JPS6092320A - High-molecular weight polyfunctional epoxy resin - Google Patents

Abstract

PURPOSE:The titled epoxy resin excellent in curability, heat resistance and mechanical properties, obtained by effecting an addition reaction between a specified long-chain amine and an epoxy resin. CONSTITUTION:An addition reaction is effected between an amine having at least two active hydrogen atoms on N in the molecule (e.g., aniline) and an epoxy resin having at least two epoxy groups in the molecule (e.g., bisphenol A- derived epoxy resin) at an equivalent ratio (active hydrogen:epoxy group) >1 to obtain a long-chain amine (A), MW of 1,000-50,000, having at least two active hydrogen atoms on N in the molecule. An addition reaction is effected between component A and an epoxy resin (B) having at least three epoxy groups in the molecule (e.g., novolak epoxy resin) at an equivalent ratio of the opoxy groups in component B to the active hydrogen atoms in component A of 3-30.

Description

[Detailed description of the invention] The present invention relates to a novel high molecular weight multifunctional epoxy resin.

The epoxy resin obtained by the present invention can be cured using a curing agent having a group reactive with an epoxy group, and is suitable for use in injection molding, transfer molding, compression molding, etc. It has particularly excellent curability, heat resistance, and mechanical properties.

A method of obtaining a cured resin by mixing an epoxy resin obtained by reacting a polyhydric phenol such as bisphenol A or phenol novolak with epihalohydrin with a curing agent that is reactive with epoxy groups such as an amine or an acid anhydride. is well known.

The cured resin products obtained by these known methods have electrical properties,
It has excellent properties in terms of dimensional stability and chemical resistance, and is widely used in various fields. However, these existing epoxy resins were not necessarily sufficient for practical use in terms of the balance of curability, heat resistance, and mechanical properties. In other words, the following J: Una disadvantages can be listed.

(1) Good curability and high heat distortion temperature of cured product (11D
When an epoxy resin with a small epoxy equivalent (lIIPE) is used to obtain T), the cured product has poor flexibility and is likely to crack when subjected to mechanical or thermal shock.

(2) What is different from (1) is that if a WPE epoxy resin is used for the road, the flexibility of the cured product will increase, but only a low 1IDT strength will be obtained, and the curability will also decrease.

An object of the present invention is to improve the above-mentioned drawbacks of existing epoxy resins and to provide an epoxy resin having excellent curability, heat resistance, and mechanical properties.

The present invention relates to an epoxy resin having a long chain amine having a molecular weight of 1,000 to 50,000 and having at least two nitrogen-1- active hydrogen atoms in one molecule and at least three or more -1-epoxy groups in one molecule. The present invention relates to a high molecular weight polyfunctional epoxy resin characterized in that an addition reaction is carried out at an equivalent ratio of active hydrogen (A) to epoxy group (B) of (B)/(A) = 3 to 30.

The present invention will be explained in detail below.

The long-chain amine used in the present invention has at least two active hydrogen atoms on nitrogen in one molecule and has a molecular weight of 1,000 to 50,000, preferably 2,000 to 20.
000 compounds, such as polyurethanes, polyurethane ureas, polyureas, polyamide resins, urea resins, polysiloxanes having amino groups and/or imino groups, polyimide resins having amino groups and/or imino groups, polyamideimides, polyvinylamines. , polyisopropenylamine, polyethyleneimine, polytriethyleneimine, polyaminostyrene, etc. 3- is preferably an amine having two active hydrogen atoms in one molecule and an epoxy group in one molecule. A long-chain amine (E) obtained by addition-reacting an epoxy resin having two epoxy groups at an equivalent ratio of active hydrogen (c) to epoxy group (D) of (C)/(D)>1 is used. In addition, if the molecular weight of the long-chain amine is less than 1000, the mechanical properties of the cured product will not be sufficient; If it is larger than OOO, the melting point will be high, making it difficult to perform an addition reaction with an epoxy resin having at least three epoxy groups in the next step.

Examples of amines having two active hydrogen atoms in one molecule include aniline, 0-toluidine, m-toluidine, ρ-toluidine, 0-ethylaniline, +n-ethylaniline, p-ethylaniline, o- 3-xylidine, m-2-xylidine, m-4-xylidine, p-2-
Xylidine, N,N'-diphenyl-1,2-diaminoethane, N,N'-dimethyl-p-phenylenediamine, 0-7minophenol, m-aminophenol, diphenyl Urea, 0-aminoanisole, m-ami7anisole, p-aminoanisole, 3-amino-2-hydroxytoluene, 2-amino-4-hydroxytoluene, 6-amino7-3-hydroxy-〇-xylene, 5 -amino-2-hydroxy-p-
Xylene, 3-ami7catechol, 4-ami7catechol, 2-aminohydroquinone, 3-aminoguaiacol, 6-aminoguaiacol, 2-aminopropane-1
-ol, 2-aminobutan-3-ol, 2-amino-2-methyl-propan-1-ol, 2-aminopropane-], 3-diol, is.

-Propylamine, tert-butylamine, biveranone, 1,4-diazacyclohebutane, 2-methylallylamine, S-diethylhydrazine, 2-imidazolitone, 4-methyl-2-imidazolitone, 3-pyrazolitone, 2-amino-6- Chloropyridine, 3-amino-2-
Chloropyridine, 2-amino-3,5-dibromopyridine, 2-amino-6-methylpyridine, 3-ethyl-2
Examples include, but are not limited to, -piperazine 7ine, 1,2,3,4-tetrahydroquinoxaline, and 2-methyl-1,2,3,4-tetrahydroquinoxaline.

Examples of epoxy resins having two epoxy groups in one molecule include bisphenol A type epoxy resin, halogenated bis7er/-A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, Alicyclic epoxy resin (e.g. 3,4-epoxy-6-methylcyclohexyl-methyl-3,4-epoxy-6-methyl-cyclohexanecarboxylate, etc.), resorcif-lunoglycinol ether/glycidyl-3-glycidyloxy benzokamate, diglycidyl 7-thaletate, alkylene glycidyl diglycidyl fiy
Examples include x-7-yl, It, N'-diglycidyl-5,5-dimethylhyguntoin, silicon-containing epoxy resins, phosphorus-containing epoxy resins, and these can be used alone or in combination. Note that the epoxy resin having two epoxy groups in one molecule is not limited to these.

Epoxy resins having at least three or more epoxy groups in one molecule to be subjected to addition reaction with the above-mentioned various long-chain amines include 7-eleven-novolac-type epoxy resin, cresol novolac-type epoxy resin, and brominated phenol novolac-type epoxy resin. , glycerin triglycidyl ether, trimethylolpropane triglycidyl ether,
Sorbitol polyglycidyl ether, p-aminophenol glycidyl ether diglycidylamine, tetraglycidyl-1,3-bis(aminomethyl)cyclohexane, 2,6-(2,3-epoxyprobyl)phenylglycidyl ether phenylethane tetraglycidyl Examples include ether, trihydroxyphenylpropane triglycidyl ether, polyallylglycidyl ether triglycidyl 7-tuluisocyanurate, and bis(4-diglycidylaminophenyl)methane, but preferably a novolac type epoxy resin is used.

These epoxy resins and long-chain amines are mixed in such a way that the equivalent ratio of the active hydrogen (A) of the amine to the epoxy group (B) of the epoxy resin is (B)/(A)=3 to 30, preferably (B)/(A). )
The desired epoxy resin can be obtained very easily by carrying out an addition reaction at a ratio of 5 to 15.

If (B)/(A) is less than 3, there is a possibility of partial gelation during synthesis, and if it is greater than 30, sufficient mechanical properties of the cured product cannot be obtained.

The epoxy resin of the present invention thus obtained has excellent curability, heat resistance and mechanical properties and can be advantageously used in a wide range of fields. The epoxy resin of the present invention can be cured with a common epoxy resin curing agent, and a curing accelerator can also be used in combination. In addition, fillers, reinforcing agents, pigments, flame retardants, etc. can also be used in combination. Incidentally, 8- The epoxy resin of the present invention can also be used in the molded product described in Japanese Patent Application No. 123975/1982.

The present invention will be specifically explained below with reference to Examples and Reference Examples.

Example 1 500 g of Ebitsu 828 (Bis 7 E/L A type epoxy resin, epoxy equivalent: 189, manufactured by Yuka Shell Epoxy Co., Ltd.) was placed in a reactor, heated to 150°C for 4 hours, and aniline was added while stirring. 141.7 g was added dropwise over 1 hour, and after the dropwise addition was completed, heating and stirring was continued for an additional 0.5 hour. During the 1.5 hours required for the addition reaction, the temperature was maintained at 150-190°C, and the completion of the reaction was confirmed by infrared absorption spectroscopy (disappearance of absorption at 91.0 cm'' by epoxy groups).

The amine equivalent weight of this amine-terminated prepolymer was 2,700. This material was crushed to a size that could pass through a 3 mm mesh.

300 g of ESCN-2201111 (cresol novolac type epoxy resin, epoxy equivalent 220, manufactured by Sumitomo Chemical Industries, Ltd.) was placed in a reactor, the temperature was raised to 180°C, and the pulverized amine-terminated prepolymer 283.2++ was added and the temperature was increased. was maintained at 180-19θ°C and stirred for 3.5 hours to carry out the addition reaction. Completion of the reaction was confirmed when the amine equivalent became practically O. The epoxy equivalent of the obtained epoxy resin was 465 Met.

Example 2 BREN-3l in the reactor: Brominated phenol novolac type epoxy resin, epoxy equivalent 285, Nippon Kayaku Co., Ltd.
The temperature was raised to 180°C, 516°7g of the pulverized amine-terminated prepolymer obtained in Example 1 was added, the temperature was kept at 180-190°C, and the temperature was raised to 180°C.
The addition reaction was carried out by stirring for a period of time. Completion of the reaction was confirmed in the same manner as in Example 1. The epoxy equivalent of the obtained epoxy resin was 950.

Example 3 ESB-400 [brominated bisphenol A type epoxy resin, epoxy equivalent weight 410, Sumitomo Chemical Co., Ltd.] was added to the reactor.
1. OOOg was charged, the temperature was raised to 160 ''C, 127.8 g of aniline was added dropwise over 1 hour while stirring, and after the dropwise addition was completed, heating and stirring was continued for another 0.5 hours. During 5 hours the temperature was 1.60-1
The temperature was maintained at 90°C, and completion of the reaction was confirmed in the same manner as in Example 1.

The amine equivalent weight of this amine-terminated prepolymer was 3,500. This material was pulverized in the same manner as in Example 1.

A reactor was charged with ESCN-22OL (cresol novolak type epoxy resin, epoxy equivalent: 215, manufactured by Sumitomo Chemical Co., Ltd. at 300 Fi), heated to 160°C, and 697.7 g of the above-mentioned pulverized amine-terminated prepolymer was added. The temperature was maintained at 180-200'C and the reaction was carried out by stirring for 1.5 hours.The completion of the reaction was confirmed in the same manner as in Example 1.The epoxy equivalent of the obtained epoxy a (fat was It was 835.

Reference Examples 1 to 3 The epoxies (31 fats) obtained in Examples 1 to 3 were
) DM (4,4'-diaminodiphenylmethane, Hojini Tani 11, manufactured by Kagaku Kogyo Co., Ltd.).The obtained properties were
Shown in the table. In Table 1, the compounding amount is parts by weight, the curing is ■,
This was carried out by continuous heating under three conditions: (1) and (2). The impact strength is Izotsu impact strength with 7 points, and the unit is kH-c.
an/cm.

Comparative Example 1 Shrimp Foot 828 was cured with I)l)M. The properties obtained are shown in Table 1.

Comparative Example 2 Epicor) 1009 [: Bisphenol A epoxy resin, epoxy equivalent 2850, oil-based shell epoxy (
Co., Ltd.] was cured with DDM. The properties obtained are shown in Table 1.

Reference Examples 4 to 5 The epoxy resins obtained in Examples 1 to 3 were each cured with phthalic anhydride. The properties obtained are shown in Table 2. Table 2, where A is phthalic anhydride and B is 2-ethyl-4
- indicates methylimidazole.

-12 = Curing was carried out by continuous heating under the conditions of ■, ■, or ■, ■, ■.

Comparative example 3 Epikote 828 was cured with 7-talic anhydride.

The properties obtained are shown in Table 2.

Comparative example 4 Ebiko) 1009 was cured with 7-talic anhydride.

The properties obtained are shown in Table 2.

Claims (3)

[Claims] (1) A long-chain amine with a molecular weight of 1,000 to 50,000 and having at least two active hydrogen atoms in one molecule and an activated epoxy resin having at least three or more epoxy groups in one molecule. Hydrogen (A) and epoxy group (
A high molecular weight polyfunctional epoxy resin characterized in that the addition reaction is carried out at an equivalent ratio of (B)/(A>=3 to 30). (2) Long-chain amine contains 2 active hydrogens on nitrogen in one molecule.
A pillow obtained by adding an amine and an epoxy resin having two epoxy groups in one molecule at an equivalent ratio of active hydrogen (C) to epoxy group (D) of (C)/(D) > 1. The high molecular weight polyfunctional epoxy resin according to claim 1, which is a polyfunctional epoxy resin. (3) The high molecular weight polyfunctional epoxy resin according to claim 1, wherein the epoxy resin having at least three or more epoxy groups in one molecule is a novolac type epoxy resin.