JP4596123B2 - Low temperature curing type epoxy resin curing agent and epoxy resin composition - Google Patents
Low temperature curing type epoxy resin curing agent and epoxy resin composition Download PDFInfo
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- JP4596123B2 JP4596123B2 JP2004034825A JP2004034825A JP4596123B2 JP 4596123 B2 JP4596123 B2 JP 4596123B2 JP 2004034825 A JP2004034825 A JP 2004034825A JP 2004034825 A JP2004034825 A JP 2004034825A JP 4596123 B2 JP4596123 B2 JP 4596123B2
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- 229920000647 polyepoxide Polymers 0.000 title claims description 110
- 239000003822 epoxy resin Substances 0.000 title claims description 102
- 239000003795 chemical substances by application Substances 0.000 title claims description 69
- 239000000203 mixture Substances 0.000 title claims description 41
- 238000001723 curing Methods 0.000 title description 93
- 238000013035 low temperature curing Methods 0.000 title description 2
- -1 aliphatic diamine Chemical class 0.000 claims description 47
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 17
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 14
- 150000002894 organic compounds Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- 150000001491 aromatic compounds Chemical class 0.000 claims description 6
- 125000004956 cyclohexylene group Chemical group 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 238000000576 coating method Methods 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- 239000007795 chemical reaction product Substances 0.000 description 14
- 238000006683 Mannich reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 6
- 235000010746 mayonnaise Nutrition 0.000 description 6
- 239000008268 mayonnaise Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 2
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 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 2
- 230000001771 impaired effect Effects 0.000 description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- BRRSNXCXLSVPFC-UHFFFAOYSA-N 2,3,4-Trihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1O BRRSNXCXLSVPFC-UHFFFAOYSA-N 0.000 description 1
- WZPLEIAOQJXZJX-UHFFFAOYSA-N 2,3-dihydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C(O)=CC2=C1 WZPLEIAOQJXZJX-UHFFFAOYSA-N 0.000 description 1
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 1
- ICBJKTLBDCTDDE-UHFFFAOYSA-N 2-(hydroxymethoxy)naphthalene-1-carboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(OCO)=CC=C21 ICBJKTLBDCTDDE-UHFFFAOYSA-N 0.000 description 1
- XGAYQDWZIPRBPF-UHFFFAOYSA-N 2-hydroxy-3-propan-2-ylbenzoic acid Chemical compound CC(C)C1=CC=CC(C(O)=O)=C1O XGAYQDWZIPRBPF-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HCJMNOSIAGSZBM-UHFFFAOYSA-N 6-methylsalicylic acid Chemical compound CC1=CC=CC(O)=C1C(O)=O HCJMNOSIAGSZBM-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BDYVWDMHYNGVGE-UHFFFAOYSA-N [2-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCCC1CN BDYVWDMHYNGVGE-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
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- 238000009408 flooring Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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Landscapes
- Epoxy Resins (AREA)
Description
本発明はポリアミノ化合物と硬化促進剤とを含む低温硬化型エポキシ樹脂硬化剤及び該エポキシ樹脂硬化剤を含むエポキシ樹脂組成物に関する。該エポキシ樹脂硬化剤は、自動車用電着塗料、船舶・橋梁・陸海上鉄構築物用重防食塗料、飲料用缶の内面塗装用塗料などの塗料用途、積層板、半導体封止材、絶縁粉体塗料、コイル含浸として家電製品、通信機器、自動車・航空機の制御系などに用いられる電気・電子用途、橋梁の耐震補強、コンクリート構造物のライニング・補強・補修、建築物の床材、上下水道設備のライニング、排水・透水舗装などの土木・建築用途、車両・航空機用などの接着剤用途、航空機、産業資材、スポーツ用品などの複合材料用途などのきわめて広い分野で利用されているエポキシ樹脂の硬化剤として利用することができる。 The present invention relates to a low temperature curing type epoxy resin curing agent containing a polyamino compound and a curing accelerator, and an epoxy resin composition containing the epoxy resin curing agent. The epoxy resin curing agent is used for coatings such as electrodeposition coatings for automobiles, heavy-duty anticorrosion coatings for ships, bridges, land and marine iron structures, coatings for the inner surface of beverage cans, laminates, semiconductor encapsulants, insulating powders Paints, coil impregnation, home appliances, communication equipment, electrical / electronic applications used in automobile / aircraft control systems, etc., earthquake-resistant reinforcement of bridges, lining / reinforcement / repair of concrete structures, flooring of buildings, water and sewage equipment Curing of epoxy resins used in a wide range of fields such as linings, civil engineering and construction applications such as drainage and permeable pavement, adhesives applications for vehicles and aircraft, composite materials applications such as aircraft, industrial materials and sports equipment It can be used as an agent.
脂肪族、脂環族アミノ化合物がエポキシ樹脂硬化剤あるいはその原料として用いられていることは広く知られている。脂肪族アミノ化合物の中で、（１）式の脂肪族ジアミンを原料とする硬化剤を使用すると、低温での硬化が速く、耐薬品性に優れた硬化物を与えるなどの特徴が得られる。 It is widely known that aliphatic and alicyclic amino compounds are used as epoxy resin curing agents or their raw materials. Among the aliphatic amino compounds, when a curing agent using the aliphatic diamine of the formula (1) as a raw material is used, characteristics such as quick curing at a low temperature and giving a cured product excellent in chemical resistance can be obtained.
Ｈ２Ｎ−Ｈ２Ｃ−Ａ−ＣＨ２−ＮＨ２ （１）
（Ａはフェニレン基またはシクロヘキシレン基を示す。）
H 2 N-H 2 C- A-CH 2 -NH 2 (1)
(A represents a phenylene group or a cyclohexylene group.)
しかしその一方で、（１）式の脂肪族ジアミンは、大気中の二酸化炭素や水蒸気を吸収してカルバミン酸塩を生成しやすいために、硬化剤として使用したエポキシ樹脂塗膜に白化現象やべたつきを発生させるという欠点がある。 However, on the other hand, since the aliphatic diamine of the formula (1) easily absorbs carbon dioxide and water vapor in the atmosphere to generate carbamate, the whitening phenomenon and stickiness are caused in the epoxy resin coating film used as a curing agent. Has the disadvantage of generating
そのため（１）式の脂肪族ジアミンは、無変性のままでエポキシ樹脂硬化剤として使用されることは少なく、種々の変性を行って使用されている。代表的な変性方法としては、カルボキシル基を有する化合物との反応による変性、エポキシ化合物との反応による変性、アルデヒド化合物とフェノール化合物とのマンニッヒ反応による変性、アクリル化合物とのマイケル付加反応による変性、などが挙げられる。 Therefore, the aliphatic diamine of the formula (1) is rarely used as an epoxy resin curing agent while remaining unmodified, and is used after various modifications. Typical modification methods include modification by reaction with a compound having a carboxyl group, modification by reaction with an epoxy compound, modification by Mannich reaction between an aldehyde compound and a phenol compound, modification by Michael addition reaction with an acrylic compound, etc. Is mentioned.
種々の変性の中で、アミノ化合物とアルデヒド化合物とフェノール化合物との変性によるマンニッヒ反応生成物は硬化速度が速いという特徴を持つ。またこの中でも、（１）式の脂肪族ジアミンのマンニッヒ反応生成物は、硬化速度が速いとう特徴を生かして、低温硬化性を要求される分野におけるエポキシ樹脂硬化剤として広く用いられている（非特許文献１参照。）。 Among various modifications, the Mannich reaction product resulting from the modification of an amino compound, an aldehyde compound, and a phenol compound is characterized by a high curing rate. Among these, the Mannich reaction product of the aliphatic diamine of the formula (1) is widely used as an epoxy resin curing agent in a field requiring low-temperature curability by taking advantage of its fast curing speed (non- (See Patent Document 1).
一般に硬化剤の粘度は、作業性の観点から低粘度であることが好ましい。マンニッヒ反応生成物はアミノ化合物とアルデヒド化合物とフェノール化合物の変性物であるため、アミノ化合物に対するアルデヒド化合物の反応モル比を減少させるか、またはアミノ化合物に対するフェノール化合物の反応モル比を増大させることにより、低粘度のマンニッヒ反応生成物を得ることができる。しかし、このような変性を行った低粘度のマンニッヒ反応生成物には、未反応のフェノール化合物が比較的多く残存する。現在、マンニッヒ反応生成物の原料フェノール化合物の中では、フェノールが一般的に用いられているが、フェノールは劇物に指定されており、また変異原性も確認されていることから、マンニッヒ反応生成物中に未反応のフェノールが残存することは好ましくないと考えられるようになり、近年フェノールを使用しない傾向が強まっている。 In general, the viscosity of the curing agent is preferably low from the viewpoint of workability. Since the Mannich reaction product is a modified product of an amino compound, an aldehyde compound, and a phenol compound, by reducing the reaction molar ratio of the aldehyde compound to the amino compound or increasing the reaction molar ratio of the phenol compound to the amino compound, A low viscosity Mannich reaction product can be obtained. However, a relatively large amount of unreacted phenolic compound remains in the low viscosity Mannich reaction product subjected to such modification. Currently, phenol is generally used among the raw material phenolic compounds of the Mannich reaction products, but since phenol has been designated as a deleterious substance and mutagenicity has been confirmed, the Mannich reaction product is generated. It is considered that it is not preferable that unreacted phenol remains in the product, and in recent years, there is an increasing tendency not to use phenol.
また、マンニッヒ反応生成物中に残存している未反応フェノール量を減少させるために、アミノ化合物に対するアルデヒド化合物の反応モル比を増大させるか、またはアミノ化合物に対するフェノール化合物の反応モル比を減少させる方法が考えられる。しかし、この方法によって生成されるマンニッヒ反応生成物は粘度が高くなる。粘度の高いマンニッヒ反応生成物を硬化剤、あるいはその原料として用いる場合には、作業性を改善するため、溶剤で希釈することが必要となる。近年、塗料用エポキシ樹脂に使用される硬化剤は、地球環境の汚染防止の観点から溶剤を使用しない傾向が強まってきており、無溶剤系での使用が可能なエポキシ樹脂硬化剤が求められている。 Further, in order to reduce the amount of unreacted phenol remaining in the Mannich reaction product, a method of increasing the reaction molar ratio of the aldehyde compound to the amino compound or decreasing the reaction molar ratio of the phenol compound to the amino compound Can be considered. However, the Mannich reaction product produced by this method has a high viscosity. When a highly viscous Mannich reaction product is used as a curing agent or its raw material, it is necessary to dilute with a solvent in order to improve workability. In recent years, curing agents used for epoxy resins for paints have been increasingly used without solvent from the viewpoint of preventing pollution of the global environment, and there is a demand for epoxy resin curing agents that can be used in solvent-free systems. Yes.
また、エポキシ樹脂硬化剤として、メタキシレンジアミン等を変性したアミノ化合物が紹介されており、該アミノ化合物は、比較的低粘度であることが開示されている（特許文献１参照。）。しかし、この文献記載の化合物は、エポキシ樹脂硬化剤として使用した場合、常温で長いポットライフを示すことが例示されており、低温条件では硬化が進行しないと考えられる。 Also, amino compounds obtained by modifying metaxylenediamine or the like have been introduced as epoxy resin curing agents, and it is disclosed that the amino compounds have a relatively low viscosity (see Patent Document 1). However, the compounds described in this document are exemplified to exhibit a long pot life at room temperature when used as an epoxy resin curing agent, and it is considered that curing does not proceed under low temperature conditions.
本発明の目的は、アミノ化合物を用いたエポキシ樹脂硬化剤であって、フェノールや溶剤のような環境に有害な物質を化合物中に残存成分として含有することなく低粘度化を実現し、且つ低温で良好な硬化性および良好な塗膜外観を示すエポキシ樹脂硬化物を与えうるエポキシ樹脂硬化剤を提供することである。 An object of the present invention is an epoxy resin curing agent using an amino compound, which realizes a low viscosity without containing environmentally harmful substances such as phenols and solvents as residual components in the compound, and is low in temperature. It is to provide an epoxy resin curing agent capable of providing an epoxy resin cured product exhibiting good curability and good coating film appearance.
本発明者らは、鋭意検討した結果、（１）式の脂肪族ジアミンとスチレンとの付加反応により得られるポリアミノ化合物、および分子内にカルボキシル基および水酸基を持つ有機化合物を含む硬化促進剤を含むエポキシ樹脂硬化剤を使用すると、得られたエポキシ樹脂組成物は低温で良好な硬化性を有すると共に、良好な塗膜外観を有することを見出して本発明に至った。 As a result of intensive studies, the inventors of the present invention include a polyamino compound obtained by the addition reaction of the aliphatic diamine of formula (1) and styrene, and a curing accelerator containing an organic compound having a carboxyl group and a hydroxyl group in the molecule. When an epoxy resin curing agent was used, the obtained epoxy resin composition was found to have good curability at low temperatures and a good coating film appearance, leading to the present invention.
すなわち、本発明は、以下の１）〜４）に示すエポキシ樹脂硬化剤、５）に示すエポキシ樹脂組成物、６）に示すエポキシ樹脂硬化物を提供する。
１）（１）式で表される脂肪族ジアミンとスチレンとの反応により得られるポリアミノ化合物、および分子内にカルボキシル基および水酸基を持つ有機化合物を含む硬化促進剤を含むエポキシ樹脂硬化剤。
Ｈ２Ｎ−Ｈ２Ｃ−Ａ−ＣＨ２−ＮＨ２ （１）
（Ａはフェニレン基またはシクロヘキシレン基を示す。）
２）前記有機化合物が、炭素数７〜１２の芳香族化合物である、１）記載のエポキシ樹脂硬化剤。
３）前記有機化合物がサリチル酸である１）記載のエポキシ樹脂硬化剤。
４）前記ポリアミノ化合物１００重量部に対し（１）式で表される脂肪族ジアミン２重量部未満を含む、１）〜３）のいずれかに記載のエポキシ樹脂硬化剤。
５）１）〜４）のいずれかに記載のエポキシ樹脂硬化剤とエポキシ樹脂を含むエポキシ樹脂組成物。
６）５）記載のエポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物。
That is, the present invention provides the epoxy resin curing agent shown in the following 1) to 4), the epoxy resin composition shown in 5), and the epoxy resin cured product shown in 6).
1) An epoxy resin curing agent comprising a curing accelerator comprising a polyamino compound obtained by the reaction of an aliphatic diamine represented by the formula (1) and styrene, and an organic compound having a carboxyl group and a hydroxyl group in the molecule.
H 2 N-H 2 C- A-CH 2 -NH 2 (1)
(A represents a phenylene group or a cyclohexylene group.)
2) The epoxy resin curing agent according to 1), wherein the organic compound is an aromatic compound having 7 to 12 carbon atoms.
3) The epoxy resin curing agent according to 1), wherein the organic compound is salicylic acid.
4) The epoxy resin curing agent according to any one of 1) to 3), comprising less than 2 parts by weight of the aliphatic diamine represented by the formula (1) with respect to 100 parts by weight of the polyamino compound.
5) An epoxy resin composition comprising the epoxy resin curing agent according to any one of 1) to 4) and an epoxy resin.
6) A cured epoxy resin obtained by curing the epoxy resin composition according to 5).
本発明のエポキシ樹脂硬化剤は、フェノールや溶剤などの環境に有害な物質を含有することなく、粘度が低く、該エポキシ樹脂硬化剤を用いたエポキシ樹脂組成物は、低温で良好な硬化性、および良好な塗膜外観等の性能を示す。 The epoxy resin curing agent of the present invention has a low viscosity without containing substances harmful to the environment such as phenol and solvent, and the epoxy resin composition using the epoxy resin curing agent has good curability at low temperature, And the performance such as good coating film appearance is shown.
本発明における（１）式で表される脂肪族ジアミンとしては、オルソキシリレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、１，２−ビス（アミノメチル）シクロヘキサン、１，３−ビス（アミノメチル）シクロヘキサン、１，４−ビス（アミノメチル）シクロヘキサン等があげられる。この中で、特に好ましいのはメタキシリレンジアミンおよび１，３−ビス（アミノメチル）シクロヘキサンである。これらは各々単独で用いても、また２種以上を併用しても良い。 Examples of the aliphatic diamine represented by the formula (1) in the present invention include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (amino). Methyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like. Of these, metaxylylenediamine and 1,3-bis (aminomethyl) cyclohexane are particularly preferred. These may be used alone or in combination of two or more.
本発明におけるポリアミノ化合物は、（１）式の脂肪族ジアミンとスチレンの付加反応によって得られ、互いに側鎖基の構成が異なる各付加物の混合物である。
互いに側鎖基の構成が異なる各付加物の例として、（１）式の脂肪族ジアミン１分子の１つの１級アミノ基にスチレン１分子が付加した付加物（１付加物）、（１）式の脂肪族ジアミン１分子の２つの１級アミノ基それぞれにスチレン１分子が付加した付加物（２付加物−１）、（１）式の脂肪族ジアミン１分子の１つの１級アミノ基にスチレン２分子が付加した付加物（２付加物−２）、（１）式の脂肪族ジアミン１分子の１つの１級アミノ基にスチレン２分子が付加し、もう１つの１級アミノ基にスチレン１分子が付加した付加物（３付加物）、および（１）式の脂肪族ジアミン１分子の２つの１級アミノ基それぞれにスチレン２分子が付加した付加物（４付加物）が挙げられる。ここで、（１）式の脂肪族ジアミンとスチレンの付加反応によって得られるポリアミノ化合物に含まれる各付加物の混合物中、１付加物、２付加物−１、および２付加物−２の含有量は５０重量％以上が好ましく、７０重量％以上がさらに好ましい。
The polyamino compound in the present invention is a mixture of adducts obtained by addition reaction of the aliphatic diamine of the formula (1) and styrene and having different side chain groups.
Examples of adducts having different side chain groups from each other include adducts (one adduct) in which one molecule of styrene is added to one primary amino group of one molecule of aliphatic diamine of formula (1), (1) An adduct obtained by adding one molecule of styrene to each of two primary amino groups of one molecule of an aliphatic diamine of formula (2-adduct-1), and one primary amino group of one molecule of an aliphatic diamine of formula (1) Two adducts of styrene (2 adduct-2), two molecules of styrene are added to one primary amino group of one molecule of the aliphatic diamine of formula (1), and styrene is added to the other primary amino group. Examples thereof include an adduct in which 1 molecule is added (3 adduct) and an adduct in which 2 molecules of styrene are added to each of the two primary amino groups of 1 molecule of the aliphatic diamine of the formula (1) (4 adduct). Here, content of 1 adduct, 2 adduct-1, and 2 adduct-2 in the mixture of each adduct contained in the polyamino compound obtained by addition reaction of aliphatic diamine of formula (1) and styrene Is preferably 50% by weight or more, and more preferably 70% by weight or more.
本発明のエポキシ樹脂硬化剤において、該ポリアミノ化合物の他には未反応の（１）式の脂肪族ジアミン等が含まれる。（１）式の脂肪族ジアミンの含有量は、該ポリアミノ化合物１００重量部に対し２重量部未満であることが好ましい。該未反応脂肪族ジアミンの含有量を２重量部未満とすることにより、エポキシ樹脂組成物が大気中の二酸化炭素や水蒸気を吸収して生成するカルバミン酸塩や炭酸塩の量を減少させ、塗膜の白化現象や粘着現象による塗膜外観の低下を抑制することができる。 In the epoxy resin curing agent of the present invention, an unreacted aliphatic diamine of the formula (1) is included in addition to the polyamino compound. The content of the aliphatic diamine of the formula (1) is preferably less than 2 parts by weight with respect to 100 parts by weight of the polyamino compound. By setting the content of the unreacted aliphatic diamine to less than 2 parts by weight, the epoxy resin composition reduces the amount of carbamate and carbonate produced by absorbing carbon dioxide and water vapor in the atmosphere. It is possible to suppress a decrease in the appearance of the coating film due to a whitening phenomenon or an adhesive phenomenon of the film.
本発明において、（１）式の脂肪族ジアミンとスチレンとの反応生成物を合成する際には、強塩基性を呈する触媒を使用することが望ましい。例えば、アルカリ金属、アルカリ金属アミド、アルキル化アルカリ金属、などがあるが、好ましくはアルカリ金属アミド（一般式ＭＮＲＲ’：Ｍはアルカリ金属、Ｎは窒素、ＲおよびＲ’は各々独立して水素またはアルキル基である）であり、特にリチウムアミド（ＬｉＮＨ２）が好ましい。また、反応終了後に得られる反応液中には、反応生成物と強塩基性の触媒が含まれるが、この触媒は塩酸、塩化水素ガス、酢酸などの酸、メタノール、エタノール等のアルコール、あるいは水等を加えて除去容易な塩に変えてから、ろ過することも可能である。 In the present invention, when synthesizing the reaction product of the aliphatic diamine of formula (1) and styrene, it is desirable to use a catalyst exhibiting strong basicity. For example, an alkali metal, an alkali metal amide, an alkylated alkali metal, and the like, preferably an alkali metal amide (general formula MNRR ′: M is an alkali metal, N is nitrogen, R and R ′ are each independently hydrogen or In particular, lithium amide (LiNH 2 ) is preferable. The reaction solution obtained after completion of the reaction contains a reaction product and a strongly basic catalyst. This catalyst is an acid such as hydrochloric acid, hydrogen chloride gas or acetic acid, an alcohol such as methanol or ethanol, or water. It is also possible to filter after changing to a salt which can be easily removed by adding, for example.
（１）式の脂肪族ジアミンとスチレンとの反応生成物中に、該ポリアミノ化合物１００重量部に対し（１）式の脂肪族ジアミンが２重量部以上含有される場合は、通常知られる方法によって、２重量部未満になるようにこれを除くことができ、その方法は特に限定されないが、抽出による除去が容易で好ましい。抽出に用いる溶媒は（１）式の脂肪族ジアミンが容易に溶解し、該脂肪族ジアミンとスチレンとの反応生成物が溶解しない溶媒であれば特に限定されないが、好ましいのは水である。 When the aliphatic diamine of the formula (1) is contained in the reaction product of the aliphatic diamine of the formula (1) and styrene in an amount of 2 parts by weight or more with respect to 100 parts by weight of the polyamino compound, a generally known method is used. This can be removed so as to be less than 2 parts by weight, and the method is not particularly limited, but removal by extraction is easy and preferable. The solvent used for the extraction is not particularly limited as long as the aliphatic diamine of the formula (1) is easily dissolved and the reaction product of the aliphatic diamine and styrene is not dissolved, but water is preferable.
本発明のエポキシ樹脂硬化剤において、硬化促進剤として用いられる有機化合物は、分子内にカルボキシル基及び水酸基を同時に持つものである。通常、エポキシ樹脂硬化剤の硬化促進剤としては、トリエチルアミン、ＤＭＰ−１０（２−ジメチルアミノメチルフェノール）、ＤＭＰ−３０（２，４，６−トリス（ジメチルアミノメチル）フェノール）等に代表されるようなアミン系の硬化促進剤、フェノールやベンジルアルコールに代表されるような水酸基を持つ硬化促進剤、蟻酸に代表されるようなカルボキシル基を持つ硬化促進剤が用いられるが、本発明が目的とする効果（低温での良好な硬化性）を十分に得るためには、分子内にカルボキシル基及び水酸基を持つものを用いる必要がある。 In the epoxy resin curing agent of the present invention, the organic compound used as a curing accelerator has a carboxyl group and a hydroxyl group in the molecule at the same time. Usually, the curing accelerator for epoxy resin curing agent is represented by triethylamine, DMP-10 (2-dimethylaminomethylphenol), DMP-30 (2,4,6-tris (dimethylaminomethyl) phenol) and the like. Such an amine-based curing accelerator, a curing accelerator having a hydroxyl group represented by phenol and benzyl alcohol, and a curing accelerator having a carboxyl group represented by formic acid are used. In order to obtain a sufficient effect (good curability at low temperature), it is necessary to use one having a carboxyl group and a hydroxyl group in the molecule.
分子内にカルボキシル基及び水酸基を持つ有機化合物としては、好ましくは炭素数２〜１５の脂肪族化合物、炭素数２〜１５の脂環式化合物、及び炭素数２〜１５の芳香族化合物の中から選択することができる。そのうち、炭素数６〜１５の芳香族化合物が好ましく、炭素数７〜１２の芳香族化合物がより好ましい。炭素数７〜１２の芳香族化合物として、サリチル酸、ジヒドロキシ安息香酸、トリヒドロキシ安息香酸、メチル-サリチル酸、２−ヒドロキシ−３−イソプロピル安息香酸、ヒドロキシナフトエ酸、ジヒドロキシナフトエ酸、ヒドロキシメトキシナフトエ酸が挙げられ、その中でも、特にサリチル酸が好適に用いられる。 The organic compound having a carboxyl group and a hydroxyl group in the molecule is preferably an aliphatic compound having 2 to 15 carbon atoms, an alicyclic compound having 2 to 15 carbon atoms, or an aromatic compound having 2 to 15 carbon atoms. You can choose. Among them, an aromatic compound having 6 to 15 carbon atoms is preferable, and an aromatic compound having 7 to 12 carbon atoms is more preferable. Examples of the aromatic compound having 7 to 12 carbon atoms include salicylic acid, dihydroxybenzoic acid, trihydroxybenzoic acid, methyl-salicylic acid, 2-hydroxy-3-isopropylbenzoic acid, hydroxynaphthoic acid, dihydroxynaphthoic acid, and hydroxymethoxynaphthoic acid. Among them, salicylic acid is particularly preferably used.
硬化促進剤の添加量は、本発明のエポキシ樹脂硬化剤の性能が損なわれない範囲であれば特に限定されないが、ポリアミノ化合物および硬化促進剤の合計に対して好ましくは１〜２０重量％、さらに好ましくは４〜１５重量％である。硬化促進剤の添加量が１重量％未満の場合には、低温条件下での該硬化剤とエポキシ樹脂との反応が十分進行せず、また、添加量が２０重量％を超える場合には、得られるエポキシ樹脂組成物の性能が低下する。 The addition amount of the curing accelerator is not particularly limited as long as the performance of the epoxy resin curing agent of the present invention is not impaired, but is preferably 1 to 20% by weight based on the total of the polyamino compound and the curing accelerator. Preferably, it is 4 to 15% by weight. When the addition amount of the curing accelerator is less than 1% by weight, the reaction between the curing agent and the epoxy resin under low temperature conditions does not proceed sufficiently, and when the addition amount exceeds 20% by weight, The performance of the resulting epoxy resin composition is reduced.
本発明に使用される硬化促進剤としては、上記有機化合物のみからなるものであってもよいが、該有機化合物とともに、他の公知の硬化促進剤を併用することもできる。併用しうる他の硬化促進剤としては、先に挙げたアミノ基、水酸基、カルボキシル基等の官能基を分子内に持つ硬化促進剤、あるいは、かかる官能基の２種以上を分子内に持つ硬化促進剤であって上記有機化合物以外のもの、すなわち例えばジエタノールアミンに代表されるような化合物等、を挙げることができる。
併用する場合は、分子内にカルボキシル基及び水酸基を持つ上記有機化合物の割合が、硬化促進剤全量に対し３０重量％以上、さらには５０重量％以上となるようにするのが望ましい。
The curing accelerator used in the present invention may be composed only of the organic compound, but other known curing accelerators can be used in combination with the organic compound. Other curing accelerators that can be used in combination include the above-described curing accelerators having functional groups such as amino groups, hydroxyl groups, and carboxyl groups in the molecule, or curing having two or more of these functional groups in the molecule. Accelerators other than the above organic compounds, that is, compounds such as diethanolamine can be mentioned.
When used in combination, the proportion of the organic compound having a carboxyl group and a hydroxyl group in the molecule is preferably 30% by weight or more, more preferably 50% by weight or more based on the total amount of the curing accelerator.
本発明のエポキシ樹脂硬化剤をエポキシ樹脂に配合する場合は、単独で使用してもよいし、他のポリアミン系エポキシ樹脂硬化剤と混合して使用してもよい。この場合、本発明のエポキシ樹脂硬化剤の含有量は、本発明のエポキシ樹脂硬化剤および他のポリアミン系エポキシ樹脂硬化剤の合計の中で通常２０重量％以上、さらに好ましくは３０重量％以上である。本発明のエポキシ樹脂硬化剤が２０重量％未満である場合、本発明のエポキシ樹脂硬化剤の特徴が損なわれる場合があり好ましくない。 When mix | blending the epoxy resin hardening | curing agent of this invention with an epoxy resin, you may use it individually and you may mix and use it with another polyamine type epoxy resin hardening | curing agent. In this case, the content of the epoxy resin curing agent of the present invention is usually 20% by weight or more, more preferably 30% by weight or more in the total of the epoxy resin curing agent of the present invention and other polyamine type epoxy resin curing agents. is there. When the epoxy resin hardening | curing agent of this invention is less than 20 weight%, the characteristics of the epoxy resin hardening | curing agent of this invention may be impaired, and it is unpreferable.
本発明のエポキシ樹脂組成物は、エポキシ樹脂と前述のエポキシ樹脂硬化剤を含むものである。本発明のエポキシ樹脂組成物に使用されるエポキシ樹脂は、本発明のエポキシ樹脂硬化剤に含まれるアミノ基由来の活性水素と反応するグリシジル基を持つエポキシ樹脂であれば、特に限定されないが、ビスフェノールＡ型エポキシ樹脂またはビスフェノールＦ型エポキシ樹脂またはこれらの混合物を主成分とするものが好適に用いられる。さらに本発明のエポキシ樹脂組成物には充填剤、可塑剤などの改質成分、反応性または非反応性の希釈剤、揺変剤などの流動調整成分、顔料、レべリング剤、粘着付与剤などの成分やハジキ防止剤、ダレ止め、剤、流展剤、消泡剤、紫外線吸収剤、光安定剤などの添加剤を用途に応じて用いることができる。 The epoxy resin composition of this invention contains an epoxy resin and the above-mentioned epoxy resin hardening | curing agent. The epoxy resin used in the epoxy resin composition of the present invention is not particularly limited as long as it is an epoxy resin having a glycidyl group that reacts with an active hydrogen derived from an amino group contained in the epoxy resin curing agent of the present invention. An A type epoxy resin, a bisphenol F type epoxy resin or a mixture thereof is preferably used as a main component. Further, the epoxy resin composition of the present invention includes a filler, a modifying component such as a plasticizer, a flow adjusting component such as a reactive or non-reactive diluent, a thixotropic agent, a pigment, a leveling agent, and a tackifier. And other components such as anti-repellent agents, anti-sagging agents, anti-sagging agents, spreading agents, antifoaming agents, ultraviolet absorbers, and light stabilizers can be used depending on the intended use.
本発明のエポキシ樹脂組成物は、公知の方法で硬化させ、エポキシ樹脂硬化物とすることができる。硬化条件は用途に応じて適宜選択され、特に限定されないが、本エポキシ樹脂組成物は１５〜３０℃の常温条件だけではなく、０〜１５℃の低温条件において硬化させたときにも優れた硬化性、塗膜表面性を示す。 The epoxy resin composition of the present invention can be cured by a known method to obtain a cured epoxy resin. Curing conditions are appropriately selected depending on the application, and are not particularly limited. However, the epoxy resin composition is excellent in curing not only at room temperature conditions of 15 to 30 ° C. but also when cured at low temperature conditions of 0 to 15 ° C. Properties and coating surface properties.
以下に、実施例を挙げて本発明を具体的に説明する。但し本発明はこれらの実施例により制限されるものではない。なお、エポキシ樹脂塗膜性能の評価は、以下の方法にて行なった。
＜エポキシ樹脂塗膜性能評価＞
エポキシ樹脂組成物を、５℃、８０％ＲＨの条件下で、鋼板に２００μｍの厚みで塗装した。
外観：硬化７日後の塗膜外観（光沢、透明性、平滑性）を目視で評価し、乾燥性（硬化１６時間後、１，４，７日後）は指触により評価した。
耐水性：硬化１６時間後、１、４および７日後の塗膜上に水滴を滴下し、１日放置後の塗膜の変化を目視にて評価した。
評価方法：４段階で評価
◎：優秀、 ○：良好 △：やや不良 ×：不良
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited by these examples. In addition, evaluation of the epoxy resin coating film performance was performed by the following method.
<Epoxy resin coating film performance evaluation>
The epoxy resin composition was applied to a steel plate with a thickness of 200 μm under conditions of 5 ° C. and 80% RH.
Appearance: The appearance (gloss, transparency, smoothness) of the coating film 7 days after curing was visually evaluated, and the drying property (16 hours after curing, 1, 4, 7 days later) was evaluated by touch.
Water resistance: After 16 hours of curing, water drops were dropped on the coating film after 1, 4 and 7 days, and the change of the coating film after standing for 1 day was visually evaluated.
Evaluation method: Evaluation in 4 stages ◎: Excellent, ○: Good △: Somewhat bad ×: Bad
＜合成例１＞
撹拌装置、温度計、窒素導入管、滴下漏斗、およびコンデンサーを備えた内容積２リットルの丸底フラスコに、メタキシリレンジアミン（ＭＸＤＡ；三菱ガス化学（株）製）８１７．２ｇ（６．０モル）とリチウムアミド（メルク（株）製試薬）２．９g（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。昇温後スチレン（和光純薬工業（株）製、試薬特級）６２５．２g（６．０モル）を２時間かけて滴下した。滴下終了後８０℃で１時間保った。
その後、８０℃の蒸留水６１８．２ｇを添加し、１５分攪拌後５分間静置した。フラスコ内の２層に分離した液の上層を除去し、さらに同量の８０℃の蒸留水を加えて、同様の操作を行なった。この操作を７回繰り返した後、下層に溶解した蒸留水を減圧留去によって除去し、ポリアミノ組成物Ａ、１１１５．２ｇを得た。ポリアミノ組成物Ａ中の未反応ＭＸＤＡ含有量は０．７重量％であり、粘度は６６ｍＰａ・ｓ（２５℃）であった。
ポリアミノ組成物Ａ中の１付加物含有量は５８．１重量％、２付加物−１含有量は３３．９重量％、２付加物−２含有量は３．５重量％、３付加物含有量は３．８重量％であった。
<Synthesis Example 1>
Metaxylylenediamine (MXDA; manufactured by Mitsubishi Gas Chemical Co., Ltd.) 817.2 g (6.0) was added to a 2 liter round bottom flask equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and condenser. Mol) and 2.9 g (0.13 mol) of lithium amide (Merck Co., Ltd. reagent) were charged, and the mixture was heated to 80 ° C. with stirring under a nitrogen stream. After the temperature increase, 625.2 g (6.0 mol) of styrene (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) was added dropwise over 2 hours. After completion of dropping, the temperature was kept at 80 ° C. for 1 hour.
Thereafter, 618.2 g of 80 ° C. distilled water was added, and the mixture was stirred for 15 minutes and allowed to stand for 5 minutes. The upper layer of the liquid separated into two layers in the flask was removed, and the same amount of distilled water at 80 ° C. was added, and the same operation was performed. After repeating this operation seven times, distilled water dissolved in the lower layer was removed by distillation under reduced pressure to obtain 115.2 g of polyamino composition A. The unreacted MXDA content in the polyamino composition A was 0.7% by weight, and the viscosity was 66 mPa · s (25 ° C.).
In polyamino composition A, the content of 1 adduct is 58.1% by weight, the content of 2 adduct-1 is 33.9% by weight, the content of 2 adduct-2 is 3.5% by weight, and the content of 3 adducts is contained. The amount was 3.8% by weight.
＜合成例２＞
実施例１と同様のフラスコにイソホロンジアミン（以下、ＩＰＤＡと略する。）６８１．２ｇ（４．０モル）を仕込み、窒素気流下、攪拌しながら８０℃に昇温した。８０℃に保ちながら、ビスフェノールＡ型液状エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８２８、エポキシ当量：１８６ｇ／ｅｑ、以下、ＤＧＥＢＡと略する。）１８６．０ｇ（０．５モル）を２時間かけて滴下した。滴下終了後、１００℃に昇温して２時間反応を行い、ＩＰＤＡのＤＧＥＢＡ付加物８６０．１ｇを得た。ＩＰＤＡのＤＧＥＢＡ付加物（ポリアミノ組成物Ｂ）の粘度は２８６５ｍＰａ・ｓ（２５℃）、活性水素当量は５８であった。
<Synthesis Example 2>
681.2 g (4.0 mol) of isophoronediamine (hereinafter abbreviated as IPDA) was charged into the same flask as in Example 1, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining at 80 ° C., 186.0 g (0.5 mol) of bisphenol A type liquid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 828, epoxy equivalent: 186 g / eq, hereinafter abbreviated as DGEBA) ) Was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 100 ° C. and the reaction was carried out for 2 hours to obtain 860.1 g of IPDA DGEBA adduct. The viscosity of the IPDA DGEBA adduct (polyamino composition B) was 2865 mPa · s (25 ° C.), and the active hydrogen equivalent was 58.
＜実施例１＞
２４０ｍｌガラス製マヨネーズ瓶に、合成例１で得られたポリアミノ組成物Ａを１９０ｇ秤取り、これにサリチル酸１０ｇを添加して、６０℃で３時間攪拌し、エポキシ樹脂硬化剤Ａ、２００ｇを得た。エポキシ樹脂硬化剤Ａの粘度は１７１ｍＰａ・ｓ（２５℃）であった。得られたエポキシ樹脂硬化剤を用い、ビスフェノールＡ型液状エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８０１、エポキシ当量：２１６ｇ／ｅｑ、）と、表１に示す割合で配合し、５℃、８０％ＲＨの条件下で硬化させてエポキシ樹脂硬化塗膜を作成し性能評価を行なった。評価結果を表１に示す。
<Example 1>
In a 240 ml glass mayonnaise bottle, 190 g of polyamino composition A obtained in Synthesis Example 1 was weighed, 10 g of salicylic acid was added thereto, and the mixture was stirred at 60 ° C. for 3 hours to obtain epoxy resin curing agent A, 200 g. . The viscosity of the epoxy resin curing agent A was 171 mPa · s (25 ° C.). Using the obtained epoxy resin curing agent, bisphenol A type liquid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 801, epoxy equivalent: 216 g / eq,) and blended in the ratio shown in Table 1, Curing was performed under conditions of 5 ° C. and 80% RH to prepare a cured epoxy resin coating, and performance evaluation was performed. The evaluation results are shown in Table 1.
＜実施例２＞
２４０ｍｌガラス製マヨネーズ瓶に、合成例１で得られたポリアミノ組成物Ａを１８０ｇ秤取り、これにサリチル酸２０ｇを添加して、６０℃で３時間攪拌し、エポキシ樹脂硬化剤Ｂ、２００ｇを得た。エポキシ樹脂硬化剤Ｂの粘度は５３７ｍＰａ・ｓ（２５℃）であった。得られたエポキシ樹脂硬化剤を用い、ビスフェノールＡ型液状エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８０１、エポキシ当量：２１６ｇ／ｅｑ、）と、表１に示す割合で配合し、５℃、８０％ＲＨの条件下で硬化させてエポキシ樹脂硬化塗膜を作成し性能評価を行なった。評価結果を表１に示す。
<Example 2>
In a 240 ml glass mayonnaise bottle, 180 g of polyamino composition A obtained in Synthesis Example 1 was weighed, 20 g of salicylic acid was added thereto, and the mixture was stirred at 60 ° C. for 3 hours to obtain epoxy resin curing agent B, 200 g. . The viscosity of the epoxy resin curing agent B was 537 mPa · s (25 ° C.). Using the obtained epoxy resin curing agent, bisphenol A type liquid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 801, epoxy equivalent: 216 g / eq,) and blended in the ratio shown in Table 1, Curing was performed under conditions of 5 ° C. and 80% RH to prepare a cured epoxy resin coating, and performance evaluation was performed. The evaluation results are shown in Table 1.
＜比較例１＞
合成例１で得られたポリアミノ組成物Ａをエポキシ樹脂硬化剤Ｃとしてそのまま用いた。エポキシ樹脂硬化剤Ｃを用い、ビスフェノールＡ型液状エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８０１、エポキシ当量：２１６ｇ／ｅｑ、）と、表２に示す割合で配合し、５℃、８０％ＲＨの条件下で硬化させてエポキシ樹脂硬化塗膜を作成し性能評価を行なった。評価結果を表２に示す。
<Comparative Example 1>
The polyamino composition A obtained in Synthesis Example 1 was used as the epoxy resin curing agent C as it was. Using epoxy resin curing agent C, bisphenol A type liquid epoxy resin (made by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 801, epoxy equivalent: 216 g / eq), blended in the ratio shown in Table 2, and 5 ° C. The epoxy resin cured coating film was prepared by curing under the condition of 80% RH, and the performance was evaluated. The evaluation results are shown in Table 2.
＜比較例２＞
２４０ｍｌガラス製マヨネーズ瓶に、合成例１で得られたポリアミノ組成物Ａを１９０ｇ秤取り、これにフェノール１０ｇを添加して、６０℃で３時間攪拌し、エポキシ樹脂硬化剤Ｄ、２００ｇを得た。エポキシ樹脂硬化剤Ｄの粘度は９４ｍＰａ・ｓ（２５℃）であった。得られたエポキシ樹脂硬化剤を用い、ビスフェノールＡ型液状エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８０１、エポキシ当量：２１６ｇ／ｅｑ、）と、表２に示す割合で配合し、５℃、８０％ＲＨの条件下で硬化させてエポキシ樹脂硬化塗膜を作成し性能評価を行なった。評価結果を表２に示す。
<Comparative example 2>
190 g of polyamino composition A obtained in Synthesis Example 1 was weighed into a 240 ml glass mayonnaise bottle, 10 g of phenol was added thereto, and the mixture was stirred at 60 ° C. for 3 hours to obtain epoxy resin curing agent D, 200 g. . The viscosity of the epoxy resin curing agent D was 94 mPa · s (25 ° C.). Using the obtained epoxy resin curing agent, bisphenol A type liquid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 801, epoxy equivalent: 216 g / eq), and blended in the ratio shown in Table 2, Curing was performed under conditions of 5 ° C. and 80% RH to prepare a cured epoxy resin coating, and performance evaluation was performed. The evaluation results are shown in Table 2.
＜比較例３＞
２４０ｍｌガラス製マヨネーズ瓶に、合成例１で得られたポリアミノ組成物Ａを１９０ｇ秤取り、これに安息香酸１０ｇを添加して、６０℃で３時間攪拌し、エポキシ樹脂硬化剤Ｅ、２００ｇを得た。エポキシ樹脂硬化剤Ｅの粘度は１７１ｍＰａ・ｓ（２５℃）であった。得られたエポキシ樹脂硬化剤を用い、ビスフェノールＡ型液状エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８０１、エポキシ当量：２１６ｇ／ｅｑ、）と、表２に示す割合で配合し、５℃、８０％ＲＨの条件下で硬化させてエポキシ樹脂硬化塗膜を作成し性能評価を行なった。評価結果を表２に示す。
<Comparative Example 3>
In a 240 ml glass mayonnaise bottle, 190 g of polyamino composition A obtained in Synthesis Example 1 was weighed, 10 g of benzoic acid was added thereto, and the mixture was stirred at 60 ° C. for 3 hours to obtain epoxy resin curing agent E, 200 g. It was. The viscosity of the epoxy resin curing agent E was 171 mPa · s (25 ° C.). Using the obtained epoxy resin curing agent, bisphenol A type liquid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 801, epoxy equivalent: 216 g / eq), and blended in the ratio shown in Table 2, Curing was performed under conditions of 5 ° C. and 80% RH to prepare a cured epoxy resin coating, and performance evaluation was performed. The evaluation results are shown in Table 2.
＜比較例４＞
２４０ｍｌガラス製マヨネーズ瓶に、合成例１で得られたポリアミノ組成物Ａを１９０ｇ秤取り、これにジエタノールアミン１０ｇを添加して、６０℃で３時間攪拌し、エポキシ樹脂硬化剤Ｆ、２００ｇを得た。エポキシ樹脂硬化剤Ｆの粘度は１０２ｍＰａ・ｓ（２５℃）であった。得られたエポキシ樹脂硬化剤を用い、ビスフェノールＡ型液状エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８０１、エポキシ当量：２１６ｇ／ｅｑ、）と、表３に示す割合で配合し、５℃、８０％ＲＨの条件下で硬化させてエポキシ樹脂硬化塗膜を作成し性能評価を行なった。評価結果を表３に示す。
<Comparative example 4>
190 g of polyamino composition A obtained in Synthesis Example 1 was weighed into a 240 ml glass mayonnaise bottle, 10 g of diethanolamine was added thereto, and the mixture was stirred at 60 ° C. for 3 hours to obtain epoxy resin curing agent F, 200 g. . The viscosity of the epoxy resin curing agent F was 102 mPa · s (25 ° C.). Using the obtained epoxy resin curing agent, bisphenol A type liquid epoxy resin (made by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 801, epoxy equivalent: 216 g / eq), and blended in the ratio shown in Table 3, Curing was performed under conditions of 5 ° C. and 80% RH to prepare a cured epoxy resin coating, and performance evaluation was performed. The evaluation results are shown in Table 3.
＜比較例５＞
２４０ｍｌガラス製マヨネーズ瓶に、合成例２で得られたポリアミノ組成物Ｂを１７０ｇ秤取り、これにサリチル酸１０ｇとベンジルアルコール２０ｇを添加して、６０℃で３時間攪拌し、エポキシ樹脂硬化剤Ｇ、２００ｇを得た。エポキシ樹脂硬化剤Ｇの粘度は３２５０ｍＰａ・ｓ（２５℃）であった。得られたエポキシ樹脂硬化剤を用い、ビスフェノールＡ型液状エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８０１、エポキシ当量：２１６ｇ／ｅｑ、）と、表３に示す割合で配合し、５℃、８０％ＲＨの条件下で硬化させてエポキシ樹脂硬化塗膜を作成し性能評価を行なった。評価結果を表３に示す。
<Comparative Example 5>
170 g of polyamino composition B obtained in Synthesis Example 2 was weighed into a 240 ml glass mayonnaise bottle, 10 g of salicylic acid and 20 g of benzyl alcohol were added thereto, and the mixture was stirred at 60 ° C. for 3 hours. 200 g was obtained. The viscosity of the epoxy resin curing agent G was 3250 mPa · s (25 ° C.). Using the obtained epoxy resin curing agent, bisphenol A type liquid epoxy resin (made by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 801, epoxy equivalent: 216 g / eq), and blended in the ratio shown in Table 3, Curing was performed under conditions of 5 ° C. and 80% RH to prepare a cured epoxy resin coating, and performance evaluation was performed. The evaluation results are shown in Table 3.
Claims (6)
Ｈ２Ｎ−Ｈ２Ｃ−Ａ−ＣＨ２−ＮＨ２ （１）
（Ａはフェニレン基またはシクロヘキシレン基を示す。） (1) An epoxy resin curing agent comprising a curing accelerator comprising a polyamino compound obtained by the reaction of an aliphatic diamine represented by the formula and styrene, and an organic compound having a carboxyl group and a hydroxyl group in the molecule.
H 2 N-H 2 C- A-CH 2 -NH 2 (1)
(A represents a phenylene group or a cyclohexylene group.)
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| CN112119106B (en) | 2018-05-24 | 2023-10-10 | 三菱瓦斯化学株式会社 | Curing agent for aqueous epoxy resin, aqueous epoxy resin composition, and cured product thereof |
| CN114686152B (en) * | 2022-04-24 | 2023-10-27 | 中国电建集团中南勘测设计研究院有限公司 | Pouring/pressure-pouring type epoxy resin structural adhesive and application thereof |
| CN116285596B (en) * | 2023-01-04 | 2024-04-26 | 广东科德环保科技股份有限公司 | Preparation method and application of anti-shrinkage cathode electrophoretic coating |
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| JP2002161076A (en) * | 2000-09-12 | 2002-06-04 | Mitsubishi Gas Chem Co Inc | Amino compound and method for producing the same |
| JP2004018711A (en) * | 2002-06-18 | 2004-01-22 | Mitsubishi Gas Chem Co Inc | Method for controlling pot life of epoxy resin composition |
| JP4310614B2 (en) * | 2002-08-07 | 2009-08-12 | 三菱瓦斯化学株式会社 | Polyamino epoxy resin curing agent and epoxy resin composition |
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2004
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001093940A (en) * | 1999-09-21 | 2001-04-06 | Sumitomo Bakelite Co Ltd | Method for assembling semiconductor device |
| JP2001163955A (en) * | 1999-12-13 | 2001-06-19 | Mitsubishi Gas Chem Co Inc | Epoxy resin curing agent and composition |
| JP2002088139A (en) * | 2000-09-12 | 2002-03-27 | Sumitomo Bakelite Co Ltd | Flame-retardant resin composition, prepreg using the same and laminate |
| JP2002161076A (en) * | 2000-09-12 | 2002-06-04 | Mitsubishi Gas Chem Co Inc | Amino compound and method for producing the same |
| JP2004018711A (en) * | 2002-06-18 | 2004-01-22 | Mitsubishi Gas Chem Co Inc | Method for controlling pot life of epoxy resin composition |
| JP4310614B2 (en) * | 2002-08-07 | 2009-08-12 | 三菱瓦斯化学株式会社 | Polyamino epoxy resin curing agent and epoxy resin composition |
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| JP2004263177A (en) | 2004-09-24 |
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