JPS6312624A - Production of rapid curing agent for epoxy compound - Google Patents
Production of rapid curing agent for epoxy compoundInfo
- Publication number
- JPS6312624A JPS6312624A JP15572986A JP15572986A JPS6312624A JP S6312624 A JPS6312624 A JP S6312624A JP 15572986 A JP15572986 A JP 15572986A JP 15572986 A JP15572986 A JP 15572986A JP S6312624 A JPS6312624 A JP S6312624A
- Authority
- JP
- Japan
- Prior art keywords
- thiourea
- condensation reaction
- curing agent
- reaction product
- epoxy
- 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
- 239000004593 Epoxy Substances 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006482 condensation reaction Methods 0.000 claims abstract description 33
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000003822 epoxy resin Substances 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- -1 amino compound Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 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
- 238000010438 heat treatment Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- MDWCEEQVTZURSU-UHFFFAOYSA-N 3-(2,4,8,10-tetraoxaspiro[5.5]undecan-5-yl)propan-1-amine Chemical compound NCCCC1OCOCC11COCOC1 MDWCEEQVTZURSU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- HMJBXEZHJUYJQY-UHFFFAOYSA-N 4-(aminomethyl)octane-1,8-diamine Chemical compound NCCCCC(CN)CCCN HMJBXEZHJUYJQY-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NHWGPUVJQFTOQX-UHFFFAOYSA-N ethyl-[2-[2-[ethyl(dimethyl)azaniumyl]ethyl-methylamino]ethyl]-dimethylazanium Chemical compound CC[N+](C)(C)CCN(C)CC[N+](C)(C)CC NHWGPUVJQFTOQX-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- DQWFTGPZPKZMAB-UHFFFAOYSA-N undecane-1,6,11-triamine Chemical compound NCCCCCC(N)CCCCCN DQWFTGPZPKZMAB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
多価アミン−チオ尿素縮合反応生成物がエポキシ化合物
の硬化剤として有効であることは、すでに公知（特許番
号５０９７１５）で、ジアミンの３．９−ビス （３−
アミノプロピル）−２，４，８，１０−テトラオキサス
ピロ（５，５）ウンデカン、キシリレンジアミンとチオ
尿素の縮合反応生成物はエポキシ樹脂の硬化剤として工
業生産されている。DETAILED DESCRIPTION OF THE INVENTION It is already known (Patent No. 509715) that a polyvalent amine-thiourea condensation reaction product is effective as a curing agent for epoxy compounds.
A condensation reaction product of aminopropyl-2,4,8,10-tetraoxaspiro(5,5)undecane, xylylenediamine, and thiourea is industrially produced as a curing agent for epoxy resins.
それらの合成において、多価アミンとチオ尿素の反応モ
ル比は１：１が適当とされ、 ＰＩ＝に１：１で、約１
４０℃以上で縮合反応させているが、それらによる各種
のエポキシ樹脂の硬化に要する時間は常温で、エポキシ
化合物と硬化剤の混合樹脂量３ｇの場合、約３０分以上
を必要とする。In their synthesis, the reaction molar ratio of polyvalent amine and thiourea is considered to be 1:1, with PI=1:1 and about 1
Although the condensation reaction is carried out at 40° C. or higher, the time required for curing various epoxy resins at room temperature is about 30 minutes or more when the mixed resin amount of the epoxy compound and curing agent is 3 g.
発明者等はエポキシ化合物の急速硬化に有効な多価アミ
ン−チオ尿素縮合反応生成物の製造条件について研究し
た結果、多価アミンとチオ尿素を反応モル比１：１．３
〜１．７、温度約１２０℃以上で、５分以上縮合反応さ
せて得られた常温で液状の多価アミン−チオ尿素縮合反
応生成物がエポキシ化合物に対して従来見られなかった
顕著な急速硬化の作用・性能を有することを見出した。The inventors researched the conditions for producing a polyvalent amine-thiourea condensation reaction product that is effective for rapid curing of epoxy compounds, and found that the reaction molar ratio of polyvalent amine and thiourea was 1:1.3.
~1.7, the polyvalent amine-thiourea condensation reaction product, which is liquid at room temperature and is obtained by condensation reaction at a temperature of about 120°C or higher for 5 minutes or more, has a remarkable rapidity that has not been previously seen for epoxy compounds. It was discovered that it has hardening action and performance.
本発明にかかるエポキシ樹脂硬化剤は、一般のエポキシ
樹脂としての用途、即ち塗料、接着剤、成型材、多孔質
材料その他の材料、織物・紙処理用、充填用、ゴム配合
用その他の硬化がかかわる各種の用途に用いられる。特
に、急速な硬化を必要とする場合に効果的で、また反応
速度が遅い硬化剤に配合して反応速度を適度に促進する
のに有効である。The epoxy resin curing agent according to the present invention can be used for general epoxy resin purposes, such as coatings, adhesives, molding materials, porous materials and other materials, textile/paper processing, filling, rubber compounding, and other curing applications. It is used for various related purposes. It is particularly effective when rapid curing is required, and is also effective when added to a curing agent with a slow reaction rate to appropriately accelerate the reaction rate.
本発明において多価アミンとは分子内に少なくとも、活
性水素基を有するアミン基（アミノ基及びイミノ基）を
２個以上有する多価アミノ化合物をいう０例えば、エチ
レンジアミン、テトラメチレンジアミン、ヘキサメチレ
ンジアミン、ノナメチレンジアミン、その他のアルキレ
ンジアミン、ジエチレントリアミン、トリエチレンテト
ラミン、テトラエチレンペンタミン、ヘキサエチレンへ
ブタミン、ジ（ヘキサメチレン）トリアミン、トリ（ヘ
キサメチレン）テトラミン、テトラ（ヘキサメチレン）
ペンタミン、ヘキサ（ヘキサメチレン）へブタミン、そ
の他のポリアルキレンポリアミン、Ｈｚ Ｎ （ＣＨ！
）ｓ ＮＲ（ＣＨ＊ ）＊ ＮＨ＊ （但しＲはア
ルキル基）、キシリレンジアミン、３．９＝ビス（３−
了ミノブロビル）−２，４，８，１０−テトラオキサス
ピロ（５，５）ウンデカン（以下、ＡＴＵで表示する）
、４−アミノメチル−１，８−オクタンジアミン（以下
、ＴＡで表示する） 、１，６．１１−ウンデカントリ
アミン（以下、ＴＵで表示する）その他のポリアミンで
ある。In the present invention, polyvalent amine refers to a polyvalent amino compound having at least two or more amine groups (amino groups and imino groups) having active hydrogen groups in the molecule. For example, ethylene diamine, tetramethylene diamine, hexamethylene diamine. , nonamethylenediamine, other alkylene diamines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexaethylenehebutamine, di(hexamethylene)triamine, tri(hexamethylene)tetramine, tetra(hexamethylene)
Pentamine, hexa(hexamethylene) hebutamine, other polyalkylene polyamines, Hz N (CH!
)s NR(CH* )* NH* (where R is an alkyl group), xylylenediamine, 3.9=bis(3-
minobrovir)-2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter expressed as ATU)
, 4-aminomethyl-1,8-octanediamine (hereinafter referred to as TA), 1,6,11-undecanetriamine (hereinafter referred to as TU) and other polyamines.
これらの多価アミンはいずれもチオ尿素とモル比１：１
．３〜１．７、反応温度１２０℃以上、反応時間５分以
上で縮合反応物を生成し、本発明に使用される。Both of these polyvalent amines have a molar ratio of 1:1 to thiourea.
．． 3 to 1.7, a condensation reaction product is produced at a reaction temperature of 120°C or more and a reaction time of 5 minutes or more, and is used in the present invention.
チオ尿素は多価アミンと反応させるとき、多価アミンの
アミノ基、イミノ基と作用し脱アンモニアにより縮合・
重縮合反応することが知られている。When thiourea is reacted with a polyvalent amine, it acts with the amino group and imino group of the polyvalent amine to cause condensation and deammonia.
It is known that polycondensation reactions occur.
なお、原料のチオ尿素としては、チオ尿素の代わりに加
熱によりチオ尿素を生成するチオシアン酸アンモニウム
（ロダンアンモン）を使用することができる。なお、反
応温度は一般に約１２０℃〜２２０℃であるが、約１２
０℃〜１５０℃が好ましい。Note that as the raw material thiourea, ammonium thiocyanate (rhodanammonium), which generates thiourea upon heating, can be used instead of thiourea. The reaction temperature is generally about 120°C to 220°C, but about 120°C
0°C to 150°C is preferred.
多価アミンとチオ尿素のモル比１：１の反応では多価ア
ミン−チオ尿素縮合物ＮＨ２−Ｒ−ＮＨ−ＣＳ Ｎ Ｈ
ｚのほかに、同時に重縮合物ＮＨ２（−Ｒ−ＮＨＣ５Ｎ
Ｈ−）ｎ Ｈが生成する（ここでＲは２価基である）、
ｎが大きいものはエポキシ樹脂との反応性は小さく急速
硬化の性能は小さい。In the reaction of polyvalent amine and thiourea at a molar ratio of 1:1, the polyvalent amine-thiourea condensate NH2-R-NH-CS NH
In addition to z, the polycondensate NH2 (-R-NHC5N
H-)n H is produced (where R is a divalent group),
When n is large, the reactivity with the epoxy resin is low and the rapid curing performance is low.
また常温で粘度が大または固体である。即ち、エポキシ
樹脂の急速硬化にはｎが大きい重縮合物の生成は好まし
くない、急速硬化に存効な多価アミン−チオ尿素反応生
成物を得るには、多価アミンとチオ尿素の縮合反応を急
速に行うとともに、ｎが大きい重縮合物の生成を極力抑
制する反応条件が必要である。It also has a high viscosity or is solid at room temperature. In other words, the formation of polycondensates with large n is not desirable for rapid curing of epoxy resins.In order to obtain polyvalent amine-thiourea reaction products that are effective for rapid curing, condensation reactions of polyvalent amines and thiourea are necessary. It is necessary to provide reaction conditions that allow rapid reaction and suppress the formation of polycondensates with large n as much as possible.
本発明は以上のような必要条件を可能にするもので、多
価アミンとチオ尿素の反応モル比を１＝１゜３〜１．７
にし、即ちチオ尿素を上記範囲で大過剰に用い、反応温
度１２０℃以上、反応温度５分以上反応させることでエ
ポキシ樹脂急速硬化剤の収率を上げ、同時にｎが大きい
重縮合物の生成を抑えることが知られた事実に基づくも
のである。The present invention enables the above-mentioned requirements, and the reaction molar ratio of polyvalent amine and thiourea is set to 1=1°3 to 1.7.
In other words, by using thiourea in large excess within the above range and reacting at a reaction temperature of 120°C or more for 5 minutes or more, the yield of the epoxy resin rapid curing agent can be increased, and at the same time the formation of polycondensates with a large n can be prevented. It is based on facts known to suppress
エポキシ化合物とは分子内にエポキシ基を有する一般に
エポキシ樹脂とよばれる物質をいい、一般にエビクロロ
ヒドリンと多価フェノール、多価アルコール、多価スル
ホンアミド、アミノ化合物との反応、分子内に二重結合
を有する化合物と退化合物（例えば過酢酸）との反応、
その他の方法で得られる、例えばジヒドロキシベンゼン
、トリヒドロキシベンゼン、ジヒドロキシナフタレン、
ジヒドロキシジフェニルメタン、ビスフェノール類、フ
ェノールフタレン、エチレングリコール、グリセリン、
ペンタエリスリトール、ソルビトール、ポリビニルアル
コール、低重合度のフェノール樹脂、タールなどとエビ
クロロヒドリンの反応、グリシジルメタクリレートとビ
ニル化合物との共重合、ポリブタジェンと過酢酸の反応
その他により得られる。Epoxy compound refers to a substance generally called epoxy resin that has an epoxy group in the molecule, and is generally produced by the reaction of shrimp chlorohydrin with polyhydric phenol, polyhydric alcohol, polyhydric sulfonamide, or amino compound. Reaction of a compound with a heavy bond and a decompound (e.g. peracetic acid),
Obtained by other methods, such as dihydroxybenzene, trihydroxybenzene, dihydroxynaphthalene,
Dihydroxydiphenylmethane, bisphenols, phenolphthalene, ethylene glycol, glycerin,
It can be obtained by reacting shrimp chlorohydrin with pentaerythritol, sorbitol, polyvinyl alcohol, a phenolic resin with a low degree of polymerization, tar, etc., copolymerizing glycidyl methacrylate with a vinyl compound, reacting polybutadiene with peracetic acid, etc.
本発明にかかる急速硬化剤はエポキシ化合物と硬化剤と
の混合・反応による他の一般的硬化樹脂の製法と同様の
方法で用いられる。例えば、エポキシ化合物と本発明に
かかる多価アミン−チオ尿素縮合反応生成物を常温また
は加熱あるいは冷却して、液状でまたは粉末にして混合
し、硬化しないうちに、成型物を得る場合には型に入れ
、接着させる場合には材料の接着面に塗付し接着面を張
り合わせ、表面加工する場合には材料の表面に塗付した
のち、加圧または常圧のもとで、常温でまたは加熱ある
いは冷却し硬化させる。The rapid curing agent according to the present invention can be used in the same manner as other general methods for producing curing resins by mixing and reacting an epoxy compound and a curing agent. For example, if the epoxy compound and the polyvalent amine-thiourea condensation reaction product according to the present invention are mixed at room temperature or heated or cooled in the form of a liquid or powder, and a molded product is obtained before curing, the mold For bonding, apply it to the adhesive surface of the material and laminate the adhesive surfaces, and for surface treatment, apply it to the surface of the material, then apply it to the surface of the material under pressure or normal pressure, at room temperature, or by heating. Alternatively, cool and harden.
エポキシ化合物としては、従って、常温で液状のもの、
また加熱により液状となるエポキシ化合物で、本発明に
かかる多価アミン−チオ尿素縮合反応生成物と反応性を
存するものはいずれも本発明の硬化剤に対して使用する
ことができる。Therefore, epoxy compounds include those that are liquid at room temperature,
Furthermore, any epoxy compound that becomes liquid upon heating and is reactive with the polyvalent amine-thiourea condensation reaction product of the present invention can be used in the curing agent of the present invention.
硬化温度及び硬化時間はエポキシ化合物の種類と本発明
にかかる多価アミン−チオ尿素縮合反応生成物の混合比
率その他の条件を変え調節することができる。The curing temperature and curing time can be adjusted by changing the type of epoxy compound, the mixing ratio of the polyvalent amine-thiourea condensation reaction product according to the present invention, and other conditions.
本発明にかかる多価アミン−チオ尿素縮合反応生成物は
単独で使用してもよく、混合物として使用しても良い。The polyvalent amine-thiourea condensation reaction product according to the present invention may be used alone or as a mixture.
また本発明の特徴を失わない程度に尿素樹脂、フェノー
ル樹脂、アルキッド樹脂その他を混合・併用することが
できる。なお、必要に応して充填剤、滑剤、着色剤、溶
剤などを加える。Furthermore, urea resins, phenol resins, alkyd resins, and others may be mixed or used in combination to the extent that the characteristics of the present invention are not lost. In addition, fillers, lubricants, colorants, solvents, etc. are added as necessary.
エポキシ化合物はエポキシ環の結合角が歪みをもってい
るため開環反応しやすいことはすでによく知られている
ことであるが、本発明の硬化の機構は本発明にかかる多
価アミン−チオ尿素縮合反応生成物がエポキシ環に対し
て著しく反応性に富み、エポキシ化合物と本発明にかか
る多価アミン−チオ尿素縮合反応生成物が混合されると
エポキシ化合物のエポキシ基と本発明にががる多価アミ
ン−チオ尿素縮合反応生成物が急速に反応し、また本発
明にかかる多価アミン−チオ尿素縮合反応生成物の強い
陽イオン性によるイオン反応により、架橋結合して三次
元構造の樹脂を生成することによるものと考えられる。It is already well known that epoxy compounds are susceptible to ring-opening reactions because the bond angles of the epoxy rings are distorted, but the curing mechanism of the present invention is due to the polyvalent amine-thiourea condensation reaction The product is extremely reactive towards epoxy rings, and when the epoxy compound and the polyvalent amine-thiourea condensation reaction product of the present invention are mixed, the epoxy group of the epoxy compound and the polyvalent amine of the present invention are mixed. The amine-thiourea condensation reaction product rapidly reacts, and due to the ionic reaction due to the strong cationic nature of the polyvalent amine-thiourea condensation reaction product according to the present invention, it is cross-linked to produce a resin with a three-dimensional structure. This is thought to be due to the
尚、反応機構については不安定なチオ尿素基が脱アンモ
ニアにより生成するイソチオシアナト基の生成とそのエ
ポキシ基に対する強い反応活性が考慮される。Regarding the reaction mechanism, consideration is given to the formation of an isothiocyanato group produced by deammoniation of an unstable thiourea group, and its strong reaction activity toward an epoxy group.
本発明について、更に実施例をあげて説明する。The present invention will be further explained by giving examples.
〔実施例１〕
多価アミンとしてＴＡを用い、チオ尿素を種々のモル比
で加え、約１３５℃で３０分反応させて縮合反応生成物
を得た。[Example 1] TA was used as a polyvalent amine, thiourea was added at various molar ratios, and the mixture was reacted at about 135° C. for 30 minutes to obtain a condensation reaction product.
これらの縮合反応生成物１ｇをエポキシ樹脂の−ｍであ
るエピコー） ８２８ Ｃ油化シヱルエボキシ（株）製
品）２ｇと混合したところ、硬化に要する時間は表１の
とおりであった。When 1 g of these condensation reaction products was mixed with 2 g of epoxy resin (-m) Epicor 828C (produced by Seil Epoxy Co., Ltd.), the time required for curing was as shown in Table 1.
表１
また、上記縮合反応生成物１ｇをエポキシ樹脂の一種で
あるユノックス２０６（ユニオン・カーバイド社製品）
２ｇと混合したところ、はぼ表１と同様の結果を得た。Table 1 In addition, 1 g of the above condensation reaction product was added to Yunox 206 (a product of Union Carbide), which is a type of epoxy resin.
When mixed with 2g, the same results as in Table 1 were obtained.
〔実施例２〕
多価アミンとしてＴＯを用い、チオ尿素を種々のモル比
で加え、約１３５℃で３０分反応させて縮合反応生成物
を得た。[Example 2] TO was used as a polyvalent amine, thiourea was added in various molar ratios, and the mixture was reacted at about 135° C. for 30 minutes to obtain a condensation reaction product.
これらの縮合反応生成物１ｇをエポキシ樹脂の一種であ
るエピコート８２８（前出）２ｇと混合したところ、硬
化に要する時間は表２のとおりであった。When 1 g of these condensation reaction products was mixed with 2 g of Epicote 828 (mentioned above), which is a type of epoxy resin, the time required for curing was as shown in Table 2.
表 ２
〔実施例３〕
ＡＴＬＪとチオ尿素をモル比１：１．５でとり、窒素ガ
ス雰囲気中で、温度１４０℃で熱すると、発泡して縮合
反応し、反応時間３０分でＡＴＵ−チオ尿素縮合反応生
成物からなる３０℃で、淡黄橙色、透明、粘稠液体（粘
度１５０００ ｃ、ｐ、）が得られた。Table 2 [Example 3] When ATLJ and thiourea are taken at a molar ratio of 1:1.5 and heated at a temperature of 140°C in a nitrogen gas atmosphere, a condensation reaction occurs with foaming, and ATU-thiourea is formed in a reaction time of 30 minutes. A pale yellow-orange, transparent, viscous liquid (viscosity 15000 c, p,) was obtained at 30° C. consisting of the urea condensation reaction product.
エピコート８２８ （油化シェルエポキシ（株）製品
）２ｇに、本発明にかかる前記ＡＴＵ−チオ尿素縮合反
応生成物を３０℃でｌＩＩ 混合したところ、１０分で
固化した。When the ATU-thiourea condensation reaction product according to the present invention was mixed with 2 g of Epicote 828 (product of Yuka Shell Epoxy Co., Ltd.) at 30°C, it solidified in 10 minutes.
比較のため同じエポキシ化合物２ｇに既存のＡＴＵ−チ
オ尿素縮合反応生成物を１ｇ 加え混合したところ、硬
化するのに約３０分を要した。For comparison, when 1 g of the existing ATU-thiourea condensation reaction product was added to 2 g of the same epoxy compound and mixed, it took about 30 minutes to harden.
本発明にかかる多価アミンとチオ尿素を、モル比１：１
．３〜１．７、反応温度１２０℃以上、反応時間５分以
上縮合反応させて得られた縮合反応生成物はエポキシ化
合物に対し強い反応性を有し、液状エポキシ樹脂を常温
で著しく急速に硬化させること、硬化時に揮発性物質の
発生が殆どないこと、硬化樹脂の強度、耐薬品性、接着
力が大きいことその他の特徴から、単独使用、それらの
併用、他の硬化剤との混合・併用により、また充填剤、
滑剤、着色剤、溶剤、その他の資材を加えて、塗料、接
着剤、成型剤、多孔質材料その他の材料、織物・紙処理
用、充填用、ゴム配合用、その他の各種の用途に用いら
れる。The polyvalent amine and thiourea according to the present invention are mixed in a molar ratio of 1:1.
．． 3-1.7, The condensation reaction product obtained by condensation reaction at a reaction temperature of 120°C or more and a reaction time of 5 minutes or more has strong reactivity with epoxy compounds, and can cure liquid epoxy resin extremely rapidly at room temperature. Due to the fact that there is no generation of volatile substances during curing, the strength of the cured resin, chemical resistance, high adhesive strength, and other characteristics, it can be used alone, in combination, or in combination with other curing agents. Also fillers,
In addition to lubricants, colorants, solvents, and other materials, it is used for paints, adhesives, molding agents, porous materials and other materials, textile and paper processing, filling, rubber compounding, and various other uses. .
他に類例のない急速硬化用材料を提供する面から本発明
の工業価値は大きい。The present invention has great industrial value in that it provides an unprecedented rapid curing material.
Claims (1)
モル量加え、約１２０℃以上で、５分以上縮合反応させ
ることを特徴とする常温で液状の多価アミン−チオ尿素
縮合反応生成物からなるエポキシ化合物硬化剤の製法。1.3 to 1.7 thiourea per mole of polyvalent amine
1. A method for producing an epoxy compound curing agent comprising a polyvalent amine-thiourea condensation reaction product that is liquid at room temperature, which comprises adding a molar amount and carrying out a condensation reaction at about 120° C. or higher for 5 minutes or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15572986A JPS6312624A (en) | 1986-07-02 | 1986-07-02 | Production of rapid curing agent for epoxy compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15572986A JPS6312624A (en) | 1986-07-02 | 1986-07-02 | Production of rapid curing agent for epoxy compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6312624A true JPS6312624A (en) | 1988-01-20 |
| JPH0432088B2 JPH0432088B2 (en) | 1992-05-28 |
Family
ID=15612183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15572986A Granted JPS6312624A (en) | 1986-07-02 | 1986-07-02 | Production of rapid curing agent for epoxy compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6312624A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694938A (en) * | 2013-12-11 | 2014-04-02 | 南昌大学 | Adhesive for compound paper pallet with good adhesive property |
-
1986
- 1986-07-02 JP JP15572986A patent/JPS6312624A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694938A (en) * | 2013-12-11 | 2014-04-02 | 南昌大学 | Adhesive for compound paper pallet with good adhesive property |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0432088B2 (en) | 1992-05-28 |
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