JPH021171B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermosetting epoxy resin composition having excellent heat resistance and electrical properties. Specifically, the present invention relates to an epoxy resin composition that has excellent latent properties, is substantially free of ionicity, is industrially available, and is easy to handle. The use of organometallic complexes as curing catalysts for epoxy resins has been known for a long time. However, most of them require long heating times for curing, are difficult to obtain industrially, and are not easy to handle. However, the use of certain limited organometallic complexes, especially acetylacetone complexes, has been actively researched recently because it is possible to obtain cured products with excellent latent properties and hardenability, as well as excellent physical properties. JP-A-56-2319, JP-A No. 56-4625,
57-10622, 57-10623, and 57-42721, systems containing silicon compounds as accelerators, and epoxy groups as described in Japanese Patent Publication Nos. 57-2735 and 55-116731. Containing silicone resin, Special Publication Showa 56-
Essential components of compositions containing phenolic accelerators described in Publication No. 25926;
Compositions containing acid anhydrides described in each publication No. 115800 are noteworthy. The organic part of the organometallic complex or salt plays an important role in its activity and must be selected with great care. It goes without saying that it is important that the material is industrially easily available. In view of the above points, an object of the present invention is to provide a thermosetting epoxy resin composition containing an industrially easily available curing catalyst that has excellent latent properties and is substantially non-ionic. A further object of the present invention is to provide a thermosetting epoxy resin composition that has excellent heat resistance and electrical properties and has a quick gelation time. The thermosetting epoxy resin composition of the present invention is characterized by containing (A) an epoxy resin and (B) a metal complex of N-nitrosophenylhydroxylamine as essential components. Furthermore, the thermosetting epoxy resin composition of the present invention may optionally contain organic carboxylic acid anhydrides, polyphenols,
It is characterized by containing one or more compounds selected from the group consisting of organosilicon compounds having a hydroxyl group, an alkoxy group, or an aryloxy group directly bonded to a silicon atom. The epoxy resin (A) used in the present invention is a conventionally known aromatic epoxy resin, alicyclic epoxy resin,
Examples include aliphatic epoxy resins. Particularly preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or their alkylene oxide adducts, such as bisphenol A or its alkylene oxide adducts and epichlorohydrin. Examples include glycidyl ether and epoxy novolak resin produced by reaction with Particularly preferred aliphatic epoxy resins include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or compounds containing cyclohexene or cyclopentene rings, which are epoxidized with a suitable oxidizing agent such as hydrogen peroxide or peracid. There are cyclohexene oxide- or cyclopentene oxide-containing compounds obtained by Typical examples of polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring include glycidyl ethers produced by reacting hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin. . Particularly preferable aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts; representative examples include diglycidyl ether of 1,6-hexanediol and triglycidyl ether of glycerin. , the addition of one or more alkylene oxides (ethylene oxide, propylene oxide) to aliphatic polyhydric alcohols such as diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, and glycerin. Examples include polyglycidyl ethers of polyether polyols obtained by. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenols, cresols, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these may also be blended as diluents. Further, as the epoxy resin (A) of the present invention, an epoxy silane or the like having an epoxy group in the molecule can be used. When using such an organosilicon compound having an epoxy group in the molecule, it may be unnecessary to use a curing accelerator (C). The metal complex (B) of N-nitrosophenylhydroxylamine, which constitutes an essential component of the present invention, is commercially available as a polymerization inhibitor and curing retardant for polymers. It can be easily produced by mixing an aqueous ammonium salt solution and a water-soluble metal salt. Although these metal complexes depend on the composition and the type of central metal, they often exhibit stronger activity than the corresponding alkoxides, carboxylates, and acetylacetone complexes. The metals constituting the metal complex of N-nitrosophenylhydroxylamine include titanium, iron, nickel, aluminum, cobalt, manganese, chromium, zirconium, magnesium, zinc, tin,
Selected from metals such as vanadium and other metallic elements. The epoxy resin (A) and the metal complex of N-nitrosophenylhydroxylamine (B) used in the present invention are usually 0.05 to 15 parts by weight of the metal complex of N-nitrosophenylhydroxylamine (B) per 100 parts by weight of the epoxy resin. used in proportion. Compounds exhibiting an accelerating effect (curing accelerator) used in the present invention include organic carboxylic acid anhydrides (C-1),
It is selected from polyphenols (C-2) and organosilicon compounds (C-3) having a hydroxyl group, an alkoxy group or an aryloxy group directly connected to a silicon atom. Useful organic carboxylic acid anhydrides (C-1) are:
Conventionally known monofunctional and polyfunctional carboxylic acid anhydrides are included. Examples of monofunctional carboxylic anhydrides are hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride,
These include methyl-tetrahydrophthalic anhydride, phthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, chloreneditsic anhydride, and the like. Examples of polyfunctional carboxylic anhydrides include pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimelitate, and polyazelaic acid polyanhydride. The polyphenols (C-2) are selected from compounds having a hydroxyl group in an aromatic ring, such as catechol, resorcinol, bisphenol A, pyrogallol, hydroxybenzaldehyde, novolac resin, and resorcinol resin. Another compound that shows a useful promoting effect is a hydroxyl group, an alkoxy group (methoxy group, ethoxy group, etc.), an aryloxy group (phenoxy group, parachlorophenyloxy group, etc.) directly bonded to a silicon atom.
It is an organosilicon compound (C-3) containing.
Examples of organosilicon compounds having a hydroxyl group include diphenylsilanediol, triphenylsilanol,
Triacetylsilanol, diphenylethylsilanol, trimethylsilanol, tributylsilanol, 1,3-dihydroxy-1,3-dimethyl-1,3-diphenyldisiloxane, 1,5-
Dihydroxy-1,1,5,5-tetraphenyl-3,3-ditolyltrisiloxane and the like.
Further, examples of organosilicon compounds having an alkoxy group and an aryloxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-methacryloxy These include propylmethoxysilane, vinyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, triphenylmethoxysilane, diphenyldiethoxysilane, bis(trimethylsilyl)catechol, and the like.
Moreover, these (partial) hydrolysates are also effective. The amount of the compound (C) having an accelerating effect is 0.1 to 100 parts by weight per 100 parts by weight of the epoxy resin (A). When organic carboxylic acid anhydride (C-1) is used, it may be used in a small amount of 5 to 20 parts by weight, but it is preferable to use 20 to 100 parts by weight as a curing agent for the epoxy resin. On the other hand, polyphenols (C-2) and organosilicon compounds having a hydroxyl group, alkoxy group or aryloxy group directly connected to a silicon atom (C-2)
3) may be used in an amount of 0.1 to 10 parts by weight. When using an organosilicon compound having an epoxy group in the molecule and a hydroxyl group, alkoxy group, or aryloxy group directly bonded to a silicon atom as the epoxy resin (A), a curing accelerator (C ) may not be used. The composition of the present invention further includes a solvent for dilution,
Reactive or non-reactive resins and prepolymers for modification can be blended. In addition, pigments, dyes, extenders, flame retardants, antistatic agents, antigelation agents, adhesion improvers, flow regulators,
Surfactants, antioxidants, etc. can also be blended. Although the amount of these additives is determined by the balance between functionality and curability, these compositions can be used in metal, wood, rubber, plastics, glass, ceramic products, and the like. Specific uses of the composition of the present invention include, for example, paints, inks, adhesives, molding materials, casting materials,
Examples include glass fiber-impregnated tape, putty, and sealant. In addition, the composition of the present invention has excellent electrical properties and can be used for various electrical materials such as capacitors, resistors, light emitting diodes, semiconductors, printed circuit boards, transformers, motors, electric wires, solar cells, relays, and switches. It can also be applied to other electrical and electronic parts. The composition of the present invention is easy to handle, and by selecting a catalyst system, it is possible to provide a room temperature curing composition or a medium to high temperature curing composition with excellent latent properties. Furthermore, the obtained cured product has particularly excellent heat resistance and electrical properties. The present invention will be explained in more detail below with reference to Examples. Production Example 1 Add 4 ml of titanium sulfate (30% aqueous solution) to 50 ml of an aqueous solution of 3.1 g of N-nitrosophenylhydroxylamine ammonium salt. The immediately formed precipitate was collected and dried under reduced pressure to obtain 3.2 g of N-nitrosophenylhydroxylamine titanium salt. Example 1 Alicyclic epoxy resin ERL-4221 (manufactured by Union Carbide), bisphenol A type epoxy resin
Ep-4100 (manufactured by Asahi Denka Kogyo Co., Ltd.), N-nitrosophenylhydroxylamine zirconium, titanium, iron, aluminum complex, catechol, phenol novolak XPS-4203B (manufactured by Gunei Chemical Industry Co., Ltd.), bisphenol A (Honshu Chemical Co., Ltd.) were selected to have the composition ratios (weight ratios) shown in Table 1, respectively, and the resin compositions were prepared. The results of measuring the gelation time at 150°C are shown in Table 1 together with the results of comparative products using aluminum acetylacetonate, zirconium salt, and aluminum stearate.

[Table] As is clear from Table 1, the epoxy resin composition of the present invention has a gelation time that is equal to or faster than the epoxy resin composition containing an acetylacetone complex, which is considered to have the shortest gelation time in the past. There is. Example 2 Alicyclic epoxy resin ERL-4221, bisphenol A type epoxy resin Ep-4100, γ-glycidoxypropyltrimethoxysilane KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.), silicon compound SH-6018 (manufactured by Toray Silicone Co., Ltd.) ), N-nitrosophenylhydroxylamine aluminum complex was blended into the composition shown in Table 2, and the gelation time of each resin composition at 150°C was measured. The results are shown in Table 2. Furthermore, in the case of a comparative product in which aluminum, isobutoxide, and aluminum stearate were used instead of aluminum acetylacetonate, gelation was extremely slow.

【table】

[Table] Example 3 Alicyclic epoxy resin ERL-4221 100 parts by weight,
γ-glycidoxypropyltrimethoxysilane
A blend consisting of 1 part by weight of KBM-403 and 0.5 parts by weight of N-nitrosophenylhydroxylamine aluminum complex was prepared, and the mixture was heated at 80°C for 4 hours.
It was cured at 180°C for 12 hours to obtain a plate with a thickness of 3 mm. The heat distortion temperature (HDT) and electrical properties (Tanδ) of this cured product are HDT 165℃, tanδ (150℃) 1.05 (%)
It was hot. Example 4 Using 0.5 parts of various metal salts (complexes) of N-nitrosophenylhydroxylamine as an accelerator, 80 parts by weight of EH-700 (liquid acid anhydride manufactured by Asahi Denka) was added to an epoxy resin (Ep-4100 or ERL-4221). Mixed with 100 parts by weight,
I saw a promoting effect. The metals that showed a strong acceleration effect (gelation within 10 minutes) at a temperature of 150℃ were iron (),
They were cobalt (), zinc, zirconium, aluminum, and tin. Those using other metals, such as titanium (), manganese (), magnesium (), nickel, and chromium (), also gelled within one hour. Products using Ep-4100 as an epoxy resin using titanium (), manganese (), magnesium (), and chromium () have good storage stability even after 3 months, and products using other metals also showed relatively long stability. Example 5 100 parts by weight of hydrolyzate of γ-glycidoxypropyltrimethoxysilane, 70 parts by weight of bisphenol A type epoxy resin composition Ep-4000 (manufactured by Asahi Denka), 1 part by weight of silicone surfactant, methanol A varnish was prepared by adding 1 part by weight of N-nitrosophenylhydroxylamine aluminum complex as a hardening agent to a formulation consisting of 300 parts by weight of silica sol (manufactured by Nissan Chemical). When this varnish was applied to a polycarbonate plate and dried and cured at 120℃, approx.
After 30 minutes to 1 hour, a coating film with excellent steel wool resistance was obtained. Also, the stability of the varnish was at least 3 months.

Claims (1)

[Scope of Claims] 1. A thermosetting epoxy resin composition containing (A) an epoxy resin and (B) a metal complex of N-nitrosophenylhydroxylamine as essential components. 2 Furthermore, as a curing accelerator (C) 1 selected from the group consisting of organic carboxylic acid anhydrides, polyphenols, and organosilicon compounds having a hydroxyl group, an alkoxy group, or an aryloxy group directly bonded to a silicon atom. The thermosetting epoxy resin composition according to claim 1, which contains at least one type of compound.