JPH01236205A - Thermosetting resin composition and cured product thereof - Google Patents
Thermosetting resin composition and cured product thereofInfo
- Publication number
- JPH01236205A JPH01236205A JP6191788A JP6191788A JPH01236205A JP H01236205 A JPH01236205 A JP H01236205A JP 6191788 A JP6191788 A JP 6191788A JP 6191788 A JP6191788 A JP 6191788A JP H01236205 A JPH01236205 A JP H01236205A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- thermosetting resin
- cured product
- composition according
- group
- 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.)
- Granted
Links
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 16
- 239000011342 resin composition Substances 0.000 title claims description 12
- -1 perfluorophenylene ring Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- CQKQSUKECBDFHR-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octafluorobiphenylene Chemical group FC1=C(F)C(F)=C(F)C2=C1C1=C(F)C(F)=C(F)C(F)=C21 CQKQSUKECBDFHR-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000000047 product Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- BUQZYTHPQVWQIR-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4,5,6-tetrafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(C=C)=C1F BUQZYTHPQVWQIR-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OJGZFWYQULDFPL-UHFFFAOYSA-N 1-chloro-4-(4-chloro-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluorobenzene Chemical group FC1=C(Cl)C(F)=C(F)C(C=2C(=C(F)C(Cl)=C(F)C=2F)F)=C1F OJGZFWYQULDFPL-UHFFFAOYSA-N 0.000 description 1
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- HNUKTDKISXPDPA-UHFFFAOYSA-N 2-oxopropyl Chemical group [CH2]C(C)=O HNUKTDKISXPDPA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- ROEHNQZQCCPZCH-UHFFFAOYSA-N tert-butyl 2-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C ROEHNQZQCCPZCH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は熱硬化性樹脂組成物に係り、符に難燃性、耐熱
性及び低誘′に率で電気特性に優れ几絶縁材料として好
適な使脂組底物及びその硬化物に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a thermosetting resin composition, which has excellent flame retardancy, heat resistance, low dielectric constant, and electrical properties, and is suitable as an insulating material. The present invention relates to a fat-used composite sole and a cured product thereof.
従来、低誘電率の絶縁材料として、ポリ四フフ化エチレ
ンに代表されるフッ素系樹脂やポリエチレン、ポリブタ
ジェンに代表される炭化水素系樹脂が知られており、一
般的に広く用いられている。Conventionally, fluororesins such as polytetrafluoroethylene, hydrocarbon resins such as polyethylene, and polybutadiene have been known as insulating materials with low dielectric constants, and are generally widely used.
しかし前者のフッ素系樹脂は耐熱性が高く、蟲燃注でろ
るが、これらはすべて熱可塑性樹脂であり、軟化温度が
低く軟化温度工り高＠側では急激７ｃ機械的強度の低下
や熱膨張率が大きくなり、使用される範囲に限足を受け
てしまう。ま７’Ｃ後者の炭化水素系樹脂はポリブタジ
ェンを始め熱硬化性樹脂が数多く開発されており、高温
での機械的Ｑ 隻、寸法安定性等を必要とする分野にも
広く適用されている（特公昭５Ｂ−２１９２６号）。し
かし、これら炭化水素系樹脂は可燃性樹脂でろるという
大きな問題点がめる０このため離燃化の検討が必要でお
るが、一般的に難燃剤の添７ＩＯは電気特性に悪影響を
与える九め、低諌電率としての特性が十分に生かせない
ことが多い。However, the former fluorine-based resin has high heat resistance and is resistant to mold injection, but these are all thermoplastic resins, and their softening temperature is low and when the softening temperature is high, the mechanical strength suddenly decreases by 7C and thermal expansion occurs. The ratio becomes large and the range in which it can be used is limited. Of the latter hydrocarbon resins, many thermosetting resins have been developed, including polybutadiene, and are widely applied in fields that require mechanical stability at high temperatures, dimensional stability, etc. Special Publication No. 5B-21926). However, these hydrocarbon resins have a major problem in that they are flammable resins.For this reason, it is necessary to consider flame retardation; In many cases, the characteristic of low electrical discharge rate cannot be fully utilized.
本発明の目的は耐熱性ｔ−損うことなく難撚性でかつ低
酵電率で電気特注に優れ之熱硬化性樹脂組成物及びその
硬化物全提供することにある。The object of the present invention is to provide a thermosetting resin composition and a cured product thereof, which is difficult to twist without impairing heat resistance, has a low fermentation rate, and is excellent in electrical customization.
本発明を概説すれば、本発明の第１の発明は熱硬化性樹
脂組成物に関する発明でろって、下記−最大ｌ：
Ｘ−Ｒ−Ｘ ・・・（１）（式中Ｒ
に、７ツ索を少なくとも１個含有する芳香環、Ｘは反応
注二亘結会を有するＩｔ換基全示す）で表される化合物
を含有していることを特徴とする０
そして、本発明の第２の発明は硬化物に関する発明でろ
って、第１の発明の熱硬化性樹脂組成物を熱硬化させて
なることを特徴とする。To summarize the present invention, the first invention of the present invention relates to a thermosetting resin composition.
The present invention is characterized in that it contains a compound represented by an aromatic ring containing at least one heptad, X is an It substituent having a reaction bond. The second invention relates to a cured product, and is characterized in that it is obtained by thermosetting the thermosetting resin composition of the first invention.
前記目的は、上記−最大ｌを過酸化物等のラジカル１合
開始剤あるいは熱１合等に工９硬化物を得ることに工す
達成される。The above object is achieved by adding the above-mentioned maximum l to a radical initiator such as peroxide or heat to obtain a cured product.
本発明における一般式［−具体的に示すと例えば、
で表される。このとさＸは反応性二重結合ｔ−有する置
換基で、このＩＥ置換基１分子中に２個あるため加熱重
合することにより三次元に架橋した耐熱性に優れた熱硬
化性樹脂組成物となる。三次元架橋し九熱硬化物は軟化
温度が尚くなり、高温での著しい機械的強度の低下や熱
膨張率の急激な上昇を抑えることができ、高温で寸法安
定性の優れた絶縁材料として使用することができる。ま
た分子骨格ｔ）ユニしン環、ビフェニレン環にスルコト
にニジ、耐熱性、機械的強度が優れたものが得られる。The general formula in the present invention is represented by [--Specifically, for example. This tosa X is a substituent having a reactive double bond t-, and since there are two of these IE substituents in one molecule, the thermosetting resin composition has excellent heat resistance and is three-dimensionally crosslinked by thermal polymerization. becomes. The three-dimensionally crosslinked nine-thermocured material has a lower softening temperature and can suppress a significant decrease in mechanical strength and a rapid increase in the coefficient of thermal expansion at high temperatures, making it an insulating material with excellent dimensional stability at high temperatures. can be used. In addition, a molecular skeleton (t) having a unicine ring and a biphenylene ring with a sulfuric acid structure and excellent heat resistance and mechanical strength can be obtained.
反応基を置換した以外のところをフッ素基に置換えるこ
とにニジ、耐熱性が更に向上し、難撚性の特注全有する
ことができる０反応注二重結合を有する置換基Ｘの例と
しては、ビニル（−ＣＨ＝ＣＨｚ ） ｂ アリル（−
ＣＨ宜−ＣＨ＝ＣＨり、イソプロペニル（−Ｃ＝ＣＨ，
） 、ビニルオキシ（−０−ＣＨ＝ＣＨ，）、占Ｈ３
アリルオキシ（−０−ＣＨ，−Ｃ）ｌ＝ｃＨ，）、イソ
プロペニルオキシ（−０−Ｃ＝ＣＨ，） 、アクリロイ
ルオキシ占Ｈ３
（−０−Ｃ−ＣＨ＝ＣＨり 、３−ブテノイルオキシ（
一〇−Ｃ−ＣＨ２−ＣＨ＝ＣＨ２）、メグクリロイルオ
かシるいは熱重合可能な二重結合を有していれば特に限
定ちれるものではない。By substituting fluorine groups in places other than the reactive groups, the heat resistance is further improved, and it is possible to have a custom-made structure with low twist resistance.As an example of the substituent X having a double bond, , vinyl (-CH=CHz) b allyl (-
CH-CH=CH, isopropenyl (-C=CH,
), vinyloxy(-0-CH=CH,), allyloxy(-0-CH,-C)l=cH,), isopropenyloxy(-0-C=CH,), acryloyloxy(- 0-C-CH=CH, 3-butenoyloxy (
There is no particular limitation as long as it has a double bond that can be thermally polymerized, such as 10-C-CH2-CH=CH2), megcrylyl, or silyl.
本発明における硬化反応について一般的な方法としでは
、ラジカル重合開始剤として退散化物を用いることが多
い。一般に使用されろ過は化物としてＵ ９１１えばベ
ンゾイルパーオキシド、シタミルパーオキシド、メチル
エチルケトンパーオキシド、２．５−ジメチルヘキサン
−２，５−シバ（ｌ’ロバ−オキシド、ｔ−ブチルパー
ベンゾエート、２．５−ジメチル−２，５−（ｔ−ブチ
ルパーオキシ）ヘキシン−３、クメンハイドロパーオキ
シド、ｔ−ブチルハツトロバ−オキシド、ジベンジルパ
ーオキシド、ジーｔ−ブチルパーオキシフタレート寺が
おる。重合開始剤の配合披としては街脂組成吻１００１
１Ｌ量部に対して、一般にａ１〜５重鼠部であるが、α
２〜ｃ１．５重置部が杵に好ましい。ま之、必要に応じ
てラジカル重合の促進剤、遅延剤や谷ａ顔料、充てん剤
等を加えても良い。In a general method for the curing reaction in the present invention, a retreated product is often used as a radical polymerization initiator. Commonly used filtration methods include U911 compounds such as benzoyl peroxide, cytamyl peroxide, methyl ethyl ketone peroxide, 2,5-dimethylhexane-2,5-shiba(l'roba-oxide), t-butyl perbenzoate, 2. 5-dimethyl-2,5-(t-butylperoxy)hexyne-3, cumene hydroperoxide, t-butyltrobar oxide, dibenzyl peroxide, di-t-butylperoxyphthalate.Polymerization initiators The combination is street fat composition 1001
For 1L part, it is generally a1 to 5 parts, but α
2 to c1.5 overlapping parts are preferred for the punch. However, if necessary, a radical polymerization accelerator, retarder, valley a pigment, filler, etc. may be added.
硬化反応としては有脂組成物ＶＣ開始剤を添フロし友だ
けの塊状重合を始め、有機溶媒を用いｆｃ浴浴室１合、
乳化重合や懸濁重合等がおる。For the curing reaction, a fatty composition was added with a VC initiator to start bulk polymerization, and an organic solvent was used to prepare the FC bath for 1 cup.
There are emulsion polymerization, suspension polymerization, etc.
以下、本発明七笑施例にエリ更に具体的に耽明するが、
本発明はこれら実施例に限定されない。Hereinafter, seven examples of the present invention will be described in more detail,
The invention is not limited to these examples.
実施例１
ジビニルテトラフルオロベンゼンの合成脱水乾燥させた
ジエチルエーテル５〇−甲に１゜４−ジクロロ−２，３
，５，６−テトラフルオロベンゼン２０ｔｆ静解し、そ
の中にマグネシウム片ｔ−３２、ヨウ素結晶を数片加え
る。還流条件下（３５℃）で約２時間反応させる。５０
−の水を刃口えて反応全終了式せ、更に希１１１ｉＩＥ
咳を加え過剰のマグネシウムを硫酸塩として分離させる
。得られた１、４−シ（クロロマグネシウム） −２，
３，５，６−チトラフルオロベンゼンのジエチルエーテ
ル浴液に７セトアルデヒドを加えて１．４−ビス（１−
ヒドロキシエチル）−２，３，５，６−チトラフルオロ
ベンゼンを得る。史に五酸化リンを加えて還流条件下で
５時間脱水反応七行う。最後に得られ九生底物を大波の
メタノール中に投入し、沈殿物として得る〇ジエチルエ
ーテルーメタノール糸で再沈殿を行いｎ表し、真空乾燥
を行い、１，４−ジビニル−２，３゜５．６−チトラフ
ルオロベンゼン’ｋ 得ｆｔ ｏ 得’）れ九生成物の
ＩＲスペクトルを第１図に示す。なお、第１図において
横＠は彼数（ロー１ン、縦軸は透過率を示す。Example 1 Synthesis of divinyltetrafluorobenzene Dehydrated and dried diethyl ether 5〇-A to 1゜4-dichloro-2,3
, 20tf of 5,6-tetrafluorobenzene is allowed to settle, and a magnesium piece T-32 and several pieces of iodine crystal are added thereto. The reaction is carried out under reflux conditions (35°C) for about 2 hours. 50
Add water to complete the reaction, and add diluted 111iIE.
Cough to separate excess magnesium as sulfate. The obtained 1,4-cy(chloromagnesium)-2,
7cetaldehyde was added to the diethyl ether bath solution of 3,5,6-titrafluorobenzene to form 1,4-bis(1-
hydroxyethyl)-2,3,5,6-titrafluorobenzene is obtained. Add phosphorus pentoxide to the mixture and carry out a dehydration reaction for 5 hours under reflux conditions. Finally, the obtained 90-year-old bottom material is poured into a large wave of methanol to obtain a precipitate. Re-precipitate with diethyl ether-methanol thread and vacuum dry to obtain 1,4-divinyl-2,3 The IR spectrum of the 5.6-titrafluorobenzene product is shown in FIG. In FIG. 1, the horizontal @ represents the number of electrons (row 1), and the vertical axis represents the transmittance.
ジビニルテトラフルオロベンゼンの重合得られたモノマ
ー１０１Ｆに過酸化物としてジクミルパーオキシドｏ、
ｏ２ｔｋ刃口え、ろらかじめ離型処理し九釡型容器に厚
さ２簡になるように入れ、８０℃／６０分、１００℃７
６０分、１２０℃７１８０分、１５０℃／１８０分加熱
硬化反応を行い、硬化物を得友。得られた硬化物の耐熱
性を調べるｔめ熱分解開始温度、電気特注として比誘電
率、雄燃注としてＵＬ試験、高温で軟化性の目安として
曲げ強度比（室温と１８０℃との曲げ強度の比）を測定
して得られ友結果七後記表１に他の例と共に示す。Polymerization of divinyltetrafluorobenzene Dicumyl peroxide o,
o2tk blade mouthpiece, Rorakaji, mold release treatment, put into a nine pot type container so that it is 2 pieces thick, 80℃ / 60 minutes, 100℃ 7
Heat curing reactions were performed for 60 minutes at 120°C, 7180 minutes at 150°C, and 180 minutes at 150°C to obtain a cured product. To check the heat resistance of the obtained cured product, check the thermal decomposition start temperature, the relative dielectric constant for electrical special orders, the UL test for male fuel injection, and the bending strength ratio (bending strength between room temperature and 180°C) as a measure of softening properties at high temperatures. The results obtained are shown in Table 1 below along with other examples.
実施例２
実施？ＩＪ １で１．４−ジクロロ−２，３，５，６−
チトラフルオロベンゼンの代９に４，４′−ジクロロオ
クタフルオロビフェニルを用いてグリニヤール化合物會
得、更にアセトアルデヒドの代υにア七トンを刃口えて
４．４′−イソプロペニルオクタフルオロビフェニルを
モノマーとして得た。得られた生成物のＩＲスペクトル
を第２図に示す。Example 2 Implementation? IJ 1 in 1,4-dichloro-2,3,5,6-
A Grignard compound was obtained by using 4,4'-dichlorooctafluorobiphenyl as the substitute for titrafluorobenzene, and then adding a7tone to the substitute for acetaldehyde to form 4,4'-isopropenyl octafluorobiphenyl as a monomer. Obtained. The IR spectrum of the obtained product is shown in FIG.
得られ念モノマー１０ｔに過酸化物としてベンゾイルパ
ーオキシドｃＬｏｓｒ’ｌ加え、実施例１と同様に金型
容器上用いて６０℃／６０分、８０℃／６０分、１００
℃／１８０分、１２０℃７１８０分、１５０℃７１８０
分７７０熱硬化して南脂板金得几。得られた特性を表１
に示す。Benzoyl peroxide cLosr'l was added as a peroxide to 10 tons of the obtained monomer, and the mixture was heated in the same manner as in Example 1 at 60°C/60 minutes, 80°C/60 minutes, 100°C.
℃/180 minutes, 120℃ 7180 minutes, 150℃ 7180
Heat cured for 770 minutes to obtain a sheet metal. Table 1 shows the obtained characteristics.
Shown below.
実施例３
１．４−ジアリルテトラフルオロベンゼンの合成１．４
−ジヒドロキシ−２，３，５，６−テトラフルオロベン
ゼン２ｏｙ２ジブチルエーテル１００ｆ！ＬｔＫ浴解さ
せアリルクロライド１０りを加え１００℃で２時間反応
場ぜる。得られ友生成物を大波のメタノール中に投入し
、沈殿物として得る。更にジエチルエーテル−メタノー
ル系で再沈殿を行い稽表し、真空乾燥を行い１．４−ジ
アリル−２，３，５，６−チトラフルオロベンゼンを得
友。得られた生成物のＩＲスペクトルを第３図に示す。Example 3 Synthesis of 1.4-diallyltetrafluorobenzene 1.4
-dihydroxy-2,3,5,6-tetrafluorobenzene 2oy2 dibutyl ether 100f! Dissolve the LtK bath, add 10 g of allyl chloride, and leave the reaction field at 100°C for 2 hours. The obtained product is poured into a large amount of methanol to obtain a precipitate. Further, reprecipitation was performed using a diethyl ether-methanol system, followed by vacuum drying to obtain 1,4-diallyl-2,3,5,6-titrafluorobenzene. The IR spectrum of the obtained product is shown in FIG.
得られ友モノマー１０ｒＶｃｉ！ｉｇ化物としてクメン
ハイドロパーオキシド（ＬＯ５ｆ’（＋−加え実施ｖＪ
１と同様に金盟谷器を用いて硬化物全作成し九〇硬化温
度は１００℃７６０分、１５０℃／１８０分、２００℃
／１８０分とし友。得られｆｃ特性を表１に示す。Obtained friend monomer 10rVci! Cumene hydroperoxide (LO5f'(+-additional vJ
90 Curing temperature was 100°C for 760 minutes, 150°C/180 minutes, 200°C.
/180 minutes Toshitomo. The obtained fc characteristics are shown in Table 1.
実施ガ４
１．４−ジメタクリロイルオキシテトラフルオロベンゼ
ンの合成
１．４−ジヒドロキシ−２，３，５，６−テトラフルオ
ロベンゼン２０ｆｔ−塩化メチレン２００ゴに溶解させ
メタクリル酸クロライド１０１Ｆ’ｉ含んだ塩化メチレ
ン浴ｆｉ１００１Ｌｔ’ｉ約３０分かけて滴下する。Example 4 Synthesis of 1.4-dimethacryloyloxytetrafluorobenzene 1.4-dihydroxy-2,3,5,6-tetrafluorobenzene 20 ft - chloride containing methacrylic acid chloride 101 F'i dissolved in 200 methylene chloride The methylene bath fi1001Lt'i is added dropwise over about 30 minutes.
この時反応液は５℃前後に冷却しながら行う。滴下後、
還流条件下（４０℃）で５時間反応を行い得られた生成
物を大量のメタノール中に投入し沈殿物として得る。更
にジエチルエーテル−メタノール糸で再沈殿七行い精製
し、真空乾燥により、１．４−ジメタクリロイルオキシ
−２，３，５，６−チトラフルオロペンセンを得友。得
られた生成物の工Ｒスペクトル全第４図に示す。At this time, the reaction solution is cooled to around 5°C. After dripping,
The reaction is carried out under reflux conditions (40° C.) for 5 hours, and the resulting product is poured into a large amount of methanol to obtain a precipitate. Further purification was carried out by seven reprecipitations using a diethyl ether-methanol thread, followed by vacuum drying to obtain 1,4-dimethacryloyloxy-2,3,5,6-titrafluoropencene. The complete R spectrum of the obtained product is shown in FIG.
得られたモノマー１０ｆＫ過酸化物としてｔ−ブチルハ
イドロパーオキシド（Ｌｌ ｔｆ刀刃口、実施例３と同
じ硬化温度により硬化物を作成した。得られｔ杵注七表
１に示す０
比較ガ１
モノマーとしてペンタフルオロスチレン１０２にジクミ
ルパーオキシド００５２加え実施例１と同峠の方法で熱
可塑性樹脂板を得た。得られた特注を表１に示す。Obtained monomer 10 fK As peroxide, t-butyl hydroperoxide (Ll tf) A cured product was prepared at the same curing temperature as in Example 3. A thermoplastic resin plate was obtained by adding dicumyl peroxide 0052 to pentafluorostyrene 102 and using the same method as in Example 1. Table 1 shows the custom-made resin plate.
比較例２
プレポリマーとして１，２−ポリブタジエン１０２にジ
クミルパーオキシド１１１ を金加え実施列１と同様な
方法で硬化′＠金得た。得られ７′ｔ−特性を表１に示
す。Comparative Example 2 Dicumyl peroxide 111 was added as a prepolymer to 1,2-polybutadiene 102 to obtain cured gold in the same manner as in Example 1. The obtained 7't-characteristics are shown in Table 1.
茨１に示″ｊＬうに央厖声」に工って得らｎた硬化物は
すべて比誘電率が２．５付近と低く、更に耐熱狂、難燃
任に潰れていることが分る。また、比較す」１のような
熱可塑性の樹脂板と異なり高温（１８０℃９でも機弧的
強度に十分保持している。It can be seen that all of the cured products obtained by fabricating "JL Sea Urchins" shown in Ibara 1 have a low dielectric constant of around 2.5, and are also heat resistant and flame retardant. Also, unlike thermoplastic resin plates like Comparison 1, it maintains sufficient mechanical strength even at high temperatures (180°C9).
本発明に工って得られ九含フッ索熱硬化性情脂組成物は
、射恐注、難燃法に潰れ、かつ比誘電率の低いｔ気％注
Ｖ？−稜れた絶縁材料として適用てれる〇ま九この時、
三次元架橋型硬化物であるため高温での機械的強度、寸
法安定性にも極めて優れており、多くの分野で使用てれ
る。The fluorine-containing thermosetting resin composition obtained by the present invention is resistant to injection and flame retardant methods, and has a low dielectric constant. - At this time, it can be applied as a ridged insulating material.
Because it is a three-dimensionally crosslinked cured product, it has excellent mechanical strength and dimensional stability at high temperatures, and is used in many fields.
第１１〜第４図は本発明の熱硬１と狂矧脂組成物に添加
されるモノマーの１り（」の赤外吸収スペクトル図でろ
る。
特許出願人 体式会社 日立製作所Figures 11 to 4 are infrared absorption spectra of the thermoset 1 of the present invention and one of the monomers added to the wax fat composition. Patent applicant: Hitachi, Ltd.
Claims (1)
Ｘは反応性二重結合を有する置換基を示す）で表される
化合物を含有していることを特徴とする熱硬化性樹脂組
成物。 ２、該基Ｒが、パーフルオロフエニレン環又はパーフル
オロビフエニレン環である請求項１記載の熱硬化性樹脂
組成物。 ３、該基Ｘの炭素数が、２〜４個である請求項１記載の
熱硬化性樹脂組成物。 ４、該基Ｘが、ビニル、アリル、イソプロペニル、ビニ
ルオキシ、アリルオキシ、イソプロペニルオキシ、アク
リロイルオキシ、３−ブテノイルオキシ又はメタクリロ
イルオキシ基である請求項１記載の熱硬化性樹脂組成物
。 ５、請求項１記載の熱硬化性樹脂組成物を熱硬化させて
なることを特徴とする硬化物。[Claims] 1. The following general formula 1: X-R-X... [1] (In the formula, R is an aromatic ring containing at least one fluorine,
A thermosetting resin composition characterized by containing a compound represented by (X represents a substituent having a reactive double bond). 2. The thermosetting resin composition according to claim 1, wherein the group R is a perfluorophenylene ring or a perfluorobiphenylene ring. 3. The thermosetting resin composition according to claim 1, wherein the group X has 2 to 4 carbon atoms. 4. The thermosetting resin composition according to claim 1, wherein the group X is a vinyl, allyl, isopropenyl, vinyloxy, allyloxy, isopropenyloxy, acryloyloxy, 3-butenoyloxy or methacryloyloxy group. 5. A cured product obtained by thermosetting the thermosetting resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63061917A JPH0796574B2 (en) | 1988-03-17 | 1988-03-17 | Thermosetting resin composition and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63061917A JPH0796574B2 (en) | 1988-03-17 | 1988-03-17 | Thermosetting resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01236205A true JPH01236205A (en) | 1989-09-21 |
| JPH0796574B2 JPH0796574B2 (en) | 1995-10-18 |
Family
ID=13184994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63061917A Expired - Lifetime JPH0796574B2 (en) | 1988-03-17 | 1988-03-17 | Thermosetting resin composition and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796574B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997003992A1 (en) * | 1995-07-14 | 1997-02-06 | Sumitomo Chemical Company, Limited | Transition metal complex, process for the preparation thereof, polymerization catalyst for olefins containing the complex, and process for producing olefin polymers |
| JP2003073435A (en) * | 2001-08-31 | 2003-03-12 | Nof Corp | Thermosetting resin composition, resin cured film and use |
| JP2003261511A (en) * | 2001-12-27 | 2003-09-19 | Merck Patent Gmbh | Polymerizable monocyclic compound |
| JP2008262931A (en) * | 2008-08-05 | 2008-10-30 | Toray Ind Inc | Paste for buffer layer formation of plasma display panel |
| JP2009139909A (en) * | 2007-08-03 | 2009-06-25 | Tokyo Ohka Kogyo Co Ltd | Fluorine-containing compound, resist composition for immersion exposure, and method of forming resist pattern |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5984910A (en) * | 1982-11-02 | 1984-05-16 | Koichi Hatada | Novel copolymer and production thereof |
| JPS59164501A (en) * | 1983-03-09 | 1984-09-17 | Tokuyama Soda Co Ltd | organic optical glass |
| JPH01168630A (en) * | 1987-12-24 | 1989-07-04 | Central Glass Co Ltd | Novel fluorine-containing aromatic unsaturated compound and production thereof |
-
1988
- 1988-03-17 JP JP63061917A patent/JPH0796574B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5984910A (en) * | 1982-11-02 | 1984-05-16 | Koichi Hatada | Novel copolymer and production thereof |
| JPS59164501A (en) * | 1983-03-09 | 1984-09-17 | Tokuyama Soda Co Ltd | organic optical glass |
| JPH01168630A (en) * | 1987-12-24 | 1989-07-04 | Central Glass Co Ltd | Novel fluorine-containing aromatic unsaturated compound and production thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997003992A1 (en) * | 1995-07-14 | 1997-02-06 | Sumitomo Chemical Company, Limited | Transition metal complex, process for the preparation thereof, polymerization catalyst for olefins containing the complex, and process for producing olefin polymers |
| US6329478B1 (en) | 1995-07-14 | 2001-12-11 | Sumitmo Chemical Company, Limited | Transition metal complex, process for producing the same, olefin polymerization catalyst containing the transition metal complex and process for producing olefin polymers |
| EP1498178A3 (en) * | 1995-07-14 | 2005-02-09 | Sumitomo Chemical Company, Limited | Transition metal complex, process for producing the same, olefin polymerization catalyst containing the transition metal complex and process for producing olefin polymers |
| JP2003073435A (en) * | 2001-08-31 | 2003-03-12 | Nof Corp | Thermosetting resin composition, resin cured film and use |
| JP2003261511A (en) * | 2001-12-27 | 2003-09-19 | Merck Patent Gmbh | Polymerizable monocyclic compound |
| US7465479B2 (en) * | 2001-12-27 | 2008-12-16 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Polymerisable monocyclic compounds |
| JP4553550B2 (en) * | 2001-12-27 | 2010-09-29 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Polymerizable monocyclic compounds |
| JP2009139909A (en) * | 2007-08-03 | 2009-06-25 | Tokyo Ohka Kogyo Co Ltd | Fluorine-containing compound, resist composition for immersion exposure, and method of forming resist pattern |
| JP2012255170A (en) * | 2007-08-03 | 2012-12-27 | Tokyo Ohka Kogyo Co Ltd | Fluorine-containing compound |
| JP2008262931A (en) * | 2008-08-05 | 2008-10-30 | Toray Ind Inc | Paste for buffer layer formation of plasma display panel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0796574B2 (en) | 1995-10-18 |
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