JPH01126322A - Epoxy curing agent - Google Patents
Epoxy curing agentInfo
- Publication number
- JPH01126322A JPH01126322A JP28301187A JP28301187A JPH01126322A JP H01126322 A JPH01126322 A JP H01126322A JP 28301187 A JP28301187 A JP 28301187A JP 28301187 A JP28301187 A JP 28301187A JP H01126322 A JPH01126322 A JP H01126322A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- oxazoline
- anhydride
- curing agent
- acid anhydride
- 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
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 23
- 239000004593 Epoxy Substances 0.000 title claims description 12
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 17
- -1 oxazoline compound Chemical class 0.000 claims abstract description 13
- 125000000962 organic group Chemical group 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 4
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 abstract description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001361 adipic acid Substances 0.000 abstract description 5
- 235000011037 adipic acid Nutrition 0.000 abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 21
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 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 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- KOAMXHRRVFDWRQ-UHFFFAOYSA-N 4,4-dimethyl-5h-1,3-oxazole Chemical compound CC1(C)COC=N1 KOAMXHRRVFDWRQ-UHFFFAOYSA-N 0.000 description 3
- IFIUFEBEPGGBIJ-UHFFFAOYSA-N 4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC=N1 IFIUFEBEPGGBIJ-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000002918 oxazolines Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- KMJHEUHUGMDAIY-UHFFFAOYSA-N 2-[10-(4,5-dihydro-1,3-oxazol-2-yl)decyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCCCCCCCC1=NCCO1 KMJHEUHUGMDAIY-UHFFFAOYSA-N 0.000 description 1
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 description 1
- UMWUESWLHCAWKP-UHFFFAOYSA-N 2-[4-(4,4-dimethyl-5h-1,3-oxazol-2-yl)butyl]-4,4-dimethyl-5h-1,3-oxazole Chemical compound CC1(C)COC(CCCCC=2OCC(C)(C)N=2)=N1 UMWUESWLHCAWKP-UHFFFAOYSA-N 0.000 description 1
- MPPNPBNSYXFIBF-UHFFFAOYSA-N 2-[8-(4,5-dihydro-1,3-oxazol-2-yl)octyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCCCCCC1=NCCO1 MPPNPBNSYXFIBF-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- AERZMMNNWVZSNB-UHFFFAOYSA-N 3-dodec-1-ynyloxolane-2,5-dione Chemical compound CCCCCCCCCCC#CC1CC(=O)OC1=O AERZMMNNWVZSNB-UHFFFAOYSA-N 0.000 description 1
- DFATXMYLKPCSCX-UHFFFAOYSA-N 3-methylsuccinic anhydride Chemical compound CC1CC(=O)OC1=O DFATXMYLKPCSCX-UHFFFAOYSA-N 0.000 description 1
- WNIHIKIDIOKGQF-UHFFFAOYSA-N 4,4-diethyl-5h-1,3-oxazole Chemical compound CCC1(CC)COC=N1 WNIHIKIDIOKGQF-UHFFFAOYSA-N 0.000 description 1
- RWGLROKEYRSHME-UHFFFAOYSA-N 4-benzyl-4,5-dihydro-1,3-oxazole Chemical compound C=1C=CC=CC=1CC1COC=N1 RWGLROKEYRSHME-UHFFFAOYSA-N 0.000 description 1
- VITTZDWCUGTYIB-UHFFFAOYSA-N 4-butyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCC1COC=N1 VITTZDWCUGTYIB-UHFFFAOYSA-N 0.000 description 1
- CJFNLGVLNYZLEA-UHFFFAOYSA-N 4-cyclohexyl-4,5-dihydro-1,3-oxazole Chemical compound C1OC=NC1C1CCCCC1 CJFNLGVLNYZLEA-UHFFFAOYSA-N 0.000 description 1
- RWMKXFCUXJWKBU-UHFFFAOYSA-N 4-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1COC=N1 RWMKXFCUXJWKBU-UHFFFAOYSA-N 0.000 description 1
- WSGMRMBWRVIQRG-UHFFFAOYSA-N 4-methyl-2-[2-(4-methyl-4,5-dihydro-1,3-oxazol-2-yl)ethyl]-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(CCC=2OCC(C)N=2)=N1 WSGMRMBWRVIQRG-UHFFFAOYSA-N 0.000 description 1
- LWMIDUUVMLBKQF-UHFFFAOYSA-N 4-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC1CC=CC2C(=O)OC(=O)C12 LWMIDUUVMLBKQF-UHFFFAOYSA-N 0.000 description 1
- DBTPMQIQJZFVAB-UHFFFAOYSA-N 4-phenyl-4,5-dihydro-1,3-oxazole Chemical compound C1OC=NC1C1=CC=CC=C1 DBTPMQIQJZFVAB-UHFFFAOYSA-N 0.000 description 1
- HLIYUPUYSLFMEB-UHFFFAOYSA-N 4-propyl-4,5-dihydro-1,3-oxazole Chemical compound CCCC1COC=N1 HLIYUPUYSLFMEB-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- 150000001412 amines Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ZTQSADJAYQOCDD-UHFFFAOYSA-N ginsenoside-Rd2 Natural products C1CC(C2(CCC3C(C)(C)C(OC4C(C(O)C(O)C(CO)O4)O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC(C(C(O)C1O)O)OC1COC1OCC(O)C(O)C1O ZTQSADJAYQOCDD-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は、オキサゾリン変成酸無水物からなるエポキシ
硬化剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to an epoxy curing agent comprising an oxazoline-modified acid anhydride.
（従来の技術）
酸無水物はアミン系硬化剤に比較して硬化条件を厳しく
する必要があるが、ポットライフが長く。(Prior art) Acid anhydrides require stricter curing conditions than amine curing agents, but have a longer pot life.
その硬化物は、電気的特性、化学的特性、機械的特性な
どのバランスがとれており、さらに、発熱量が小さいた
め大形の成型品を作りやすいことや、皮膚刺激性が小さ
いなどの特色を有するため、エポキシ樹脂用硬化剤とし
て広く使用されている。The cured product has well-balanced electrical, chemical, and mechanical properties, and has other features such as low heat generation, making it easy to make large molded products, and low skin irritation. Because of this, it is widely used as a curing agent for epoxy resins.
しかし、酸無水物硬化エポキシ樹脂は、一般に脆性的で
あるため、内部に金物をうめこんだ成型物などでは、ク
ラックの発生に十分注意をする必要がある。耐クラツク
性を改善するため、分子量の大きいエポキシ樹脂を用い
ることや、長鎖脂肪族酸無水物、可とう性付与剤のブレ
ンドが行われている。しかし、一方で、これらの方法は
硬化物の物理的耐熱性を低下させるという欠点があった
。However, since acid anhydride-cured epoxy resins are generally brittle, sufficient care must be taken to prevent cracks from forming in molded products with metal fittings embedded inside. In order to improve crack resistance, epoxy resins with large molecular weights are used, and long-chain aliphatic acid anhydrides and flexibility-imparting agents are blended. However, on the other hand, these methods have the drawback of lowering the physical heat resistance of the cured product.
本発明者らは、すでにオキサゾリン化合物とエポキシ樹
脂から得られる硬化物が、従来の酸無水物硬化エポキシ
樹脂よりも物理的耐熱性、耐クラツク性、機械的強度の
いずれにおいても同等以上の特性が得られることを見出
だしたが、これまでの研究成果をもとに、本発明者らは
、さらに優れたエポキシ硬化剤を得ることを目的として
鋭意研究を進めた結果、ある特定の条件下でオキサゾリ
ンにより変成した酸無水物が、非常に優れたエポキシ樹
脂硬化剤になることを見出だした。オキサゾリンが酸無
水物と反応し、特定の触媒下で三次元架橋構造を形成す
ることは、すでに特開昭５５−１５１００８号公報など
で明らかにされているが、本発明の場合は、オキサゾリ
ンと二塩基酸により変成した酸無水物をエポキシ樹脂の
新規な硬化剤として用いる。The present inventors have already discovered that a cured product obtained from an oxazoline compound and an epoxy resin has properties that are equivalent to or better than conventional acid anhydride-cured epoxy resins in terms of physical heat resistance, crack resistance, and mechanical strength. However, based on the research results to date, the present inventors conducted intensive research with the aim of obtaining an even better epoxy curing agent. It has been discovered that an acid anhydride modified with oxazoline is an excellent curing agent for epoxy resins. It has already been revealed in JP-A-55-151008 that oxazoline reacts with acid anhydrides to form a three-dimensional crosslinked structure under a specific catalyst, but in the case of the present invention, oxazoline and Acid anhydrides modified with dibasic acids are used as new curing agents for epoxy resins.
（発明が解決しようとする問題点）
平均エポキシ当量が１３５〜２５０である室温で液状の
エポキシ樹脂を従来の酸無水物で硬化させた場合、その
硬化物のガラス転移温度と引張り強さ。(Problems to be Solved by the Invention) When a liquid epoxy resin having an average epoxy equivalent weight of 135 to 250 is cured at room temperature with a conventional acid anhydride, the glass transition temperature and tensile strength of the cured product.
あるいは破壊しん性値との間には、それぞれ第１図及び
第２図のような限界領域が存在し、物理的耐熱性と機械
的強度を高次元で両立させることば困難であった。Alternatively, there are limit regions as shown in FIGS. 1 and 2, respectively, between the fracture toughness values, and it has been difficult to achieve both physical heat resistance and mechanical strength at a high level.
また、オキサゾリン化合物を硬化剤としたエポキシ樹脂
では、この限界領域を越える特性を持つ硬化物が得られ
るが、化学的耐熱性に問題があり加熱硬化時に酸化によ
り着色するという問題点があった。Furthermore, with epoxy resins using oxazoline compounds as curing agents, cured products with properties exceeding this limit can be obtained, but they have problems with chemical heat resistance and coloration due to oxidation during heat curing.
本発明は、以上のような問題点を解決するためになされ
たものであり、機械的強度、物理的耐熱性、破壊しん性
値のいずれの特性においても従来の酸無水物硬化エポキ
シ樹脂以上の特性を有するとともに１作業性が良好であ
り、また、硬化時の酸化による着色を防止した硬化物が
得られるエポキシ硬化剤を提供することにある。The present invention was made to solve the above-mentioned problems, and is superior to conventional acid anhydride-cured epoxy resins in terms of mechanical strength, physical heat resistance, and fracture resistance. It is an object of the present invention to provide an epoxy curing agent which has the following characteristics, has good workability, and can provide a cured product that prevents coloring due to oxidation during curing.
（問題点を解決するための手段）
上記目的を達成するために、本発明においては、（ａ）
酸無水物 １モル
（ｂ）下記一般式であらわされるオキサゾリン化合物
０．０５〜０．４モル
（ｃ）二塩基酸 ０．０１〜０．４モルの構成比からな
るエポキシ硬化剤を提供する。(Means for solving the problems) In order to achieve the above object, in the present invention, (a)
Acid anhydride 1 mol (b) Oxazoline compound represented by the following general formula
An epoxy curing agent having a composition ratio of 0.05 to 0.4 mol (c) dibasic acid 0.01 to 0.4 mol is provided.
（作用）
本発明に使用される酸無水物としては、無水フタル酸、
ヘキサヒドロ無水フタル酸、メチルへキサヒドロ無水フ
タル酸、テトラヒドロ無水フタル酸、メチルテトラヒド
ロ無水フタル酸、無水ナジック酸、メチル無水ナジック
酸、クロレンディック酸無水物、ドデシニル無水コハク
酸、メチル無水コハク酸、無水ピロメリット酸、無水マ
レイン酸、ベンゾフェノン無水テトラカルボン酸、等が
挙げられる。これらは、単独または２種以上の混合物と
して使用される６作業性の点からは、−価の酸無水物や
液状の酸無水物で充分であるが特に耐熱性や機械特性な
どが重要な場合には、多価の酸無水物を単独か、液状酸
無水物との混合で使用するのが望ましい。(Function) The acid anhydrides used in the present invention include phthalic anhydride,
Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, chlorendic anhydride, dodecynyl succinic anhydride, methyl succinic anhydride, anhydride Examples include pyromellitic acid, maleic anhydride, benzophenone tetracarboxylic anhydride, and the like. These are used alone or as a mixture of two or more.6 From the point of view of workability, -valent acid anhydrides and liquid acid anhydrides are sufficient, but in cases where heat resistance and mechanical properties are particularly important. It is desirable to use a polyvalent acid anhydride alone or in a mixture with a liquid acid anhydride.
オキサゾリン化合物としては、次のごとき化合物を例示
できる。Examples of oxazoline compounds include the following compounds.
（１）ｎ＝ｏのときの化合物
２．２゛−ビス（２−オキサゾリン）、２．２’−ビス
（４−メチル−２−オキサゾリン）、２゜２′−ビス（
４，４−ジメチル−２−オキサゾリン）、２，２′−ビ
ス（４−エチル−２−オキサゾリン）、２，２′−ビス
（４，４−ジエチル−２−オキサゾリン）、２，２゛−
ビス（４−プロピル−２−オキサゾリン）、２，２′−
ビス（４−ブチル−２−オキサゾリン）、２，２′−ビ
ス（４−フェニル−２−オキサゾリン）、２．２’−ビ
ス（４−シクロへキシル−２−オキサゾリン）、２．２
’−ビス（４−ベンジル−２−オキサゾリン）等のビス
オキサゾリン化合物。(1) Compounds when n=o 2.2゛-bis(2-oxazoline), 2.2'-bis(4-methyl-2-oxazoline), 2゛2'-bis(
4,4-dimethyl-2-oxazoline), 2,2'-bis(4-ethyl-2-oxazoline), 2,2'-bis(4,4-diethyl-2-oxazoline), 2,2'-
Bis(4-propyl-2-oxazoline), 2,2'-
Bis(4-butyl-2-oxazoline), 2,2'-bis(4-phenyl-2-oxazoline), 2.2'-bis(4-cyclohexyl-2-oxazoline), 2.2
Bisoxazoline compounds such as '-bis(4-benzyl-2-oxazoline).
（Ｉｌ）ｎ＝１のときの化合物
２．２’−ｐ−フェニレンビス（２−オキサゾリン）、
２．２’−ｍ−フェニレンビス（２−オキサゾリン）、
２．２’−ｏ−フェニレンビス（２−オキサゾリン）、
２．２’−Ｐ−フェニレンビス（４−メチル−２−オキ
サゾリン）、２．２’−ｐ−フェニレンビス（４，４−
ジメチル−２−オキサゾリン）、２．２’−ｍ−フェニ
レンビス（４−メチル−２−オキサゾリン）、２．２’
−ｍ−フェニレンビス（４，４−ジメチル−２−オキサ
ゾリン）、２．２゛−エチレンビス（２−オキサゾリン
）、２゜２′−テトラメチレンビス（２−オキサゾリン
）、２．２′−へキサメチレンビス（２−オキサゾリン
）、２，２′−オクタメチレンビス（２−オキサゾリン
）、２，２゛−デカメチレンビス（２−オキサゾリン）
、２．２’−エチレンビス（４−メチル−２−オキサゾ
リン）、２，２゛−テトラメチレンビス（４，４−ジメ
チル−２−オキサゾリン）。(Il) Compound 2.2'-p-phenylenebis(2-oxazoline) when n=1,
2.2'-m-phenylenebis(2-oxazoline),
2.2'-o-phenylenebis(2-oxazoline),
2.2'-p-phenylenebis(4-methyl-2-oxazoline), 2.2'-p-phenylenebis(4,4-
dimethyl-2-oxazoline), 2.2'-m-phenylenebis(4-methyl-2-oxazoline), 2.2'
-m-phenylenebis(4,4-dimethyl-2-oxazoline), 2.2゛-ethylenebis(2-oxazoline), 2゛2'-tetramethylenebis(2-oxazoline), 2.2'- xamethylenebis(2-oxazoline), 2,2'-octamethylenebis(2-oxazoline), 2,2'-decamethylenebis(2-oxazoline)
, 2,2'-ethylenebis(4-methyl-2-oxazoline), 2,2'-tetramethylenebis(4,4-dimethyl-2-oxazoline).
２．２′−シクロヘキシレンビス（２−オキサゾリン）
、２．２′−ジフェニレンビス（２−オキサゾリン）等
のビスオキサゾリン化合物。2.2'-cyclohexylenebis(2-oxazoline)
, 2. Bisoxazoline compounds such as 2'-diphenylenebis(2-oxazoline).
これらの化合物は、単独または２種以上の混合物として
使用される。これらの中でも酸無水物との相溶性の良さ
、及び、取り扱い易さの点から、２．２’−ｍ−フェニ
レンビス（２−オキサゾリン）が好ましい。These compounds may be used alone or as a mixture of two or more. Among these, 2,2'-m-phenylenebis(2-oxazoline) is preferred from the viewpoint of good compatibility with acid anhydrides and ease of handling.
二塩基酸としては、マロン酸、コハク酸、アジピン酸、
ピメリン酸、スペリン酸、アゼライン酸、セバシン酸、
ドデカンニ酸、ダイマー酸、エイコサンニ酸、等の脂肪
族ジカルボン酸や、フタル酸、イソフタル酸、ナフタレ
ンジカルボン酸、ジフェニルスルホンジカルボン酸、ジ
フェニルメタンジカルボン酸１２等の芳香族ジカルボン
酸があり、取扱い易さの点から、アジピン酸等の低級脂
肪族ジカルボン酸が好ましい。これらは、２種以上混合
して用いても良い。Dibasic acids include malonic acid, succinic acid, adipic acid,
pimelic acid, speric acid, azelaic acid, sebacic acid,
There are aliphatic dicarboxylic acids such as dodecanoic acid, dimer acid, and eicosanniic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenylsulfone dicarboxylic acid, and diphenylmethane dicarboxylic acid 12, which are easy to handle. Therefore, lower aliphatic dicarboxylic acids such as adipic acid are preferred. These may be used in combination of two or more types.
これらの化合物の配合量は、酸無水物１モルに対して、
オキサゾリン化合物Ｏ，ＯＳ〜０．４モル、二塩基酸０
．０１−０．４モルの範囲であることが好ましい。この
範囲より少ない場合にはエポキシ硬化剤として使用した
場合、その硬化物の耐熱性、じん性の改善効果が少なく
、一方、多い場合には成分の析出や沈澱が生じるなど変
成酸無水物の保存安定性が悪くなる。反応温度は１００
℃〜１６０℃であることが好ましい。この範囲以下の温
度では、オキサゾリン又は二塩基酸が酸無水物に完全に
溶解しないため、反応が均一に進行しない、一方、この
範囲以上の温度では、酸無水物の脱炭酸ガス反応が生じ
、オキサゾリンと酸無水物の反応が阻害される。The blending amount of these compounds is as follows per 1 mole of acid anhydride:
Oxazoline compound O, OS ~ 0.4 mol, dibasic acid 0
．． The preferred range is 0.01-0.4 mol. If the amount is less than this range, when used as an epoxy curing agent, the effect of improving the heat resistance and toughness of the cured product will be small; if the amount is more than this range, precipitation or precipitation of components will occur, resulting in storage of modified acid anhydrides. Stability deteriorates. The reaction temperature is 100
It is preferable that it is 160 degreeC. At temperatures below this range, the oxazoline or dibasic acid does not completely dissolve in the acid anhydride, so the reaction does not proceed uniformly.On the other hand, at temperatures above this range, a decarboxylation reaction of the acid anhydride occurs, The reaction between oxazoline and acid anhydride is inhibited.
反応時間は、０．１時間〜４時間であることが好ましい
。この範囲より短い反応時間では、オキサゾリンと酸無
水物の反応が不十分であり、この範囲以上の反応時間に
なると、オキサゾリン変成酸無水物の粘度上昇が著しく
、作業性が損なわれる。The reaction time is preferably 0.1 to 4 hours. If the reaction time is shorter than this range, the reaction between the oxazoline and the acid anhydride will be insufficient, and if the reaction time is longer than this range, the viscosity of the oxazoline-modified acid anhydride will increase significantly, impairing workability.
以上に述べた組成、及び製法からなるオキサゾリン変成
酸無水物は、通常の酸無水物の長所である作業性を損な
わずに、オキサゾリン変成無水物により硬化したエポキ
シ樹脂硬化物のガラス転移温度、破壊しん性値、機械的
強度が改善される。The oxazoline-modified acid anhydride having the composition and manufacturing method described above can be used without impairing the workability, which is an advantage of ordinary acid anhydrides, and the glass transition temperature and fracture of the cured epoxy resin cured with the oxazoline-modified anhydride. Toughness value and mechanical strength are improved.
また、オキサゾリン化合物で直接エポキシ樹脂を硬化し
た場合に見られるような、加熱硬化時の硬化物表面の酸
化による着色も生じない。Furthermore, coloration due to oxidation of the surface of the cured product during heat curing does not occur, which occurs when an epoxy resin is directly cured with an oxazoline compound.
（実施例）
以下に、実施例ならびに比較例をあげ、本発明をさらに
詳細に説明する。(Example) Below, the present invention will be explained in further detail with reference to Examples and Comparative Examples.
実施例１
酸無水物としてメチルへキサヒドロ無水フタル酸（商品
名：ＨＮ−５５００、日立化成社製）１００部、オキサ
ゾリン化合物として２．２’−ｍ−フェニレンビス（２
−オキサゾリン）（武田薬品工業社製）２０部、二塩基
酸としてアジピン酸１０部（旭化成社１１１）を配合し
、１３０℃で１時間反応させて均一系液状組成物を得た
。Example 1 100 parts of methylhexahydrophthalic anhydride (trade name: HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as an acid anhydride, and 2.2'-m-phenylenebis(2) as an oxazoline compound.
-oxazoline) (manufactured by Takeda Pharmaceutical Co., Ltd.) and 10 parts of adipic acid (Asahi Kasei Co., Ltd. 111) as a dibasic acid were blended and reacted at 130° C. for 1 hour to obtain a homogeneous liquid composition.
実施例２
酸無水物としてテトラヒドロ無水フタル酸（商品名：リ
カシッドＴＨ１新日本理化社＠） １００部、オキサゾ
リン化合物として ２，２’−ｍ−フェニレンビス（２
−オキサゾリン）４０部、二塩基酸としてセバシン酸１
５部（伊藤製油社製）を配合し、１２０℃で２時間反応
させて均一系液状組成物を得た。Example 2 100 parts of tetrahydrophthalic anhydride (trade name: Rikacid TH1 Shin Nippon Chemical Co., Ltd.) as the acid anhydride, 2,2'-m-phenylenebis(2) as the oxazoline compound
-oxazoline) 40 parts, sebacic acid 1 as dibasic acid
5 parts (manufactured by Ito Oil Co., Ltd.) were blended and reacted at 120° C. for 2 hours to obtain a homogeneous liquid composition.
実施例３
酸無水物としてメチルテトラヒドロ無水フタル酸（商品
名：フィンハード２００１日本ゼオン社製）１００部、
オキサゾリン化合物として２．２’−ｍ−フェニレンビ
ス゛（２−オキサゾリン） ３０部、二塩基酸としてア
ジピン酸８部（Ｍ化成社製）を配合し、１５０℃で１６
５時間反応させて均一系液状組成物を得た。Example 3 100 parts of methyltetrahydrophthalic anhydride (trade name: Finhard 2001 manufactured by Nippon Zeon Co., Ltd.) as an acid anhydride,
30 parts of 2.2'-m-phenylene bis(2-oxazoline) as an oxazoline compound and 8 parts of adipic acid (manufactured by M Kasei Co., Ltd.) as a dibasic acid were blended, and
A homogeneous liquid composition was obtained by reacting for 5 hours.
比較例１
酸無水物硬化剤としてメチルへキサヒドロ無水フタル酸
（商品名： ＨＮ −５５００，日立化成社ｌｌ）を使
用した。Comparative Example 1 Methylhexahydrophthalic anhydride (trade name: HN-5500, Hitachi Chemical Co., Ltd.) was used as an acid anhydride curing agent.
比較例２
酸無水物硬化剤としてテトラヒドロ無水フタル酸（商品
名：リカシッドＴＨ１新日本理化社爬）を使用した。Comparative Example 2 Tetrahydrophthalic anhydride (trade name: Rikacid TH1, manufactured by Shinnihon Rikasha Co., Ltd.) was used as an acid anhydride curing agent.
比較例３
酸無水物硬化剤としてメチルテトラヒドロ無水フタル酸
（商品名：フィンハード２００、 日本ゼオン社製）を
使用した。Comparative Example 3 Methyltetrahydrophthalic anhydride (trade name: Finhard 200, manufactured by Nippon Zeon Co., Ltd.) was used as an acid anhydride curing agent.
これらの酸無水物硬化剤を、ビスフェノールＡ−ジグリ
シジルエーテル型エポキシ樹脂（商品名：エピコート８
２８、シェル社製、エポキシ当量１９０）に対して、（
酸無水物モル／エポキシ当量）＝０．９になるように配
合し、さらに硬化促進剤としてトリス−２，４，６−シ
メチルアミノメチルフエノール（商品名：に−５４、油
化シェル社製）を０．００５モル、充填剤としてアルミ
ナ粉末（平均粒径：１ＯＩＪＩＡ）を４０容量％配合し
たものを９０℃×６時間＋１３０℃×１０時間硬化して
、硬化物の特性を調査した。These acid anhydride curing agents are combined with bisphenol A diglycidyl ether type epoxy resin (trade name: Epicoat 8).
28, manufactured by Shell Co., epoxy equivalent weight 190), (
Tris-2,4,6-dimethylaminomethylphenol (trade name: Ni-54, manufactured by Yuka Shell Co., Ltd.) was added as a curing accelerator. ) and 40% by volume of alumina powder (average particle size: 1OIJIA) as a filler was cured at 90°C for 6 hours + 130°C for 10 hours, and the properties of the cured product were investigated.
その結果を表１に示す。また、硬化物はいずれも硬化時
の酸化による着色は見られなかった。The results are shown in Table 1. Furthermore, no coloration due to oxidation during curing was observed in any of the cured products.
（以下余白）
この表より明らかなように１本発明の実施例は比較例に
比べて、機械特性及び靭性が非常に優れており、従来な
しえなかった耐熱性と機械特性（特に靭性）を高次元で
両立することができる。(Leaving space below) As is clear from this table, the example of the present invention has extremely superior mechanical properties and toughness compared to the comparative example, and has achieved heat resistance and mechanical properties (particularly toughness) that were previously unachievable. It is possible to achieve both at a high level.
以上、詳述したように、本発明によれば耐熱性と機械的
特性（特に靭性）を高次元で両立することができるエポ
キシ硬化剤を提供することが可能であり、その工業的価
値は極めて大きい。As detailed above, according to the present invention, it is possible to provide an epoxy curing agent that can achieve both heat resistance and mechanical properties (particularly toughness) at a high level, and its industrial value is extremely high. big.
第１図は従来のエポキシ硬化剤によるガラス転移温度と
引張強さとの関係を示す図、□第２図は従来のエポキシ
硬化剤によるガラス転移温度と破壊しん性値との関係を
示す図である。
代理人 弁理士 則 近 憲 佑
同 第子丸 健
引っ張り強り（Ｋ２７７Ｆ１７Ｆ＋２）力゛ラス十ｒ、
オ多温座と弓１つ張り強Ｓの関イ系第１図
第２図Figure 1 is a diagram showing the relationship between glass transition temperature and tensile strength using a conventional epoxy curing agent, □Figure 2 is a diagram showing the relationship between glass transition temperature and fracture toughness value using a conventional epoxy curing agent. . Agent Patent Attorney Noriyuki Chika Ken Yudo Daishimaru Ken Tenjiri (K277F17F+2) Power Plus 10R,
Figure 1 Figure 2
Claims (1)
．０５〜０．４モル ▲数式、化学式、表等があります▼ 〔但し式中、Ｘは２価の有機基、Ｄは２価の有機基、ｎ
は０又は１であり、▲数式、化学式、表等があります▼
の環構造は５員環である。〕 （ｃ）二塩基酸０．０１〜０．４モル の構成比からなることを特徴とするエポキシ硬化剤。[Claims] (a) 1 mol of acid anhydride (b) 0 oxazoline compound represented by the following general formula
．． 05 to 0.4 mol ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [However, in the formula, X is a divalent organic group, D is a divalent organic group, n
is 0 or 1, and there are ▲mathematical formulas, chemical formulas, tables, etc.▼
The ring structure is a 5-membered ring. (c) An epoxy curing agent characterized by having a composition ratio of 0.01 to 0.4 mol of a dibasic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62283011A JPH0721044B2 (en) | 1987-11-11 | 1987-11-11 | Epoxy curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62283011A JPH0721044B2 (en) | 1987-11-11 | 1987-11-11 | Epoxy curing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01126322A true JPH01126322A (en) | 1989-05-18 |
| JPH0721044B2 JPH0721044B2 (en) | 1995-03-08 |
Family
ID=17660068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62283011A Expired - Lifetime JPH0721044B2 (en) | 1987-11-11 | 1987-11-11 | Epoxy curing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0721044B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001213940A (en) * | 2000-02-04 | 2001-08-07 | Nitto Denko Corp | Epoxy resin composition and semiconductor device |
| CN114292404A (en) * | 2021-12-30 | 2022-04-08 | 广东盈骅新材料科技有限公司 | POSS (polyhedral oligomeric silsesquioxane) modified oxazoline derivative, preparation method thereof and epoxy resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62104837A (en) * | 1985-10-31 | 1987-05-15 | Showa Electric Wire & Cable Co Ltd | Thermosetting resin composition |
| JPS6375024A (en) * | 1986-09-19 | 1988-04-05 | Toshiba Corp | Curable resin composition |
-
1987
- 1987-11-11 JP JP62283011A patent/JPH0721044B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62104837A (en) * | 1985-10-31 | 1987-05-15 | Showa Electric Wire & Cable Co Ltd | Thermosetting resin composition |
| JPS6375024A (en) * | 1986-09-19 | 1988-04-05 | Toshiba Corp | Curable resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001213940A (en) * | 2000-02-04 | 2001-08-07 | Nitto Denko Corp | Epoxy resin composition and semiconductor device |
| CN114292404A (en) * | 2021-12-30 | 2022-04-08 | 广东盈骅新材料科技有限公司 | POSS (polyhedral oligomeric silsesquioxane) modified oxazoline derivative, preparation method thereof and epoxy resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0721044B2 (en) | 1995-03-08 |
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