JPS6354300B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for curing polyepoxy resin using a 2-substituted-4,6-diamino-s-triazine compound (hereinafter abbreviated as triazine compound). The epoxy resin cured using the triazine compound of the present invention has a remarkable effect of preventing migration of gold, silver, copper, etc. that constitute the wiring circuit.
The method of the present invention is considered to be particularly useful in the field of manufacturing encapsulating materials for electronic components, copper-clad laminates, and coating materials for organic and inorganic substrates. (Prior art) Epoxy resin has excellent heat resistance, electrical insulation, and adhesive properties, so it has traditionally been widely used as a sealing material, insulating material, and substrate matrix material, especially in the fields of electronic components and printed circuit boards. I've been However, epoxy resin has a low ability to prevent migration, a phenomenon in which the metal constituting the wiring or electrode on the insulating material migrates on the insulating material due to the action of potential difference in a high humidity environment, resulting in poor insulation. Alternatively, problems such as short circuits may occur. (Problems to be Solved by the Invention) As the miniaturization and density of components and the miniaturization of wiring circuits progress, prevention of migration in particular has become increasingly required within the industry. Various commercially available resins aimed at preventing migration have flaws such as harsh curing conditions, large curing shrinkage, and low adhesion, and are not necessarily in a satisfactory state. . Furthermore, although the glass frit used in ceramic substrates has an excellent anti-migration effect, it is expensive and has drawbacks such as a high baking temperature. (Means for Solving the Problems) In view of the above circumstances, the inventors of the present invention have conducted extensive research and have found that a 2-substituted-4,6-diamino-s-triazine compound is included as an essential component in polyepoxy resin. The inventors have now completed the present invention by discovering that by adding these compounds, a cured product can be produced that is rich in heat resistance, insulation, and adhesion, and has an excellent anti-migration effect. 2-substitution-4 used in the method of the present invention,
6-Diamino-s-triazine can be prepared by known methods [for example, Journal of Chemical, Society
1952, 1279 pages (S. Birtwell: JCS, 1952
1279)], it is a compound obtained by the reaction of nitrile and dicyandiamide, and it is also a compound obtained by the reaction of biguanide and acrylic acid chloride [2-vinyl-4,6-diamino-s-triazine [e.g., Journal of American Chemical Society]. 1958 Volume 80, Page 988 (CG
Overberger et al.: JACS, 80, 988, 1958)] and an alcohol, amine, or carboxylic acid containing active hydrogen. Next, a method for curing polyepoxy resin using a triazine compound will be described. When a triazine compound is used as a curing agent for polyepoxy resin, the cured product is rich in heat resistance, insulation, and adhesion, and has an excellent migration prevention effect. In the method for curing the polyepoxy resin of the present invention, aliphatic amines, aromatic amines,
Tertiary amines, polyamide resins and acid anhydrides can be used in combination, especially 2,4-diamino-6-{2'-methylimidazolyl-(1')}ethyl-s-triazine for triazine compounds. ,
2,4-diamino-6-{2'-methylimidazolyl-(1')}ethyl-s-triazine isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl -5-hydroxymethylimidazole, 4,
4'-methylene-bis-(2-ethyl-5-methylimidazole), 2-phenyl-4-benzyl-
When 5-hydroxymethylimidazole is used in combination, it can be used as a so-called one-component formulation. In addition, triazine compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-
Phenylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl -2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-
When cyanoethyl-2-phenyl-4-methylimidazole and 1-benzyl-2-methylimidazole are used together, they do not have the storage stability required for one-component formulations, but they cannot be combined with polyepoxy resins. By blending and heating immediately before use, a cured product with excellent anti-migration effects can be obtained. The polyepoxy resin of the present invention contains an average of more than one epoxy group per molecule, and this group is located at the terminal position of the molecule.

[Formula] may be used, or it may be inserted in the middle of the molecular formula.

A group of the form [Formula] may also be formed. This polyepoxy compound is aliphatic, cycloaliphatic,
They may be aromatic or heterocyclic and may be substituted with non-interfering substituents such as hydroxyl, alkyl, alkoxy, ester, acetal, and ether groups. Typical polyepoxy resins suitable for the practice of the present invention include polyglycidyl ethers of polyhydric phenols, such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, other epoxidized phenolic novolac resins, alicyclic These include epoxy resins and their brominated epoxy resins. The amount of the triazine compound added to the polyepoxy resin should be 5 to 50 parts by weight per 100 parts by weight of the polyepoxy resin, and the amount of the curing agent or curing accelerator used in conjunction with this should be 5 to 50 parts by weight. is used in a proportion of 1 to 120 parts by weight in the case of aliphatic amines, aromatic amines, tertiary amines, polyamide resins and acid anhydrides, and in a proportion of 0.025 to 10 parts by weight in the case of the aforementioned imidazole compounds. It is preferable to use If the amount of these compounds added exceeds this range, the heat deformation temperature of the cured product will decrease, and if it is too small, it will take a long time to cure, making it impractical. The curing conditions for the polyepoxy resin may need to be changed somewhat depending on the components and blending amounts of the resin and curing agent, but it is usually sufficient to heat the resin at a temperature of 100 to 250°C for 2 minutes to 8 hours. The method of the present invention will be specifically explained below using Examples and Reference Examples. Example 1 100 to 20 parts by weight of 2-substituted 4,4- as an essential component to 100 parts by weight of polyepoxy resin (trade name: Epicote #828, manufactured by Yuka Ciel Epoxy)
Diamino-s-triazine compound and 2.2 to
4.4 parts by weight of 2,4-diamino-6-{2'-methylimidazolyl-(1')}ethyl-s-triazine isocyanuric acid adduct (trade name: Kyuazol 2MAOK, manufactured by Shikoku Kasei Kogyo) and 5 parts by weight Add three viscosity modifiers (trade name: Aerosil #300, manufactured by Nippon Aerosil) and mix in a three-roll mill to prepare various polyepoxy resin formulations.
Gel time and temperature of each formulation at a temperature of 150°C
A migration resistance test was conducted on a coating film cured by heating at a temperature of 150°C for 15 minutes. The results of these tests are shown in Table 1, and the formulation containing the triazine compound showed migration resistance for more than 1000 hours, while the formulation that did not contain it showed migration resistance for only 48 hours or less. Nakatsuta.

【table】

【table】

【table】

[Table] Example 2 Table 2 shows a test example in which the method for curing the epoxy resin of the present invention was applied to a one-component solder resist ink for printed circuit boards.

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[Table] Example 3 Menthanediamine, an alicyclic polyamine, was mixed as a curing agent at a ratio of 22 parts by weight to 100 parts by weight of epoxy resin, and the properties of the cured product were measured, as shown in Table 3. The result was The curing conditions for the compound were as follows: after being left at room temperature for 12 hours, it was heated at 100°C for 2 hours and at 150°C for 4 hours.

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Claims (1)

[Scope of Claims] 1. 5 to 50 parts by weight of a 2-substituted-4,6-diamino-s-triazine compound represented by the following formula based on 100 parts by weight of a polyepoxy resin, an aliphatic amine, an aromatic amine, A polyepoxy resin characterized in that at least one curing agent selected from the group of curing agents consisting of tertiary amines, polyamide resins and acid anhydrides is mixed in a proportion of 1 to 120 parts by weight and heated. Curing method. formula: However, in the formula, R is a methoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, n-octadecyloxyethyl group, δ-cyano-n-butyl group, aminoethyl group, allyl aminoethyl group. group, n-propylaminoethyl group, n-dodecylaminoethyl group, n-octadecylaminoethyl group, β-aminoethylaminoethyl group, o-cyanophenyl group, m-cyanophenyl group, p-cyanophenyl group, m-tolyl group , phenylaminoethyl group, o-tolylaminoethyl group, m-tolylaminoethyl group,
p-tolylaminoethyl group, naphthyl group, benzylaminoethyl group, β-naphthylaminoethyl group, acryloyloxyethyl group, methacryloyloxyethyl group, isocyanurethyl group, 2-
Ethylimidazolyl-(4)-dithiocarbonylethyl group, or β-pyridylaminoethyl group,
R′ is bis-(diethylenetriamino-1.3)-ethyl group or bis-(m-xylylene diamino)
- Represents an ethyl group. 2 2-substituted-4,6-diamino-s-triazine compound represented by the following formula based on 100 parts by weight of polyepoxy resin Formula: (However, in the formula, R and R' are the same as above) and 5 to 50 parts by weight of 2,4-diamino-6-
{2′-methylimidazolyl-(1′)}ethyl-s-
Triazine, 2,4-diamino-6-{2'-methylimidazolyl-(1')}ethyl-s-triazine isocyanuric acid adduct, 2-phenyl-4,
5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 4,4'-methylene-bis-(2-ethyl-5-methylimidazole), 2-phenyl-4
-Benzyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dibenzylimidazole, 2-methylimidazole, 2-ethyl-4
-Methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-
Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-
At least one imidazole selected from the group of imidazole compounds consisting of phenyl-4-methylimidazole and 1-benzyl-2-methyl-imidazole is mixed in a proportion of 0.025 to 10 parts by weight, and the mixture is heated. Method of curing polyepoxy resin.