JPS62230842A - Thermosetting resin composition - Google Patents
Thermosetting resin compositionInfo
- Publication number
- JPS62230842A JPS62230842A JP7502886A JP7502886A JPS62230842A JP S62230842 A JPS62230842 A JP S62230842A JP 7502886 A JP7502886 A JP 7502886A JP 7502886 A JP7502886 A JP 7502886A JP S62230842 A JPS62230842 A JP S62230842A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- resin composition
- condensed polycyclic
- thermosetting resin
- aromatic hydrocarbon
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 12
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 25
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002989 phenols Chemical class 0.000 claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 14
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 14
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 13
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 8
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 239000003377 acid catalyst Substances 0.000 claims abstract description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 4
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 claims abstract description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkylphenol Chemical compound 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 31
- 239000011347 resin Substances 0.000 description 31
- 125000003367 polycyclic group Chemical group 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006482 condensation reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 125000006839 xylylene group Chemical group 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- GKROKAVBUIADBS-UHFFFAOYSA-N phenanthrene-2-carbaldehyde Chemical compound C1=CC=C2C3=CC=C(C=O)C=C3C=CC2=C1 GKROKAVBUIADBS-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、易成形硬化性で、かつ、耐酸化性、耐熱分
解性の非常に優れた熱硬化性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a thermosetting resin composition that is easily molded and hardened, and has excellent oxidation resistance and thermal decomposition resistance.
従来技術
熱硬化性樹脂としては、フェノール樹脂、尿素樹脂、メ
ラミン樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、
ポリイミド樹脂等が知られている（昭和６０年６月１５
日、−新技術開発センター発行、「エンジニアリングプ
ラスチック便覧」第１４９〜１５１頁参照）。Conventional thermosetting resins include phenolic resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin,
Polyimide resin etc. are known (June 15, 1985)
(Refer to pages 149-151 of "Engineering Plastics Handbook" published by New Technology Development Center).
一般にこれらの樹脂は、熱可塑性樹脂に比べて熱
優れた斐を有しているが、それてもポリイミド樹脂を除
けは、長期使用可能温度は最高１５０〜２００℃程度で
ある。Generally, these resins have superior thermal properties compared to thermoplastic resins, but except for polyimide resins, the maximum temperature at which they can be used for a long time is about 150 to 200°C.
一方、ポリイミド樹脂は、長期使用可能温度が２５０〜
３００℃と非常に優れた耐熱性を有するが、半面、成形
加工性に劣る欠点がある。On the other hand, polyimide resin has a long-term usable temperature of 250~
Although it has excellent heat resistance of 300°C, it has the disadvantage of poor moldability.
最近、新規の熱硬化性樹脂として、縮合多環多核芳香族
樹脂が注目されている。Recently, fused polycyclic polynuclear aromatic resins have been attracting attention as new thermosetting resins.
縮合多環多核芳香族樹脂は、縮合多環芳香族炭化水素と
して、ピレン、フェナントレン、ナフタリン、アントラ
セン、それらを含有するピッチ等を単独または混合物で
用い、架橋剤としてｐ−キシリレングリコール、酸触媒
としてｐ−）ルエンスルホン酸等を用い、不活性ガス雰
囲気下、重縮合させることにより得られる（昭和６０年
１０月３日間催の第５１回日本化学会秋季年会の講演要
旨集、第５３９〜５４１頁、および昭和６０年１２月１
１〜１３日開催、炭素材料学会第１２回年金の要旨集、
第１８３頁参照）。The condensed polycyclic polynuclear aromatic resin uses pyrene, phenanthrene, naphthalene, anthracene, pitch containing them, etc. alone or in a mixture as a condensed polycyclic aromatic hydrocarbon, and p-xylylene glycol and an acid catalyst as a crosslinking agent. p-) obtained by polycondensation in an inert gas atmosphere using luenesulfonic acid, etc. (Collection of lecture abstracts of the 51st Autumn Annual Meeting of the Chemical Society of Japan held for 3 days in October 1985, No. 539) ~541 pages, and December 1, 1985
Collection of abstracts from the 12th annual meeting of the Carbon Materials Society, held from 1st to 13th.
(See page 183).
この縮合多環多核芳香族樹脂は、Ｂステージ状態の樹脂
を１００〜３００℃で加熱することにより三次元化し、
その硬化物は、非常に優れた耐酸化性および耐熱分解性
を示す。This condensed polycyclic polynuclear aromatic resin is made three-dimensional by heating the B-stage resin at 100 to 300°C,
The cured product exhibits excellent oxidation resistance and thermal decomposition resistance.
しかるにこの縮合多環多核芳香族樹脂は、フェノール樹
脂、エポキシ樹脂等他の汎用熱硬化性樹脂に比べて硬化
速度が遅く、その成形加工性対策が重要な課題である。However, this condensed polycyclic polynuclear aromatic resin has a slow curing speed compared to other general-purpose thermosetting resins such as phenol resins and epoxy resins, and its moldability is an important issue.
また、架橋剤として、通常ｐ−キシリレングリコールが
使用されるが、高耐熱性を実現するためには、架橋密度
を上げる必要があるため、一定量以上の架橋剤を使用す
る必要がある。しかし、ｐ−キシリレングリコールは、
現在、工業的に有利な生産技術が確立されておらず、経
済性を満足する合成法の確立や、代替品の開発が重要な
ｒＩＢとなっている。Further, p-xylylene glycol is usually used as a crosslinking agent, but in order to achieve high heat resistance, it is necessary to increase the crosslinking density, so it is necessary to use a certain amount or more of the crosslinking agent. However, p-xylylene glycol
Currently, no industrially advantageous production technology has been established, and it is important to establish a synthetic method that satisfies economic efficiency and to develop alternative products.
解決しようとする問題点
いて
この発明は、上記縮合多環多核芳香族樹脂に線成形硬化
性を改善し、また、架橋剤として、ヘキサメチレンテト
ラミンが使用できる熱硬化性樹脂組成物を提供するもの
である。SUMMARY OF THE INVENTION In view of the problems to be solved, the present invention provides a thermosetting resin composition in which the above-mentioned condensed polycyclic polynuclear aromatic resin has improved linear molding curability and in which hexamethylenetetramine can be used as a crosslinking agent. It is.
発明の詳細
な説明者等は、種々試験研究の結果、原料として多環芳
香族炭化水素と共に、フェノール類を用いると、硬化時
に架橋剤としてヘキサメチレンテトラミンが使用できる
こと、および前記縮合多環多核芳香族樹脂の耐熱性を損
なうことなく、硬化性が大きく、向上することを見い出
し、この発明を完成した。As a result of various tests and studies, the person explaining the invention in detail found that when phenols are used together with polycyclic aromatic hydrocarbons as raw materials, hexamethylenetetramine can be used as a crosslinking agent during curing, and that the fused polycyclic polynuclear aromatic The present invention was completed based on the discovery that the curability of group resins can be greatly improved without impairing the heat resistance.
すなわちこの発明は、縮合多環芳香族炭化水素、フェノ
ール類、一般式ＣＨ２Ｘ（ただし、Ｘ＝０１１、ＣＩ！
、８ｒ）で表される官能基を２個以上有する芳香族化合
物を、酸触媒の存在下、加熱せしめてなる重縮合物とへ
キサメチレンテトラミンとからなる熱硬化性樹脂組成物
である。That is, this invention is directed to fused polycyclic aromatic hydrocarbons, phenols, and general formula CH2X (where X=011, CI!
, 8r) is a thermosetting resin composition comprising a polycondensate obtained by heating an aromatic compound having two or more functional groups represented by , 8r) in the presence of an acid catalyst and hexamethylenetetramine.
従来の縮合多環多核芳香族樹脂は、架橋剤として通常ｐ
−キシリレングリコールを用いるが、架橋剤が被架橋原
料に対し、モル比で０．８以下の場合、生成する樹脂は
一般に熱硬化性を示さない。Conventional fused polycyclic polynuclear aromatic resins usually contain p as a crosslinking agent.
- When xylylene glycol is used, but the molar ratio of the crosslinking agent to the raw material to be crosslinked is 0.8 or less, the resulting resin generally does not exhibit thermosetting properties.
それに対して本発明の樹脂は、樹脂骨格にフェノール核
を有しているため、従来の縮合多環多核芳香族樹脂には
ない特性、すなわぢ、硬化時に架橋剤として、ヘキサメ
チレンテトラミンを添加し・て熱処理することにより、
容易に熱硬化体を与えるという特性を有する。On the other hand, since the resin of the present invention has a phenol nucleus in its resin skeleton, it has characteristics that conventional condensed polycyclic polynuclear aromatic resins do not have, namely, hexamethylenetetramine is added as a crosslinking agent during curing. By heat treatment,
It has the property of easily forming a thermosetting product.
したがって、ｐ−キシリレングリコールを縮合多環多核
芳香族炭化水素に対し、多量に添加して熱硬化体とする
ことなく、安価なヘキサメチレンテトラミンを添加して
熱処理することにより、ｐ−キシリレングリコールを多
量に使用したと同様の熱硬化体を得ることができるので
ある。Therefore, instead of adding a large amount of p-xylylene glycol to a condensed polycyclic polynuclear aromatic hydrocarbon to form a thermoset, by adding inexpensive hexamethylenetetramine and heat-treating it, p-xylylene It is possible to obtain a thermoset product similar to that obtained by using a large amount of glycol.
また、本発明の樹脂は、縮合反応性の高いフェノール核
を有しているため、従来の縮合多環多核芳香族樹脂に比
較し、硬化性が大きく向上する。Moreover, since the resin of the present invention has a phenol nucleus with high condensation reactivity, the curability is greatly improved compared to conventional condensed polycyclic polynuclear aromatic resins.
さらに、得られる熱硬化体は、従来の縮合多環多核芳香
族樹脂の優れた耐熱性を引き継いでおり、一般のフェノ
ール樹脂に比べ、非常に優れた耐酸化性、耐熱分解性を
有している。Furthermore, the resulting thermoset inherits the excellent heat resistance of conventional condensed polycyclic polynuclear aromatic resins, and has extremely superior oxidation resistance and thermal decomposition resistance compared to general phenolic resins. There is.
この発明における縮合多環芳香族炭化水素としては、ナ
フタリン、フェナントレン、アントラセン、とレン、フ
ルオランテン、アセナフテン、メチルナフタレン、それ
らの誘導体、またはそれらを含有するコールタール分留
留分の単独または混合物が使用できる。As the condensed polycyclic aromatic hydrocarbon in this invention, naphthalene, phenanthrene, anthracene, torene, fluoranthene, acenaphthene, methylnaphthalene, derivatives thereof, or coal tar fractions containing them alone or in mixtures are used. can.
また、フェノール類としては、フェノール、アルキルフ
ェノール、レゾルシン、ナフトール等の１価または多価
の単核フェノール、あるいはフェノール、アルキルフェ
ノールで代表されるフェノール類とホルムアルデヒド、
ホルムアルデヒドと同効物質であるバラホルムアルデヒ
ド、または、アセトンのごときケトンとの酸触媒による
縮合て得られる架橋基を介して結合する多核フェノール
であって、未だフェノール核中に活性反応水素を有する
ものが使用できる。In addition, phenols include monovalent or polyvalent mononuclear phenols such as phenol, alkylphenol, resorcinol, and naphthol, or phenols represented by phenol and alkylphenol, and formaldehyde.
Paraformaldehyde, which is a substance with the same effect as formaldehyde, or a polynuclear phenol that is bonded through a crosslinking group obtained by acid-catalyzed condensation with a ketone such as acetone, and which still has active reactive hydrogen in the phenol nucleus. Can be used.
一般式一〇Ｈ２Ｘ（ただし、Ｘ ＝ＯＨ，ＣＩ！ 、Ｂ
ｒ ）で表される官能基を２個以上有する芳香族化合物
としては、キシリレングリコール、ナフタリンジメタツ
ール、ビフェニルジメタツール、キシリレンジクロライ
ド、キシリレンジクロライド等が使用できる。General formula 10H2X (where, X = OH, CI!, B
As the aromatic compound having two or more functional groups represented by r), xylylene glycol, naphthalene dimetatool, biphenyl dimetatool, xylylene dichloride, xylylene dichloride, etc. can be used.
酸触媒としては、トルエンスルホン酸、フェノールスル
ホン酸、キシレンスルホン酸、硫酸、塩化錫、塩化アル
ミニウム、塩化亜鉛等の各種有機酸、無機酸、ルイス酸
を使用することができる。As the acid catalyst, various organic acids, inorganic acids, and Lewis acids such as toluenesulfonic acid, phenolsulfonic acid, xylenesulfonic acid, sulfuric acid, tin chloride, aluminum chloride, and zinc chloride can be used.
本発明においては、フェノール類が単核フェノールの場
合、縮合多環芳香族炭化水素との合計モルに対し、フェ
ノール類の割合がモル比で０．２以下になると、ヘキサ
メチレンテトラミンとの活性点が乏しくなる。このため
、単核フェノール類は、縮合多環芳香族炭化水素との合
計モルに対して、モル比で０．２以上が好ましく、より
好ましい範囲としては、０．４以上である。In the present invention, when the phenol is a mononuclear phenol, if the molar ratio of the phenol to the total mole of the condensed polycyclic aromatic hydrocarbon is 0.2 or less, the active site with hexamethylenetetramine is becomes scarce. Therefore, the molar ratio of the mononuclear phenol to the total mole of the condensed polycyclic aromatic hydrocarbon is preferably 0.2 or more, and more preferably 0.4 or more.
また、一般式−ＣＨ２Ｘ（ただし、Ｘ＝０１１．ＣＪ！
、Ｂ「）で表される官能基を２個以上有する芳香族化合
物の配合比は、被架橋原料であるフェノール類と縮合多
環芳香族炭化水素の合計モルに対して、モル比で０．３
以下であると、ヘキサメチレンテトラミンを多配合して
も、十分な熱硬化性を示さず、逆に５．０以上になると
、芳香族化合物同志の反応でエーテル結合が増加し、耐
熱分解特性が低下すると共に、機械特性（特に耐衝撃性
）も劣化する。このため、芳香族化合物は、被架橋原料
の合計モルに対し、モル比で０．３〜５．０が好ましく
、より好ましい範囲としては０．４〜３．０である。Also, the general formula -CH2X (where X=011.CJ!
The blending ratio of the aromatic compound having two or more functional groups represented by , B") is 0.00 molar ratio to the total mole of the phenols and the condensed polycyclic aromatic hydrocarbon, which are the raw materials to be crosslinked. 3
If it is less than 5.0, even if a large amount of hexamethylenetetramine is blended, it will not show sufficient thermosetting properties, and if it is more than 5.0, the number of ether bonds will increase due to the reaction between aromatic compounds, and the heat decomposition resistance will deteriorate. At the same time, mechanical properties (particularly impact resistance) also deteriorate. Therefore, the molar ratio of the aromatic compound to the total mole of the raw materials to be crosslinked is preferably 0.3 to 5.0, more preferably 0.4 to 3.0.
この発明により得られる樹脂は、高耐熱性を有しており
、従来の縮合多環多核芳香族樹脂に比較し、８成形硬化
性で、かつ、コスト的に自有利であり、耐熱性の要求さ
れる構造材料、電子材料として極めて価値の高いものと
判断される。The resin obtained by this invention has high heat resistance, has 8 mold curability compared to conventional condensed polycyclic polynuclear aromatic resins, is advantageous in terms of cost, and meets the requirements for heat resistance. It is judged to be extremely valuable as a structural material and electronic material.
以下実施例を示すが、本発明は何らこれらに限定される
ものではない。Examples will be shown below, but the present invention is not limited to these in any way.
実施例
フェナントレン４４．６重量部（以下重量部を単に部と
記載する） ［０，２５ｍｏｌ］ 、ｐ−キシリレン
グリコール５１．８部［０，３７５ｍｏｌ ］ 、ｒ）
−）ルエンスルホン酸（１水和物）６部をガラス製反
応器に仕込み、窒素気流中、撹拌しながら１２０℃で１
５分間反応させたのち、フェノール２３．５部［０，２
５ｆｆＩｏｔコを投入してさらにｌＯ５分間縮合反応さ
せ、第１表試料１の樹脂を得た。Example 44.6 parts by weight of phenanthrene (hereinafter, parts by weight are simply referred to as parts) [0.25 mol], 51.8 parts of p-xylylene glycol [0,375 mol], r)
-) 6 parts of luenesulfonic acid (monohydrate) was charged into a glass reactor, and heated to 120°C with stirring in a nitrogen stream.
After reacting for 5 minutes, 23.5 parts of phenol [0.2
5 ffIot was added and the condensation reaction was further carried out for 5 minutes to obtain the resin of Sample 1 in Table 1.
次に、フェナントレン３０．３部［０，１７ｍｏｌコ、
ｐ−キシリレングリコール３４６５部［０，２５ｍｏｌ
コ、ｐ−）ルエンスルホン酸（１水和物）４．８部をガ
ラス製反応器に仕込み、窒素気流中、１２０ ’Ｃで１
５分間反応させたのち、フェノール３１．０部 ［０，
３３ｍｏｌ ］を投入し、さらに１０５分間縮合反応さ
せ、第１表試料２の樹脂を得た。Next, 30.3 parts of phenanthrene [0.17 mol]
p-xylylene glycol 3465 parts [0.25 mol
4.8 parts of co-,p-)luenesulfonic acid (monohydrate) were charged into a glass reactor, and heated at 120'C in a nitrogen stream for 1
After reacting for 5 minutes, 31.0 parts of phenol [0,
33 mol] was added, and the condensation reaction was further carried out for 105 minutes to obtain the resin of Sample 2 in Table 1.
得られた各樹脂は、２００℃で何分間熱処理しても硬化
せず流動点も変わらなかフた。Each of the obtained resins did not harden and its pour point did not change even after heat treatment at 200° C. for several minutes.
前記試料ｌ、２の樹脂にそれぞれヘキサメチレンテトラ
ミンを１５重量％添加し、１６０℃でフローテスター（
ノズル直径ＩＩＩＩＩｌ、長さ１ＩＩ１１、圧力１０ｋ
ｇｆ／ｃｉ）のノズルから流出がなくなることを硬化と
する硬化特性を測定したところ、それぞれ５分間、４分
間で硬化した。15% by weight of hexamethylenetetramine was added to each of the resins of Samples 1 and 2, and a flow tester (
Nozzle diameter IIIIIIl, length 1II11, pressure 10K
When curing characteristics were measured, with curing being defined as no outflow from the nozzle of gf/ci), curing occurred in 5 minutes and 4 minutes, respectively.
これをさらに２００℃で１８０分間ポストキュアすると
、さらに硬化が進み、黒色の熱硬化体となった。When this was further post-cured at 200°C for 180 minutes, curing progressed further and a black thermoset was obtained.
ボストキュア後の熱硬化体を空気中、常圧下、５℃／ｍ
ｉｎで加熱昇温し、１０％重量減少時の温度を測定した
。その結果を第２表に示す。After post-curing, the thermoset material is placed in air, under normal pressure, at 5°C/m.
The temperature was increased by heating in an inlet, and the temperature at the time of 10% weight loss was measured. The results are shown in Table 2.
なお、比較のため市販のフェノール・ノボラック−へキ
サミン系樹脂の熱硬化体（平均分子量６００、ヘキサミ
ン８ｗｔ％、高炭化収率グレード、硬化条件２００℃−
１８０分間）を前記と同条件で加熱昇温し、１０％重量
減少時の温度を測定し′た。その結果を第２表に示す。For comparison, a commercially available thermoset of phenol/novolac-hexamine resin (average molecular weight 600, hexamine 8 wt%, high carbonization yield grade, curing condition 200°C-
The temperature was increased for 180 minutes) under the same conditions as above, and the temperature at the time of 10% weight loss was measured. The results are shown in Table 2.
第 ２ 表
第１表および第２表から明らかなとおり、ｐ−キシリレ
ングリコールの配合量が少量で熱硬化しない試料１およ
び２の樹脂の場合でも、ヘキサメチレンテトラミンを架
橋剤として添加することにより、容易に熱硬化体となる
。Table 2 As is clear from Tables 1 and 2, even in the case of the resins of Samples 1 and 2, which contain a small amount of p-xylylene glycol and are not thermoset, by adding hexamethylenetetramine as a crosslinking agent. , easily becomes a thermoset.
しかも、得られる熱硬化体は、耐酸化性、耐熱分解性が
従来のフェノール樹脂の硬化体に比べ、非常に優れてい
る特徴を有する。Moreover, the resulting thermoset has excellent oxidation resistance and thermal decomposition resistance compared to conventional cured phenol resins.
比較例１
フェナントレン８９．３部［０，５ｍｏｌ］ 、 ｐ−
キシリレングリコール５１，８部［０，３７５ｍｏｆ］
、ｐ−トルエンスルホン酸（１水和物）７部をカラス製
反応器に仕込み、窒素気流下、撹拌しながら１２０℃で
１２０分間縮合反応させ、第３表に示す性での樹脂を得
た。得られた樹脂は２００℃で何分間１処理をしても硬
化せず、流動点も変わらなかつまた、ヘキサメチレンテ
トラミンを１５重蛍％ニ加し、１６０℃で３０分間の熱
処理を行ったが、流動点１１３℃の熱可塑性であり、硬
化体とはならなかった。これをさらに２００℃で１８０
分間熱処理したが、同様であった。Comparative Example 1 Phenanthrene 89.3 parts [0.5 mol], p-
Xylylene glycol 51.8 parts [0,375mof]
, 7 parts of p-toluenesulfonic acid (monohydrate) was placed in a glass reactor, and a condensation reaction was carried out at 120°C for 120 minutes with stirring under a nitrogen stream to obtain a resin with the properties shown in Table 3. . The obtained resin did not harden no matter how many minutes it was treated at 200°C, and its pour point did not change. It was thermoplastic with a pour point of 113°C, and did not form a cured product. This is further heated to 180℃ at 200℃.
The results were the same after heat treatment for a minute.
比較例２
フェナントレン８９．３部［０，５ｍｏｌ］ 、ｐ−キ
シリレングリコール６９．１部［０，５ｍｏｌ］ 、ｐ
−トルエンスルホン酸（１水和物）７．９部をガラス
製反応器に仕込み、窒素気流下、撹拌しながら１２０℃
で！２０分間縮合反応させ、第３表に示す性状の樹脂を
得た。得られた樹脂を実施例と同条件で硬化特性を測定
したところ、硬化には１５分間必要であった。Comparative Example 2 Phenanthrene 89.3 parts [0.5 mol], p-xylylene glycol 69.1 parts [0.5 mol], p
- 7.9 parts of toluenesulfonic acid (monohydrate) was charged into a glass reactor and heated to 120°C with stirring under a nitrogen stream.
in! A condensation reaction was carried out for 20 minutes to obtain a resin having the properties shown in Table 3. When the curing characteristics of the obtained resin were measured under the same conditions as in the examples, it was found that 15 minutes were required for curing.
Claims (7)
ＣＨ＿２Ｘ（ただし、Ｘ＝ＯＨ、Ｃｌ、Ｂｒ）で表され
る官能基を２個以上有する芳香族化合物を、酸触媒の存
在下、加熱せしめてなる重縮合物とヘキサメチレンテト
ラミンとからなる熱硬化性樹脂組成物。(1) Condensed polycyclic aromatic hydrocarbons, phenols, aromatic compounds having two or more functional groups represented by the general formula CH_2X (where X=OH, Cl, Br) in the presence of an acid catalyst, A thermosetting resin composition comprising a heated polycondensate and hexamethylenetetramine.
ール類との合計モルに対し、モル比で０．２以上である
特許請求の範囲第１項記載の熱硬化性樹脂組成物。(2) The thermosetting resin composition according to claim 1, wherein the molar ratio of the phenols to the total mole of the condensed polycyclic aromatic hydrocarbon and the phenols is 0.2 or more.
ｒ）で表される官能基を２個以上有する芳香族化合物が
、縮合多環芳香族炭化水素とフェノール類の合計モルに
対して、モル比で０．３〜５．０である特許請求の範囲
第１〜２項記載の熱硬化性樹脂組成物。(3) General formula CH_2X (where X=OH, Cl, B
The aromatic compound having two or more functional groups represented by r) has a molar ratio of 0.3 to 5.0 with respect to the total mole of the condensed polycyclic aromatic hydrocarbon and the phenol. Thermosetting resin composition according to items 1 and 2.
トレン、アントラセン、ピレン、フルオランテン、アセ
ナフテン、メチルナフタリン、それらを含有するピッチ
等の単独または混合物である特許請求の範囲第１〜３項
記載の熱硬化性樹脂組成物。(4) The heat according to claims 1 to 3, wherein the condensed polycyclic aromatic hydrocarbon is naphthalene, phenanthrene, anthracene, pyrene, fluoranthene, acenaphthene, methylnaphthalene, pitch containing them, etc. alone or in mixtures. Curable resin composition.
、レゾルシン、ナフトール等の１価または多価の単核フ
ェノールである特許請求の範囲第１〜４項記載の熱硬化
性樹脂組成物。(5) The thermosetting resin composition according to claims 1 to 4, wherein the phenol is a monovalent or polyvalent mononuclear phenol such as phenol, alkylphenol, resorcinol, or naphthol.
、レゾルシン、ナフトール等の１価または多価の単核フ
ェノールとホルムアルデヒド、またはパラホルムアルデ
ヒド、またはアセトンとの酸触媒による縮合で得られる
架橋基を介して結合する多核フェノールであって、未だ
フェノール核中に活性反応水素を有するものである特許
請求の範囲第１〜４項記載の熱硬化性樹脂組成物。(6) Polynuclear in which phenols are bonded via a crosslinking group obtained by acid-catalyzed condensation of a monovalent or polyvalent mononuclear phenol such as phenol, alkylphenol, resorcinol, or naphthol with formaldehyde, paraformaldehyde, or acetone. 5. The thermosetting resin composition according to claim 1, which is phenol and still has active reactive hydrogen in the phenol nucleus.
ｒ）で表される官能基を２個以上有する芳香族化合物が
キシリレングリコールである特許請求の範囲第１〜６項
記載の熱硬化性樹脂組成物。(7) General formula CH_2X (where X=OH, Cl, B
7. The thermosetting resin composition according to claim 1, wherein the aromatic compound having two or more functional groups represented by r) is xylylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7502886A JPH0725995B2 (en) | 1986-03-31 | 1986-03-31 | Thermosetting resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7502886A JPH0725995B2 (en) | 1986-03-31 | 1986-03-31 | Thermosetting resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62230842A true JPS62230842A (en) | 1987-10-09 |
| JPH0725995B2 JPH0725995B2 (en) | 1995-03-22 |
Family
ID=13564314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7502886A Expired - Lifetime JPH0725995B2 (en) | 1986-03-31 | 1986-03-31 | Thermosetting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725995B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998566A (en) * | 1994-12-05 | 1999-12-07 | Mitsubishi Gas Chemical Company, Inc. | Phenol derivatives and process for their production |
-
1986
- 1986-03-31 JP JP7502886A patent/JPH0725995B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998566A (en) * | 1994-12-05 | 1999-12-07 | Mitsubishi Gas Chemical Company, Inc. | Phenol derivatives and process for their production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0725995B2 (en) | 1995-03-22 |
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