JPH02175756A - Thermosetting resin composition - Google Patents
Thermosetting resin compositionInfo
- Publication number
- JPH02175756A JPH02175756A JP32890488A JP32890488A JPH02175756A JP H02175756 A JPH02175756 A JP H02175756A JP 32890488 A JP32890488 A JP 32890488A JP 32890488 A JP32890488 A JP 32890488A JP H02175756 A JPH02175756 A JP H02175756A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- thermosetting resin
- resins
- thermosetting
- resin composition
- 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
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 38
- 239000011342 resin composition Substances 0.000 title claims description 21
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 10
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 7
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 5
- 229920003180 amino resin Polymers 0.000 claims abstract description 4
- 239000005011 phenolic resin Substances 0.000 claims abstract description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229920001225 polyester resin Polymers 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- -1 Allyl cyanurate Chemical compound 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 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 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000002023 wood 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］ 本発明は耐熱性に優れた熱硬化性樹脂組成物に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a thermosetting resin composition having excellent heat resistance.
熱硬化性樹脂はアミノ樹脂、フェノール樹脂に代表され
るようにホルムアルデヒドを架橋剤に用いるもの、また
は不飽和ポリエステル樹脂、アリル樹脂、ビスマレイミ
ド樹脂に代表されるように不飽和結合を介して架橋させ
るもの、さらにエポキシ系樹脂、ウレタン系樹脂のよう
に重付加反応により架橋させるもの等がある。然るにこ
れら熱硬化性樹脂はそれぞれの特性に応じて各種の用途
に利用されている。とくに電気・電子工業、自動車など
の諸工業においては現状の熱硬化性樹脂をより高温でも
使用できように、それぞれの樹脂の耐熱性を向上させる
目的でいろんな改良研究がなされている。然し、いまだ
満足のいく状態には至っていない。Thermosetting resins are those that use formaldehyde as a crosslinking agent, as typified by amino resins and phenolic resins, or are crosslinked through unsaturated bonds, as typified by unsaturated polyester resins, allyl resins, and bismaleimide resins. There are also those that are crosslinked by polyaddition reaction, such as epoxy resins and urethane resins. However, these thermosetting resins are used for various purposes depending on their characteristics. Particularly in the electrical/electronic industry, automobile industry, and other industries, various improvements are being made to improve the heat resistance of current thermosetting resins so that they can be used at higher temperatures. However, we have not yet reached a satisfactory state.
本発明の目的は、従来公知の熱硬化性樹脂が有する耐熱
性を大幅に改良した組成物を提供することにある。An object of the present invention is to provide a composition that significantly improves the heat resistance of conventionally known thermosetting resins.
（問題を解決するための手段〕
本発明者らは、上記問題を解決すべ（鋭意検討した結果
、特定の樹脂があらゆる熱硬化性樹脂の耐熱性向上に効
果があることを見出し本発明を完成した。(Means for Solving the Problems) The present inventors have solved the above problems (as a result of intensive studies, they have discovered that a specific resin is effective in improving the heat resistance of all thermosetting resins), and have completed the present invention. did.
即ち、本発明は熱硬化性樹脂１００重量部とポリカルボ
ジイミド樹脂及びｌまたはその前駆体１〜１０００重量
部よりなる熱硬化性樹脂組成物である。That is, the present invention is a thermosetting resin composition comprising 100 parts by weight of a thermosetting resin and 1 to 1000 parts by weight of a polycarbodiimide resin and a precursor thereof.
本発明に使用される熱硬化性樹脂は従来公知のものはす
べて利用できるが、特に次に示すものが好ましい。Although all conventionally known thermosetting resins can be used in the present invention, the following are particularly preferred.
即ち、アミノ樹脂、フェノール樹脂に代表されるように
ホルムアルデヒドを架橋剤に用いるもの、これにはノボ
ラック樹脂、レゾール樹脂、キシレン樹脂、メラミン樹
脂、尿素樹脂等が好ましい。That is, those using formaldehyde as a crosslinking agent, as typified by amino resins and phenol resins, include novolac resins, resol resins, xylene resins, melamine resins, urea resins, and the like.
また、不飽和ポリエステル樹脂、アリル樹脂、ビスマレ
イミド樹脂に代表されるように不飽和結合を介して架橋
させるもの、これにはアリルアルコール誘導体からなる
アリル系熱硬化性樹脂、例えばジアリルフタレート樹脂
、トリアリルシアヌレート樹脂等、またはビスマレイミ
ド系熱硬化性樹脂、例えばポリアミノビスマレイミド樹
脂、ビスマレイミドトリアジン樹脂等が好ましい。In addition, those that are crosslinked through unsaturated bonds, such as unsaturated polyester resins, allyl resins, and bismaleimide resins, include allyl thermosetting resins made of allyl alcohol derivatives, such as diallyl phthalate resins, Allyl cyanurate resin, etc., or bismaleimide thermosetting resin, such as polyamino bismaleimide resin, bismaleimide triazine resin, etc. are preferable.
さらにエポキシ系樹脂、ウレタン系樹脂のように重付加
反応により架橋したもの、例えばグリシジルエーテルエ
ポキシ樹脂、環式脂肪族エポキシ樹脂、グリシジルエス
テルエポキシ樹脂、グリシジルアミンエポキシ樹脂等、
さらにポリイソシアナートとポリオールを原料とするウ
レタン系樹脂等が好ましい。Furthermore, epoxy resins and urethane resins crosslinked by polyaddition reactions, such as glycidyl ether epoxy resins, cycloaliphatic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, etc.
Further preferred are urethane resins made from polyisocyanate and polyol.
本発明で使用されるポリカルボジイミドとは分子鎖中に
多数のカルボジイミド結合を存する高分子化合物であっ
て、有機ポリイソシアネートからイソシアネートのカル
ボジイミド化を促進する触媒の存在下に製造することが
できる。使用される有機ポリイソシアネートとしては具
体的には、２゜４−トリレンジイソシアネート、２．６
−）リレンジイソシアネート、２．４−と２．６−）リ
レンジイソシアネートの混合物、４．４°、４’−）リ
フェニルメチレントリイソシアネート、４，４′ジメチ
ルジフェニルメタン−２，２’、５，５° −テトライ
ソシアネート、キシレンジイソシアネート、ヘキサメチ
レン−１，６−ジイソシアネート、リジンジイソシアネ
ートメチルエステル、ｐ−フェニレンジイソシアネート
、ｍ−フェニレンジイソシアネート、ナフチレン−１，
５−ジイソシアネート、ｌ−メトキシフェニル−２，４
−ジイソシアネート、ジフェニルメタン−４，４°−ジ
イソシアネート、４．４′−ビフェニレンジイソシアネ
ート、３．３’−ジメトキシ−４１４゛−ビフェニルジ
イソシアネート、３．３゛−ジメチル−４，４°−ビフ
ェニルジイソシアネート、３．３’ −ジメチルジフェ
ニルメタン−４，４′−ジイソシアネート、インホロン
ジイソシアネートやこれらの有機ポリイソシアネートの
二量体以上の多核体や有機ポリイソシアネートを多官能
性活性水素化合物に対し化学量論的に過剰に用いて得ら
れる末端インシアネートプレポリマーなどを例示するこ
とができるが、中でも末端に２以上のイソシアネート基
を有する育機ジイソシアネートの一種以上を、脱炭酸す
ることにより重縮合せしめた線状のものあるいは一部架
橋したものが好ましい。The polycarbodiimide used in the present invention is a polymer compound having a large number of carbodiimide bonds in its molecular chain, and can be produced from an organic polyisocyanate in the presence of a catalyst that promotes carbodiimidation of isocyanate. Specifically, the organic polyisocyanate used is 2°4-tolylene diisocyanate, 2.6
-) lylene diisocyanate, 2.4- and 2.6-) mixture of lylene diisocyanate, 4.4°, 4'-) liphenylmethylene triisocyanate, 4,4'dimethyldiphenylmethane-2,2', 5,5 ° -tetraisocyanate, xylene diisocyanate, hexamethylene-1,6-diisocyanate, lysine diisocyanate methyl ester, p-phenylene diisocyanate, m-phenylene diisocyanate, naphthylene-1,
5-diisocyanate, l-methoxyphenyl-2,4
-diisocyanate, diphenylmethane-4,4°-diisocyanate, 4.4′-biphenylene diisocyanate, 3.3′-dimethoxy-414′-biphenyl diisocyanate, 3.3′-dimethyl-4,4°-biphenyl diisocyanate, 3. 3'-dimethyldiphenylmethane-4,4'-diisocyanate, inphorone diisocyanate, dimer or higher polynuclear forms of these organic polyisocyanates, and organic polyisocyanates in stoichiometric excess with respect to the polyfunctional active hydrogen compound. Among them, linear incyanate prepolymers obtained by polycondensation by decarboxylation of one or more types of nucleated diisocyanates having two or more isocyanate groups at the terminals can be mentioned. Partially crosslinked materials are preferred.
本発明で使用されるポリカルボジイミドはその分子末端
をモノイソシアネート化合物、−官能性活性水素化合物
等で封止したものも使用できる。The polycarbodiimide used in the present invention may also have its molecular terminals sealed with a monoisocyanate compound, a -functional active hydrogen compound, or the like.
本発明で使用されるポリカルボジイミド前駆体とは有機
ポリイソシアネートとイソシアネートのカルボジイミド
化を促進する触媒の混合物、有機ポリイソシアネートの
イソシアネート基をフェノール、アニリン等の一官能性
活性水素化合物でブロックしたものと、触媒の混合物等
が挙げられ、又この両者の混合物を使用してもよい。The polycarbodiimide precursor used in the present invention is a mixture of an organic polyisocyanate and a catalyst that promotes carbodiimidation of the isocyanate, or a mixture of an organic polyisocyanate in which the isocyanate group is blocked with a monofunctional active hydrogen compound such as phenol or aniline. , a mixture of catalysts, etc., and a mixture of both may also be used.
尚、イソシアネートのカルボジイミド化を促進する触媒
には、種々のものが挙げられるが、１−フェニル−３−
メチル−３−ホスホシン−１−オキシド、１−エチル−
３−メチル−３−ホスホルソーｌ−オキシド、ｌ−フェ
ニル−３−ホスホシン−１−オキシド、３−メチル−３
−ホスホシン−１−オキシド、１−フェニル−３−ホス
ホシン−１−スルフィド、１−エチル−３−ホスホレン
＝１−オキシドが良好である。There are various catalysts that promote carbodiimidation of isocyanate, including 1-phenyl-3-
Methyl-3-phosphosine-1-oxide, 1-ethyl-
3-Methyl-3-phosphorso l-oxide, l-phenyl-3-phosphosine-1-oxide, 3-methyl-3
-phosphosine-1-oxide, 1-phenyl-3-phosphosine-1-sulfide, and 1-ethyl-3-phosphorene 1-oxide are preferred.
本発明におけるポリカルボジイミド及び／又はその前駆
体の配合量は熱硬化性樹脂１００重量部に対して、１〜
１０００重量部の割合で使用される。In the present invention, the blending amount of polycarbodiimide and/or its precursor is 1 to 1 to 100 parts by weight of the thermosetting resin.
It is used in a proportion of 1000 parts by weight.
ポリカルボジイミド及び／又はその前駆体が１！量部未
満では本発明の目的である耐熱性向上の効果は得られな
い。また１０００重量部以上使用すると、樹脂組成物に
使用した熱硬化性樹脂の特性が失われる。Polycarbodiimide and/or its precursor is 1! If the amount is less than 1 part, the effect of improving heat resistance, which is the objective of the present invention, cannot be obtained. If 1000 parts by weight or more is used, the properties of the thermosetting resin used in the resin composition will be lost.
本発明による樹脂組成物は通常公知の方法により製造で
きるが、特に次に示す方法が好ましい。The resin composition according to the present invention can be produced by a generally known method, but the following method is particularly preferred.
（１）熱硬化性樹脂ベレット又は粉末とポリカルボジイ
ミド粉末及び／又はその前駆体を乳鉢、ヘンシェルミキ
サー、ドラムブレンダー、タンブラーブレンダー、ボー
ルミルなどを利用して混合し、必要に応じて熔融混合機
、熱ロール等で混練した後、ベレント又は粉状にする。(1) Mix thermosetting resin pellets or powder with polycarbodiimide powder and/or its precursor using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill, etc., and use a melt mixer or heat as necessary. After kneading with a roll or the like, make it into berent or powder.
尚、溶融混合機、熱ロール等の温度は本発明樹脂組成物
の一成分である熱硬化性樹脂の溶融点以上で使用するこ
とが望ましい。The temperature of the melt mixer, hot roll, etc. is desirably higher than the melting point of the thermosetting resin, which is one of the components of the resin composition of the present invention.
（２）熱硬化性樹脂とポリカルボジイミド及び／又はそ
の前駆体を有ｊａ溶媒に溶解あるいは懸濁させた後、該
溶剤を除去して組成物とすることもできる使用可能な有
ｍ溶媒としては両成分と実質的に反応しない溶媒であれ
ばよく、それぞれ使用する熱硬化性樹脂及びポリカルボ
ジイミドに応じて適宜選択すると良い。(2) Usable solvents that can be used include dissolving or suspending the thermosetting resin, polycarbodiimide, and/or its precursor in a solvent, and then removing the solvent to obtain a composition. Any solvent may be used as long as it does not substantially react with both components, and may be appropriately selected depending on the thermosetting resin and polycarbodiimide used.
また、本発明の樹脂組成物に対して、本発明の目的をそ
こなわない範囲で、酸化防止剤および熱安定剤、紫外線
吸収剤、難燃助剤、帯電防止剤、滑剤、着色剤などの通
常の添加剤を１種以上添加することができる。In addition, antioxidants, heat stabilizers, ultraviolet absorbers, flame retardant aids, antistatic agents, lubricants, colorants, etc. may be added to the resin composition of the present invention within a range that does not impair the purpose of the present invention. One or more conventional additives can be added.
また、ガラス繊維、炭素繊維、芳香族ポリアミド繊維、
アルミナ繊維、チタン酸カリウム繊維などの補強材やク
レー、マイカ、シリカ、グラファイト、ガラスピーズ、
アルミナ炭酸カルシウムなどの充填材もその目的に応じ
て適当量を配合することも可能である。In addition, glass fiber, carbon fiber, aromatic polyamide fiber,
Reinforcing materials such as alumina fiber, potassium titanate fiber, clay, mica, silica, graphite, glass beads,
Fillers such as alumina and calcium carbonate can also be blended in appropriate amounts depending on the purpose.
本発明の樹脂組成物は射出成形法、圧縮成形法、トラン
スファー成形法、押出成形法、流延フィルム決算公知の
成形法により成形され実用に供される。The resin composition of the present invention is molded and put to practical use by injection molding, compression molding, transfer molding, extrusion molding, or cast film casting.
〔実施例］ 以下に実施例を挙げて本発明をさらに詳しく説明する。〔Example] The present invention will be explained in more detail with reference to Examples below.
ただし、本発明はこれらの実施例に限定されるものでは
ない。However, the present invention is not limited to these examples.
実施例１
エポキシ樹脂（油化シェルエポキシ社製：商品名エピコ
ート８２８） １００重量部にジエチレントリアミン６
重量部これに２．４−）リレンジイソシアネートを原料
としたポリカルボジイミド粉末１０重量部を添加し、混
練して樹脂組成物を得た。 この樹脂組成物を金型（１
１０ＸＬ２．７Ｘ６．４ｆｆｉｍ）に注入し、常温で２
４時間放置して成形物を得た。Example 1 Diethylenetriamine 6 was added to 100 parts by weight of epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.: trade name Epicote 828).
Parts by weight 10 parts by weight of polycarbodiimide powder made from 2.4-)lylene diisocyanate was added and kneaded to obtain a resin composition. This resin composition was poured into a mold (1
10XL 2.7
A molded product was obtained by leaving it for 4 hours.
得られた成形体はＪＩＳ Ｋ−６９１１に準して熱変形
温度を測定したところ、１１５°Ｃであった。The heat distortion temperature of the obtained molded body was measured according to JIS K-6911, and it was found to be 115°C.
比較例１
ポリカルボジイミド粉末を使用しない以外は実施例１と
同様にして成形物をえた。このものの熱変形温度は１０
５°Ｃであった。Comparative Example 1 A molded article was obtained in the same manner as in Example 1 except that the polycarbodiimide powder was not used. The heat distortion temperature of this item is 10
It was 5°C.
実施例２
ノボラック樹脂（三井東圧化学社製：商品名ミレックス
２０００） １００重量部、木粉１００重量部、ヘキサ
メチレンテトラミン１１１部にジフェニルメタン−４，
４゛−ジイソシアネートを原料としたポリカルボジイミ
ド粉末５１１部を加え、ヘンシェル・ミキサーで混合し
て粉状の樹脂組成物を得た、このものを圧縮成形機によ
り、金型（１１０Ｘ１２．７Ｘ６．４ｍｍ）を使用し、
１８０″Ｃ１圧力１００Ｋｇ／ｃａ＋”の条件で５分間
、圧縮成形した。得られた成形体はＪＩＳ Ｋ−６９１
１に準じて熱変形温度を測定したところ、１４３’Ｃで
あった。Example 2 100 parts by weight of novolac resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name Mirex 2000), 100 parts by weight of wood flour, 111 parts of hexamethylenetetramine, diphenylmethane-4,
511 parts of polycarbodiimide powder made from 4'-diisocyanate was added and mixed in a Henschel mixer to obtain a powdered resin composition. This was molded into a mold (110 x 12.7 x 6.4 mm) using a compression molding machine. using
Compression molding was carried out for 5 minutes under the conditions of 180" C1 pressure 100 Kg/ca+". The obtained molded product conforms to JIS K-691
The heat distortion temperature was measured according to 1 and found to be 143'C.
比較例２
ポリカルボジイミド粉末を使用しない以外は実施例１と
同様にして成形物をえた。このものの熱変形温度は１３
０°Ｃであった。Comparative Example 2 A molded article was obtained in the same manner as in Example 1 except that the polycarbodiimide powder was not used. The heat distortion temperature of this item is 13
It was 0°C.
実施例３
実施例２のポリカルボジイミドの代わりに、ポリカルボ
ジイミド前駆体として、２．４−及び２．６−ドリレン
ジイソシアネートＩＸ１ （モル比）のフェノールブロ
ック体３０重量部及び触媒１−フェニル−３−メチル−
３−ホスホシン−１オキ２１０．２重量部を用いた他は
実施例２と同様にして成形物をえた。このものの熱変形
温度は１４５°Ｃであった。Example 3 Instead of the polycarbodiimide of Example 2, 30 parts by weight of a phenol block of 2,4- and 2,6-tolylene diisocyanate IX1 (molar ratio) and a catalyst 1-phenyl-3 were used as a polycarbodiimide precursor. -Methyl-
A molded product was obtained in the same manner as in Example 2, except that 210.2 parts by weight of 3-phosphosine-1-oxygen was used. The heat distortion temperature of this product was 145°C.
実施例４
ポリアミノビスマレイミド樹脂（日本ポリイミド社製：
商品名ケルイミド６０１）１００重量部に２゜６−ドリ
レンジイソシアネートを原料としたポリカルボジイミド
粉末２０重量部を用いて、均一に混合して樹脂組成物を
えた。Example 4 Polyamino bismaleimide resin (manufactured by Nippon Polyimide Co., Ltd.:
A resin composition was obtained by uniformly mixing 20 parts by weight of polycarbodiimide powder made from 2°6-lylene diisocyanate with 100 parts by weight of Kerimide (trade name 601).
このものを圧縮成形機により、金型（１１０ＸＩ２．７
Ｘ６．４ｍｍ）を使用し、２００℃、圧力５０Ｋｇ／ａ
ｍ”、の条件で３０分間、圧縮成形した。得られた成形
体の熱変形温度を測定したところ、１８２ ’Ｃであっ
た。This material was molded into a mold (110XI2.7
x6.4mm), 200℃, pressure 50Kg/a
The molded product was compression-molded for 30 minutes under the conditions of 182'C.
比較例３
ポリカルボシイ幾ド粉末を使用しない以外は実施例４と
同様にして成形体を得た。このものの熱変形温度は１６
０°Ｃであった。Comparative Example 3 A molded article was obtained in the same manner as in Example 4, except that the polycarboxylic acid powder was not used. The heat distortion temperature of this item is 16
It was 0°C.
（発明の効果〕
本発明の樹脂組成物は、それぞれ原料とする熱硬化性樹
脂の耐熱性を大幅に改良しており、産業上の利用価値は
極めて大きい。(Effects of the Invention) The resin compositions of the present invention have greatly improved the heat resistance of the thermosetting resins used as raw materials, and have extremely high industrial utility value.
特許出願人 三井東圧化学株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
脂及び／またはその前駆体１〜１０００重量部よりなる
熱硬化性樹脂組成物。 ２、熱硬化性樹脂がフェノール系樹脂である請求項１記
載の熱硬化性樹脂組成物。 ３、熱硬化性樹脂がアミノ系樹脂である請求項１記載の
熱硬化性樹脂組成物。 ４、熱硬化性樹脂が不飽和ポリエステル系樹脂である請
求項１記載の熱硬化性樹脂組成物。 ５、熱硬化性樹脂がエポキシ系樹脂である請求項１記載
の熱硬化性樹脂組成物。 ６、熱硬化性樹脂がアリル系樹脂である請求項１記載の
熱硬化性樹脂組成物。 ７、熱硬化性樹脂がウレタン樹脂である請求項１記載の
熱硬化性樹脂組成物。 ８、熱硬化性樹脂がビスマレイミド系樹脂である請求項
１記載の熱硬化性樹脂組成物。Claims: 1. A thermosetting resin composition comprising 100 parts by weight of a thermosetting resin and 1 to 1000 parts by weight of a polycarbodiimide resin and/or its precursor. 2. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is a phenolic resin. 3. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is an amino resin. 4. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is an unsaturated polyester resin. 5. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is an epoxy resin. 6. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is an allyl resin. 7. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is a urethane resin. 8. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is a bismaleimide resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32890488A JPH02175756A (en) | 1988-12-28 | 1988-12-28 | Thermosetting resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32890488A JPH02175756A (en) | 1988-12-28 | 1988-12-28 | Thermosetting resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02175756A true JPH02175756A (en) | 1990-07-09 |
Family
ID=18215389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32890488A Pending JPH02175756A (en) | 1988-12-28 | 1988-12-28 | Thermosetting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02175756A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001207055A (en) * | 2000-01-25 | 2001-07-31 | Nitto Denko Corp | Carbodiimide resin composition |
| JP2016079220A (en) * | 2014-10-10 | 2016-05-16 | 日立化成株式会社 | Compound having imide group and carbodiimide group in molecule, producing method thereof, resin composition, prepreg, laminated sheet and film |
| KR20170057248A (en) | 2014-09-11 | 2017-05-24 | 데이진 가부시키가이샤 | Thermosetting resin composition |
-
1988
- 1988-12-28 JP JP32890488A patent/JPH02175756A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001207055A (en) * | 2000-01-25 | 2001-07-31 | Nitto Denko Corp | Carbodiimide resin composition |
| KR20170057248A (en) | 2014-09-11 | 2017-05-24 | 데이진 가부시키가이샤 | Thermosetting resin composition |
| US10865272B2 (en) | 2014-09-11 | 2020-12-15 | Teijin Limited | Thermosetting resin composition |
| JP2016079220A (en) * | 2014-10-10 | 2016-05-16 | 日立化成株式会社 | Compound having imide group and carbodiimide group in molecule, producing method thereof, resin composition, prepreg, laminated sheet and film |
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