意に優れ
ていることは明らかである。[Table 1] As is evident from the results shown in Table 1, the polyborosiloxane produced by the method of the present invention exhibited flexibility, heat resistance, moisture resistance, stickiness after firing at a low temperature, and loss on heating. However, it is clear that it is significantly superior to that of the comparative example.
【0063】[0063]
【発明の効果】本発明のポリボロシロキサンの製造方法
によれば、高い可撓性を有し、比較的低い温度での焼成
によりべたつきを示さず、加熱減量が少なく、高い耐熱
性と耐湿性を有する無機ポリマーを形成することができ
る。According to the method for producing a polyborosiloxane of the present invention, it has high flexibility, does not show stickiness when calcined at a relatively low temperature, has little heat loss, and has high heat resistance and moisture resistance. Can be formed.
Claims (5)
基を表し、Xはアルコキシ基、ヒドロキシル基またはハ
ロゲン原子を表す)の化合物をホウ素化合物と反応さ
せ、得られた生成物をさらに、下記式(b) 【化2】 (式中、R及びXは上記と同じ意味を表す)の化合物及
びホウ素化合物と反応させることを含む、ポリボロシロ
キサンの製造方法。(1) The following formula (a): (Wherein R represents an alkyl group, an alkenyl group or an aryl group, and X represents an alkoxy group, a hydroxyl group or a halogen atom), and the resulting product is further reacted with a boron compound according to the following formula ( b) Wherein R and X have the same meanings as described above, and a boron compound.
式(c) 【化3】 (式中、Rはアルキル基、アルケニル基またはアリール
基を表す)で表される単位が平均で2〜10個含まれる
縮合化合物に変換されるまで式(a) の化合物とホウ素化
合物との反応を行う、請求項1に記載の方法。2. The compound of formula (a) and a boron compound are represented by the following formula (c): (Wherein R represents an alkyl group, an alkenyl group or an aryl group). The reaction of the compound of the formula (a) with a boron compound until it is converted into a condensed compound containing an average of 2 to 10 units represented by the following formula: The method of claim 1, wherein:
物との反応物に液体状態の式(b) の化合物を加える、請
求項1または2に記載の方法。3. The process according to claim 1, wherein the compound of formula (b) is added to the reaction product of the compound of formula (a) in liquid form with the boron compound.
より製造されたポリボロシロキサンを含む塗料を塗布し
焼成することにより得られる塗膜。4. A coating film obtained by applying a coating containing the polyborosiloxane produced by the method according to claim 1 and firing the coating.
有する無機絶縁電線。5. An inorganic insulated wire having the coating film according to claim 4 as an insulating coating.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8314654A JPH10152561A (en) | 1996-11-26 | 1996-11-26 | Production of polysiloxane, polysiloxane coating and inorganically insulated wire having the same coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8314654A JPH10152561A (en) | 1996-11-26 | 1996-11-26 | Production of polysiloxane, polysiloxane coating and inorganically insulated wire having the same coating |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10152561A true JPH10152561A (en) | 1998-06-09 |
Family
ID=18055937
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8314654A Pending JPH10152561A (en) | 1996-11-26 | 1996-11-26 | Production of polysiloxane, polysiloxane coating and inorganically insulated wire having the same coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH10152561A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007177219A (en) * | 2005-11-14 | 2007-07-12 | Rohm & Haas Electronic Materials Llc | Silicon-containing polymer and optical waveguide formed by the same |
WO2008044521A1 (en) * | 2006-10-13 | 2008-04-17 | Nitto Boseki Co., Ltd. | Polymeric composition comprising metal alkoxide condensation product, organic silane compound and boron compound |
EP2014702A1 (en) | 2007-07-11 | 2009-01-14 | Nitto Denko Corporation | Resin for optical semiconductor element encapsulation containing polyborosiloxane |
JP2009127020A (en) * | 2007-11-28 | 2009-06-11 | Nitto Denko Corp | Photosemiconductor element-sealing resin containing polyborosiloxane, and photosemiconductor device obtained by using the same |
JP2009167361A (en) * | 2008-01-21 | 2009-07-30 | Nitto Denko Corp | Method of producing resin composition for sealing optical semiconductor device |
EP2159607A1 (en) * | 2008-08-27 | 2010-03-03 | Nitto Denko Corporation | Microlens Array |
JP2011518893A (en) * | 2008-03-04 | 2011-06-30 | ダウ・コーニング・コーポレイション | Borosiloxane composition, borosiloxane adhesive, painted substrate and laminated substrate |
WO2012077529A1 (en) | 2010-12-09 | 2012-06-14 | 株式会社ダイセル | Addition-curable metallosiloxane compound |
CN108929545A (en) * | 2018-07-30 | 2018-12-04 | 苏州太星新材料科技有限公司 | A kind of water base boron-silicon rubber can porcelain composite material and preparation method and application |
CN109943076A (en) * | 2019-03-29 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of sulphurated siliastic and preparation method thereof |
CN114672030A (en) * | 2022-04-28 | 2022-06-28 | 上海矽璃材料科技有限公司 | Multi-element modified organic boron siloxane copolymer and preparation method thereof |
-
1996
- 1996-11-26 JP JP8314654A patent/JPH10152561A/en active Pending
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007177219A (en) * | 2005-11-14 | 2007-07-12 | Rohm & Haas Electronic Materials Llc | Silicon-containing polymer and optical waveguide formed by the same |
KR101299116B1 (en) * | 2005-11-14 | 2013-08-21 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Silicon-containing polymers and optical waveguides formed therefrom |
WO2008044521A1 (en) * | 2006-10-13 | 2008-04-17 | Nitto Boseki Co., Ltd. | Polymeric composition comprising metal alkoxide condensation product, organic silane compound and boron compound |
JPWO2008044521A1 (en) * | 2006-10-13 | 2010-02-12 | 日東紡績株式会社 | Polymer composition containing metal alkoxide condensate, organosilane compound, and boron compound |
US9029449B2 (en) | 2006-10-13 | 2015-05-12 | Nitto Boseki Co., Ltd. | Polymeric composition comprising metal alkoxide condensation product, organic silane compound and boron compound |
JP5594558B2 (en) * | 2006-10-13 | 2014-09-24 | 日東紡績株式会社 | Polymer composition containing metal alkoxide condensate, organosilane compound, and boron compound |
KR101153652B1 (en) * | 2007-07-11 | 2012-06-18 | 닛토덴코 가부시키가이샤 | Resin for optical semiconductor element encapsulation containing polyborosiloxane |
EP2014702A1 (en) | 2007-07-11 | 2009-01-14 | Nitto Denko Corporation | Resin for optical semiconductor element encapsulation containing polyborosiloxane |
JP2009019104A (en) * | 2007-07-11 | 2009-01-29 | Nitto Denko Corp | Resin for optical semiconductor element encapsulation containing polyborosiloxane |
JP2009127020A (en) * | 2007-11-28 | 2009-06-11 | Nitto Denko Corp | Photosemiconductor element-sealing resin containing polyborosiloxane, and photosemiconductor device obtained by using the same |
JP2009167361A (en) * | 2008-01-21 | 2009-07-30 | Nitto Denko Corp | Method of producing resin composition for sealing optical semiconductor device |
JP2011518893A (en) * | 2008-03-04 | 2011-06-30 | ダウ・コーニング・コーポレイション | Borosiloxane composition, borosiloxane adhesive, painted substrate and laminated substrate |
US8021756B2 (en) | 2008-08-27 | 2011-09-20 | Nitto Denko Corporation | Microlens array |
EP2159607A1 (en) * | 2008-08-27 | 2010-03-03 | Nitto Denko Corporation | Microlens Array |
WO2012077529A1 (en) | 2010-12-09 | 2012-06-14 | 株式会社ダイセル | Addition-curable metallosiloxane compound |
US8791221B2 (en) | 2010-12-09 | 2014-07-29 | Daicel Corporation | Addition-curable metallosiloxane compound |
CN108929545A (en) * | 2018-07-30 | 2018-12-04 | 苏州太星新材料科技有限公司 | A kind of water base boron-silicon rubber can porcelain composite material and preparation method and application |
CN108929545B (en) * | 2018-07-30 | 2021-04-16 | 苏州太星新材料科技有限公司 | Water-based borosilicate rubber ceramizable composite material and preparation method and application thereof |
CN109943076A (en) * | 2019-03-29 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of sulphurated siliastic and preparation method thereof |
CN114672030A (en) * | 2022-04-28 | 2022-06-28 | 上海矽璃材料科技有限公司 | Multi-element modified organic boron siloxane copolymer and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5601212B2 (en) | Silicon-containing polymer compound, heat-resistant resin composition, and heat-resistant film | |
US5962067A (en) | Method for coating an article with a ladder siloxane polymer and coated article | |
EP0725103B1 (en) | Thermosetting silicone resins | |
JP6423821B2 (en) | Polyarylene material | |
KR0135514B1 (en) | Organosilicone resin coating compositions | |
JP2810760B2 (en) | Liquid silicone resin composition and method for producing the same | |
EP0390154B1 (en) | Solventless silicone coating composition | |
JPS5898367A (en) | Silicone film forming composition and production thereof | |
JP2844896B2 (en) | Heat resistant insulation paint | |
JPH10152561A (en) | Production of polysiloxane, polysiloxane coating and inorganically insulated wire having the same coating | |
JPS62230828A (en) | Insulating film for semiconductor, formation thereof and coating solution | |
JP2002212503A (en) | Film-forming composition, method for producing the composition, method for forming porous film, and the porous film | |
EP0705866B1 (en) | Process for producing organopolysiloxanes | |
JPH07300528A (en) | Production of organic-modified thermosetting silicone resin,and resin obtained thereby | |
JPH0633335B2 (en) | Method for producing organopolysiloxane | |
JP3150731B2 (en) | Method for producing silicone resin | |
JPH07278497A (en) | Coating composition for covering | |
US6211307B1 (en) | Organopolysiloxane composition for forming fired film | |
JPH0422190B2 (en) | ||
JPS6320271B2 (en) | ||
JPH07278307A (en) | Production of alkoxy group-containing silicone resin | |
JPH05156176A (en) | Heat-resistant antifouling coating material and heat-resistant antifouling coating film | |
JPS6338381B2 (en) | ||
JPH04252229A (en) | Silicone compound and production thereof | |
JP2002265788A (en) | Highly dielectric, addition-curable composition |