JPS59227925A - Curing of epoxy resin - Google Patents
Curing of epoxy resinInfo
- Publication number
- JPS59227925A JPS59227925A JP10387883A JP10387883A JPS59227925A JP S59227925 A JPS59227925 A JP S59227925A JP 10387883 A JP10387883 A JP 10387883A JP 10387883 A JP10387883 A JP 10387883A JP S59227925 A JPS59227925 A JP S59227925A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- isocyanate
- curing
- imidazole
- curing agent
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 15
- 150000002460 imidazoles Chemical class 0.000 abstract description 8
- -1 isocyanate compounds Chemical class 0.000 abstract description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract description 4
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- 241000207961 Sesamum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はエポキシ樹脂の硬化方法に関する。従来、イミ
ダゾール類はエポキシ樹脂の硬化剤として汎用されてい
るが、それはイミダゾール類を用いて硬化せしめたエポ
キシ樹脂が優れた熱的、機械的、電気的および化学的特
性を有しているためである。しかし、なから、これらの
イミダゾール類を硬化剤として使用する場合、配合物の
ボッ１−ライフの長いものは、硬化温度を高くしたり、
硬化時間を長くする必要があり、配合物の硬化がより低
温で行えるものは、ボッ１−ライフが短いものとなって
しまう。また、保存安定性が悪い。そこで、これらの欠
点を改良するため、最近イソシアホー１〜基含有化合へ
とイミダゾール類を反応させ、かつ、ノボラック系樹脂
と塩を形成せしめた化合物をエポキシ樹脂の硬化剤とし
て用いる技術が開発されたが、しかしながら、より低温
での硬化性に問題がある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for curing epoxy resins. Conventionally, imidazoles have been widely used as curing agents for epoxy resins, because epoxy resins cured using imidazoles have excellent thermal, mechanical, electrical, and chemical properties. be. However, when these imidazoles are used as curing agents, it is necessary to increase the curing temperature or
It is necessary to lengthen the curing time, and if the compound can be cured at a lower temperature, the bottle life will be shortened. In addition, storage stability is poor. Therefore, in order to improve these shortcomings, a technology has recently been developed in which a compound containing one or more isothiaphor groups is reacted with imidazole and a salt is formed with a novolac resin as a curing agent for epoxy resin. However, there is a problem with curability at lower temperatures.
本発明者等は、かかる情況に鑑み、鋭意研究を重ねた結
果、本発明を提供するに至ったものである。すなわち、
エポキシ樹脂を硬化剤で硬化ネー１−を使用することを
特徴とするエポキシ樹脂の硬化方法である。In view of this situation, the present inventors have conducted extensive research and have now provided the present invention. That is,
This is a method for curing epoxy resin, which is characterized by using a curing agent as a curing agent.
本発明に使用するイソシアネート化合物としては、例え
ば、１，６−へキサメチレンジイソシアネート、■、８
−オクタメチレンジイソシアネー１−１２，２．４−１
−リメチルへキサメチレンジイソシアネート等のアルキ
レンジイソシアネー１−１３．３′−ジイソシアホー１
−ジプロピルエーテル、３−インシアホー１−メチル−
３，５，５−トリメチルシクロヘキシルイソシアネ−１
〜、１−ランスビニレンジイソシアホー１−等の不飽和
インシアホー１−１Ｉ−ルエンジイソシアネ−１〜、キ
シリレンジイソシアネー１〜．４．／Ｉ’−ジフェニル
メタンジイソシアネ−１−、フェニルイソシアネ−１・
４．４’ −ヒフェニルシイソシアネ゛−１〜等の芳香
族インシアネー１−１さらに両末端イソシアネー１−の
ブリポリマーが挙げられるが、これらの化合物に限定さ
れるものではない。Examples of the isocyanate compound used in the present invention include 1,6-hexamethylene diisocyanate,
-Octamethylene diisocyanate 1-12, 2.4-1
-Alkylene diisocyanate 1-13.3'-diisocyafol 1 such as lymethylhexamethylene diisocyanate
-dipropyl ether, 3-insiapho-1-methyl-
3,5,5-trimethylcyclohexyl isocyanate-1
~, unsaturated insiapho 1-1I-ruene diisocyane-1~ such as 1-ranyl diisocyanate 1~, xylylene diisocyanate 1~. 4. /I'-diphenylmethane diisocyanate-1-, phenylisocyane-1.
Examples include aromatic incyanes 1-1 such as 4.4'-hyphenylcyisocyanes 1-1 and bripolymers of isocyanes 1- at both terminals, but are not limited to these compounds.
また、イミダゾール類としでは、通常のイミダゾール誘
導体、例えば、イミダゾール、２−メチルイミダゾール
、２−エチルイミダツール、２−エチル−４−メチルイ
ミダゾール、２−ウンデシルイミダゾール、２−フェニ
ルイミタソール、２−フェニル−４−エチルイミダツー
ル等の活性水素基を残した化合物等が挙げられる。Further, as imidazoles, common imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimitasol, Compounds that retain active hydrogen groups such as 2-phenyl-4-ethylimidatool and the like can be mentioned.
本発明において、インシアネー１−化合物をイミダゾー
ル類でブロックする場合、公知の方法に従って行う。ブ
ロックする場合、反応促進のために触媒を加えることも
ｉｉｌ能であるが、必ずしも必要ではなく、また、非溶
媒系、溶媒系のどちらでも可能である。In the present invention, when the incyane 1-compound is blocked with imidazoles, it is carried out according to a known method. In the case of blocking, it is possible to add a catalyst to promote the reaction, but it is not always necessary, and either a non-solvent system or a solvent system is possible.
本発明は、このようにして得られるブロックイソシアネ
−１−を、エポキシ樹脂用の硬化剤として使用し、エポ
キシ樹脂を硬化せしめる方法である。The present invention is a method of curing an epoxy resin by using the thus obtained blocked isocyanate-1- as a curing agent for an epoxy resin.
本発明の硬化方法における硬化剤の作用は、次のように
考えられる。The effect of the curing agent in the curing method of the present invention can be considered as follows.
硬化剤は７０〜１１０℃の温度域で、インシアネ−１−
とイミダゾールとに解離することがｆｉＪ能であり、再
生したインシアネー１−どイミダゾールは共にエポキシ
環と反応する。すなわち、再生したイミダゾールがまず
エポキシ環の開環に作用し、生成したヒドロキシル基が
さらにイソシアネー１−と反応すると考えられる。The curing agent is incyane-1-
It is fiJ's ability to dissociate into and imidazole, and the regenerated incyane-1-dimidazole both react with the epoxy ring. That is, it is thought that the regenerated imidazole first acts to open the epoxy ring, and the generated hydroxyl group further reacts with the isocyanate 1-.
本発明の硬化法においては、他の硬化剤もしくミン鉗体
、アミンイミドどいったいわゆる潜在性硬化剤として公
知の化合物と併用し得ることは言うまでもなく、また、
必要に応じ、通常の反応性希釈剤、１■撓性賦与剤、補
強剤、充填剤、顔料、繊維物質、または、他の樹脂を添
加することもＨＪ能である。In the curing method of the present invention, it goes without saying that other curing agents or compounds known as so-called latent curing agents such as min-linkers and amine imides can be used in combination.
If desired, it is also possible to add conventional reactive diluents, flexibility agents, reinforcing agents, fillers, pigments, fibrous materials, or other resins.
本発明の硬化方法に従えば、従来と比較して、より低湿
でのエポキシ樹脂の硬化が可能となる。According to the curing method of the present invention, it is possible to cure an epoxy resin at lower humidity than in the past.
以（；、実施例により本発明をさらに詳細に説明するが
１本発明は、これらの特定の具体例に決して限定される
ものではない。なお、実施例中の部は１重量部基準であ
る。Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is in no way limited to these specific examples. Note that parts in Examples are based on 1 part by weight. .
実施例＝１
攪拌器、温度計、冷却器を取り付けた三ツ１」フラシコ
に２−メチルイミダゾール８，３部と１゜６−へキサメ
チレンジイソソアネー１−８．４部を仕込み、反応温度
を室温より７５℃まで昇温した後、遊離インシアネート
が確認されなくなるまで反応を行い、ブロックイソシア
ネー１−を得た。Example = 1 8.3 parts of 2-methylimidazole and 1-8.4 parts of 1°6-hexamethylene diisoane were charged into a three-piece 1" flask equipped with a stirrer, a thermometer, and a cooler, and reacted. After raising the temperature from room temperature to 75° C., the reaction was carried out until no free incyanate was observed to obtain blocked isocyanate 1-.
実施例−２
実施例−１と同一の装置を用い、２−エチル−４−メチ
ルイミダゾール２２，２部と１，６−へキサメチレンジ
イソシアネー１−１６．８部およびメチルエチルケトン
１０部を加えて還流ＩＳ１時間反応を行った後、反応物
を室温まで冷却し、次に５０℃で減圧（〜４０ｎｗｎＨ
ｇ）乾燥し、白色結晶のブロックイソシアネートを得た
。Example-2 Using the same equipment as in Example-1, 22.2 parts of 2-ethyl-4-methylimidazole, 1-16.8 parts of 1,6-hexamethylene diisocyanate, and 10 parts of methyl ethyl ketone were added. After carrying out the reaction for 1 hour under reflux IS, the reaction mixture was cooled to room temperature and then heated under reduced pressure (~40 nwnH) at 50°C.
g) Dried to obtain white crystalline blocked isocyanate.
実施例−３
実施例−１と同一の装置を用い、２−フェニルイミダゾ
ール５．９部と４．４′−ジェフェニルメタンジイソシ
アネー１〜２５０部およびジメチルホルムアミド１８部
を１１０℃まで昇温し、２時間反応を行い、ブロックイ
ソシアネートを得た。Example-3 Using the same equipment as in Example-1, 5.9 parts of 2-phenylimidazole, 1 to 250 parts of 4,4'-jephenylmethane diisocyanate, and 18 parts of dimethylformamide were heated to 110°C. The reaction was then carried out for 2 hours to obtain a blocked isocyanate.
実施例−４
プチルアジペ−１−（平均分子量１υ００）１００部に
１〜ルエンジイソンアネ−１−３５，０部を滴１コシな
がら反応し、両末端インシアネー１−のプレポリマーを
得た。このプレポリマーに２−メチルイミダゾール１６
．０部を加えて１０５℃で２時間加熱し、ブロックイン
シアネ−１−を得た。Example 4 100 parts of Butyl Adipate-1-(average molecular weight 1υ00) were reacted with 35.0 parts of Incyane-1-1-1 dropwise to obtain a prepolymer having incyane-1- at both ends. This prepolymer contains 2-methylimidazole 16
．． 0 part was added and heated at 105° C. for 2 hours to obtain Block in Cyane-1-.
実施例−５
メチルエチルケトン６０部に硬化剤５部およびエポキシ
樹脂（エピツー１−８２８；油化シェル■製月００部を
加え、溶解し、均一なエポキシ樹脂組成物を得た。この
エポキシ胡脂組成物の硬化皮膜形成温度およ−びゲル化
時間を測定した。同様に比較例も行った。結果を第１表
に示す。Example 5 5 parts of a curing agent and 00 parts of an epoxy resin (Epitsu 1-828; Yuka Shell ■) were added to 60 parts of methyl ethyl ketone and dissolved to obtain a uniform epoxy resin composition.This epoxy sesame composition The cured film forming temperature and gelation time of the product were measured.Comparative examples were also conducted in the same manner.The results are shown in Table 1.
注−１；エポキシ樹脂組成物を７０℃、９０℃、１１０
℃、１３０°Ｃの恒温槽中で各々３０分間加熱し、鉛筆
硬度３ Ｈの鉛筆により樹脂表面の変化が認められない
温度。Note-1: The epoxy resin composition was heated at 70°C, 90°C, and 110°C.
℃ and 130°C for 30 minutes each in a constant temperature bath, and the temperature at which no change in the resin surface is observed with a pencil with a pencil hardness of 3H.
注−２：エポキシ樹脂組成物の４０°Ｃの初期粘度が２
倍となるまでの時間（日数）
注−３；実施例−４で得られたプロツターイソシアネ−
１−にフェノール樹脂（郡栄化学社製、ＸＳＩ’−、ｘ
２ｏＩ−ｕ）を加えて反応し、イミダソール塩としたも
の
特許出願人
第一工業製薬株式会社Note-2: The initial viscosity of the epoxy resin composition at 40°C is 2.
Time until doubling (number of days) Note-3: Procter isocyanate obtained in Example-4
Phenol resin (manufactured by Gunei Chemical Co., Ltd., XSI'-, x
2oI-u) and reacted to form an imidazole salt Patent applicant Dai-ichi Kogyo Seiyaku Co., Ltd.
Claims (1)
として、イソシアホー１−化合物をイミダソール類でブ
ロックし起ブロックインシアネー１−を使用することを
特徴とするエポキシ樹脂の硬化方法。1. A method for curing an epoxy resin, which comprises using, as a curing agent, an isocyanate 1- compound obtained by blocking an isocyanate 1-compound with an imidasol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10387883A JPS59227925A (en) | 1983-06-09 | 1983-06-09 | Curing of epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10387883A JPS59227925A (en) | 1983-06-09 | 1983-06-09 | Curing of epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59227925A true JPS59227925A (en) | 1984-12-21 |
| JPS6225684B2 JPS6225684B2 (en) | 1987-06-04 |
Family
ID=14365688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10387883A Granted JPS59227925A (en) | 1983-06-09 | 1983-06-09 | Curing of epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59227925A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010261032A (en) * | 2009-04-29 | 2010-11-18 | Air Products & Chemicals Inc | Fast curable epoxy composition comprising imidazole- and 1-(aminoalkyl)imidazole-isocyanate adducts |
| JP2020125422A (en) * | 2019-02-06 | 2020-08-20 | 東ソー株式会社 | Low-temperature dissociable aqueous block polyisocyanate and coating containing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0669190U (en) * | 1993-03-08 | 1994-09-27 | 益弘 光山 | Exhibit |
-
1983
- 1983-06-09 JP JP10387883A patent/JPS59227925A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010261032A (en) * | 2009-04-29 | 2010-11-18 | Air Products & Chemicals Inc | Fast curable epoxy composition comprising imidazole- and 1-(aminoalkyl)imidazole-isocyanate adducts |
| US8357764B2 (en) | 2009-04-29 | 2013-01-22 | Air Products And Chemicals, Inc. | Fast curable epoxy compositions containing imidazole- and 1-(aminoalkyl) imidazole-isocyanate adducts |
| EP2246380A3 (en) * | 2009-04-29 | 2016-05-25 | Air Products and Chemicals, Inc. | Fast curable epoxy compositions containing imidazole- and 1-(aminoalkyl) imidazole-isocyanate adducts |
| JP2020125422A (en) * | 2019-02-06 | 2020-08-20 | 東ソー株式会社 | Low-temperature dissociable aqueous block polyisocyanate and coating containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6225684B2 (en) | 1987-06-04 |
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