JPS59210935A - Hardener for epoxy resin and blend composition - Google Patents

Abstract

PURPOSE:To provide a quick-curing hardener for epoxy resins, which is excellent in reliability and suitable for use in epoxy resins for sealing semiconductors, by co-condensing a phenol, a prim. amine and formaldehyde. CONSTITUTION:A phenol such as phenol, cresol, xylenol or resorcinol, a prim. amine such as aniline, phenylenediamine, toluylenediamine or hydrazine and formaldehyde are co-condensed. The resulting co-condensate of formula I (wherein R1 is -H, -CH3, -OH, etc.; R2 is a group of formula II, III or IV, etc.) is used as main component to obtain the desired hardener for epoxy resins. The co- condensate of formula I has nitrogen atoms in the backbone, which have an excellent effect as a curing catalyst for epoxy resins and the distance between phenol nuclei is long so that the co-condensate has a quick-curing property and low stress.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hardening agent for hardening resin having excellent hardening properties and a compounded composition thereof, which is characterized by the use of a resin having family atoms in the skeleton. There it is.

In recent years, metal parts and ceramic parts have rapidly become more durable due to increased quantity and cost reduction.

As these plastics, phenolic resins, polyester resins, epoxy resins, etc. were rejected, and initially phenol resins were used for general purposes, polyester resins were used for core wires, and epoxy resins were used for cylindrical grade insulation wires. However, in the past few years, due to the shift to plastic parts for surface quality parts and the demand for the same quality (Glasnuck LJ), epoxy resins have also been used in large quantities, and their character as a general-purpose resin has been reduced.

In the field of epoxy (both-sided molding materials), in order to respond to this generalization (mass production and cost reduction), the molding cycle is shortened and streamlined by molding automation.For example, Hamura molding for expansion sealing is This has led to the shift to plastic tights, where materials can be transported by hand, and the introduction of multi-silane gloss molding machines, leading to the lack of automation systems.

Currently, a problem in semi-dedicated sealing applications is that when the material is made continuous, the 1i-roughness decreases.

Measures Qi taken to improve current conduction and curing properties of the material
Although the amount of hardening additive is increased, this curing catalyst is considered to be a low-molecular impurity in terms of material purity, and is considered to be the cause of decreasing filter reliability. Furthermore, as the material becomes m lit, the internal stress of the J molded product becomes less strong and the adhesion with the 9 insert becomes weaker, which is thought to reduce reliability.

The present invention provides a curing agent for epoxy t-t MW that enables a significantly shorter length of the epoxy resin, and an epoxy resin composition containing the curing agent that can be twisted particularly reliably.

The gist of the present invention is (1) A co-condensate of phenols such as phenol, cresol, xylenol or halesorcin, primary amines such as aniline, phenylene diane, tolylene diamine or hydrazi 7, and formaldehyde. A curing agent for epoxy resin with characteristics and an epoxy resin composition containing the curing agent are required.

The average structural formula of the curing agent for epoxy resin of the present invention is as shown below.

R1 knee 14 , -aHl,, (OH3)s ,”'
The curing agent for epoxy resins of the present invention has fixed nitrogen atoms, which are recognized to be effective as curing catalysts for epoxy resins, in its skeleton, and also prevents φ from increasing the distance between phenol nuclei. We were able to achieve both rapid curing and low stress. This is because the curing agent is a curing catalyst that is not harmful as an impurity and has a stress-relaxing structure.

Further, in the case of a curing agent, the higher the molar ratio of fluorine atoms to hydroxyl groups, the better the curability becomes. The nitrogen atomic ratio of the curing agent and the composition properties are summarized in the table below.

The anti-barking agent for epoxy resins of the present invention can be used alone or in combination with other 1ml-forming agents by appropriately blending them into epoxy resins. If necessary, other curing agents, curing accelerators, pigments, surface treatment agents, j'ilk type agents, etc. can be added.

The epoxy used in the present invention (Kono B'F1 can be any type of epoxy), such as bisphenol type epoxy side layer, phenol novolac type epoxy resin, cresol noydrach epoxy kl 11*% triazine nucleus-containing epoxy resin, etc. can be mentioned.

Other curing agents that can be used in combination with the curing agent of the present invention include those that react with epoxy resins, but
For example, phenol novolaks such as phenol novolak and orthocresol novolac, tetrachlorophthalic anhydride (TCPA), hexahydrophthalic anhydride (HH?A), tetrahydrophthalic anhydride (Tg
Acid anhydrides such as PA), nocyanthamide (DDA
), and amines such as noaminophenylmethane (DDM'). If you want to further promote one stool, you can use trimethylaminomethylphenol, piperazine, 2,3.4,6,7.8,9゜lO-octahydro-viramide (1,2-a) azepine, etc. Tertiary amines, octylphosphine, nophenylphosphine,
Organic phosphine compounds such as butylphenylphosphine, tricyclohexylphosphine, triphenylphosphine, 2-phenylimidazole (2''z), 2ethenoatelimidazole (2JU4MZ), l-pennolimidazole (IBZ), 2-butyl'+ mif Curing accelerators such as sole (2MZ)%t/) imidazoles may also be used.

In addition to the above-mentioned formulations, the composition of the present invention can contain fillers, pigments, flame retardants, mold release agents, etc. Fillers used include silica, glass, charcoal, calcium, mica, clay, Examples include inorganic fillers such as alumina, asbestos, aluminum hydroxide, and magnesium hydroxide, and bale fillers such as wood flour, crushed pulp, and pulp. The surface of the filler may be modified with a surface treatment agent such as a ring agent. Mold release agents such as carnauba wax, stearic acid, stearates, polyethylene wax, etc. can be used.

The Examples and Comparative Examples are added dropwise while cooling. After that, phenols were added and heated to about 100°C to carry out a reflux reaction, and then from 150°C to
It is heated to 300°C, dehydrated, and served as a resin co-condensate.

The curing agent of the cocondensate used in the examples obtained by the above method was Anianiline liquid resorcin cocondensate (N10H=(,
1,3) B Nianiline-modified phenol copolymer (ff10H=
0.6) C: Funinidine diamine modified resol co-conjugate (Mu1
0H=1.2) Their number average molecular weight is approximately 600.

Ortho-cresol novolac type epoxy resin Koron N-670 (manufactured by Dainippon Ink Chemical Industry Co., Ltd., number average molecular weight IL) 00) and cured qlj A, B, O and filler: crystalline silica (Ryuga Sunrex" 20 (1) 70 coulometric parts,
Curing accelerator: 2E4MZ (manufactured by Shikoku Kasei), surface treatment agent Nijirankanorifuging agent A-187 (E1 Unicar 4) 0-b parts by weight, crystal forming agent: Hoechst wax 01) Q, 5 parts by weight, Several molding materials were manufactured using a heated roll using a composition containing 8 sets of pigments, etc. and the compounding ratio shown in Table 1. Also, as a comparative example, the other formulations were the same as in the examples, but phenol novolac ptq was used as a curing agent.
-1oo (Nippon Kayakusami, number average molecular weight 600) was used. The evaluation results are shown in Table 1, and all of them were behind the comparative example in terms of hardness and hardness and i=8.

Relative comparison score if the number (G ratio/column is set to 100) and the fc ratio is 100.

In the test, a molded product with a simulated aluminum element was placed in an atmosphere of 2 atm, 121°C, and 100 wet farts, and the reaction rate of aluminum was determined.

Claims (1)

[Claims] A classifier for boxy resin. (2) An epoxy resin composition containing a co-condensate of phenol ALL-class amines and formaldehyde.