JPS6244564B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel resin composition useful for adhesives, paints, laminated materials, molding materials, and the like. Conventionally, epoxy resins have been widely used for the above-mentioned purposes, but although these resins have various excellent properties, they have insufficient heat resistance. On the other hand, products with excellent heat resistance are made by further prepolymerizing a dicyanate compound produced by the reaction of bisphenol A and chlorocyan, for example.
A triazine-based resin called Triazine A is known, and although this resin has various excellent properties in addition to heat resistance, the cyanate group present in the resin is easily hydrolyzed, resulting in poor storage stability. It had the disadvantage of being inferior. For this reason, the present inventors have conducted intensive studies to develop a curable resin composition that has properties equivalent to or better than triazine resins and also has excellent storage stability. The inventors discovered that a triazine resin obtained from propenylphenol and s-triazine trihalide not only has excellent physical properties but also excellent storage stability, leading to the present invention. That is, the present invention includes a polymerizable unsaturated compound obtained by reacting m-isopropenylphenol and s-triazine trihalide in the presence of a base at a molar ratio of 3:0.8 to 1.2 and a curing catalyst. It is a curable resin composition. The polymerizable unsaturated compound used in the present invention is obtained by the reaction of m-isopropenylphenol and s-triazine trihalide, such as s-triazine trichloride, and
As shown in the structural formula below, it has a triazine skeleton in the molecule. In the reaction between m-isopropenylphenol and s-triazine trihalide, the reaction molar ratio is usually 3:0.8 to 1.2, and since this reaction is a dehydrohalogenation reaction, the amount of hydrogen halide produced is removed. Therefore, it is necessary to have about 1 mol of base present in the reaction system per 1 mol of by-produced hydrogen halide. Such bases include, for example, alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates such as sodium or potassium carbonate, alcoholates such as sodium methylate or potassium tertiary butyrate, or triethylamine, diethyl Tertiary amines such as aniline and pyridine. The reaction is usually carried out in a solution or suspension system, and suitable reaction solvents for such reactions include, for example, lower aliphatic alcohols such as methanol, ethanol, n-propanol or iso-propanol, acetone, methyl ethyl ketone,
aliphatic ketones such as diethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, aliphatic hydrocarbons, which are the fractions that accumulate during distillation of natural product mixtures such as petroleum ether, light petrol or petrol; Hydrogen, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, perchloroethylene, chlorobenzene, dichlorobenzene, ethers such as diethyl ether or diisopropyl ether, nitromethane, nitrobenzene. Examples include nitrohydrocarbons such as nitrotoluene, and water. The reaction is usually carried out at a temperature of 0 to 100°C, preferably 70°C or lower. The reaction mixture obtained by such a reaction can be prepared according to a known method, for example, when an organic solvent is used as the reaction solvent, water is added to the reaction mixture to dissolve the by-produced hydrohalide salt in water. After separating the aqueous solution, the desired polymerizable unsaturated compound is obtained by removing the solvent by distillation or the like. Of course, this treatment is not limited to the above method, and any method may be selected depending on the respective manufacturing conditions. The polymerizable unsaturated compound thus obtained can be polymerized by mere heating, but it is thought that it can be polymerized more effectively by using a curing catalyst to form a polymer having an indane structure. . The curable resin composition of the present invention is a resin composition containing such a polymerizable unsaturated compound and a curing catalyst, and the composition has not only excellent storage stability but also excellent heat resistance. The cured product exhibits a variety of excellent properties. Examples of curing catalysts used here include organic acids such as p-toluenesulfonic acid, salicylic acid, acetic acid, and maleic acid; acid anhydrides such as maleic anhydride, methylnadic anhydride, phthalic anhydride, and methyltetrahydrophthalic acid; and hydrochloric acid. Examples include mineral acids such as phosphoric acid and sulfuric acid, Lewis acids such as BF ₃ -monoethylamine, aluminum chloride, and metal salts of organic acids, imidazole and its derivatives. In the present invention, the amount of the curing catalyst to be used is not particularly limited, and is appropriately set depending on the type of catalyst used and the type and amount of the combined resin described below. In the curable resin composition of the present invention, various compounds can be added depending on the purpose and use, but in particular m-isopropenyl phenyl glycidyl ether or furthermore two or more epoxy compounds in the molecule. By adding and blending an epoxy compound having a group, the resulting curable resin composition also has the excellent properties of an epoxy resin, and exhibits extremely excellent performance. In this case, the mixing ratio of the polymerizable unsaturated compound and m-isopropenylphenyl glycidyl ether is:
Usually, the weight ratio is 5-100:0-95, and m
- The mixing ratio of isopropenyl phenyl glycidyl ether and epoxy compound is usually 5 to 5 by weight.
The ratio is more preferably 20-100:0-80 than 100:5-95. Examples of such epoxy compounds include bisphenol A-based epoxy resins, resorcinol-based epoxy resins, cresol novolak-type epoxy resins, diglycidyl ether of polyethylene glycol, and meta-aminophenol-based epoxy resins. Furthermore, the curable resin composition of the present invention may contain various natural, semi-synthetic, or synthetic resins in order to improve the properties of the resin in the final coating film, adhesive layer, molded product, etc. can. Such resins include oleoresins such as drying oils and semi-drying oils, rosins, Sierraks, Kobals, oil-modified rosins, phenolic resins, alkyd resins, urea resins, melamine resins, polyester resins, unsaturated polyester resins, and epoxy acrylates. , vinyl butyral resin, vinyl acetate resin,
One type or a combination of two or more of vinyl chloride resins, acrylic resins, and silicone resins can be mentioned, and these resins can be used within a range that does not impair the original properties of the curable resin composition of the present invention, such as the total resin amount. of 30
It can be blended in an amount of less than % by weight. In addition, carbon fiber, glass fiber, alumina fiber,
Alternatively, organic fibers such as nylon and polyester, reinforcing materials and fillers such as calcium carbonate, alumina, kaolin, diatomaceous earth, glass powder, finely powdered silica, and graphite can be used. Although these reinforcing materials and fillers vary depending on the application, they can be used in amounts up to about 4 times the weight per solid resin content for laminated materials and molding materials.
Further, for the purpose of coloring, pigments and dyes such as titanium dioxide, yellow lead, carbon black, red iron oxide, red radish, and silver oxide can be contained. Furthermore, when the resin composition of the present invention is used for paint purposes, it may be used as a coloring dye, a rust preventive pigment, an anti-sagging agent, a dispersant, a thickener, a paint film modifier, an extender pigment, a flame retardant, etc. It can contain paint formulations that are well known per se. The curable resin composition of the present invention may exist in any form such as a solid solution or a dispersion. For example, the above ingredients may be dissolved in ketones such as methyl ethyl ketone, esters such as ethyl acetate, methyl methacrylate, ethers such as dibutyl ether, aromatic hydrocarbons such as toluene, xylene, styrene, dimethylstyrene, or mixtures thereof. It can be used after being dispersed. It is also possible to add an emulsifier and use it as an aqueous dispersion. Furthermore, it can be used for various purposes in the form of a dry powder, pellet, impregnated product, compound, or the like. When using the curable resin composition of the present invention, the temperature required for curing depends on the type of catalyst,
It varies depending on the amount used, etc., but generally 70℃ to 250℃
Preferably it is in the range of 100°C to 200°C. The required heating time varies considerably depending on the conditions of use, such as whether the resin composition is a thin coating, a relatively thick molded product, or a laminate, but generally speaking, it is 30 seconds. ~10 hours, and a time sufficient for the resin component to be completely cured may be selected depending on each usage condition. Molded products using the resin composition of the present invention,
When used in the production of laminated products or adhesive structures, it is generally desirable to apply a pressure of 10 to 100 kg/cm ² during curing. The present invention will be explained below using examples. However, in the examples, parts mean parts by weight. Reference example 1 s-triazine trichloride 184g (1 mol)
was dissolved in acetone 2.5. A dispersion of 402 g (3 mol) of m-isopropenylphenol and 120 g (3 mol) of caustic soda dispersed in 500 ml of distilled water was added dropwise to this at 20°C, and then the mixture was kept at 50°C for 1 hour to react. I did this. After the reaction is complete, the reaction mixture is distilled to remove acetone, then 50% of water is added to dissolve the sodium chloride produced during the reaction, the crystals are taken out by filtration, washed with water, and dried to obtain the target compound (compound A). ) was obtained. Yield: 463 g (yield: 97%) Example 1 Compound A obtained in Reference Example 1 was dissolved in methyl ethyl ketone to prepare a varnish with a solid content of 70% by weight.
A resin composition was prepared by adding 1 part of boron trifluoride-monoethylamine to 100 parts of this varnish. After impregnating a plain weave glass cloth with the resin composition, the solvent was removed. This was air-dried at room temperature until there was no tack, and then dried at 120-130°C for 7 minutes to B-stage the impregnated resin. The obtained prepreg and copper foil were layered and heated at 180℃ for 2 hours.
The copper-clad laminate was then cured using a hot press at 190° C. for 2 hours to obtain a copper-clad laminate. The properties of the obtained laminate (according to the test method specified in JIS C-6481) are shown in Table 1. Comparative Example 1 KU-6573 (a triazine resin derived from 2,2-bis(4-cyanatophenyl)propane, a varnish with a solid content of 70% by weight using methyl ethyl ketone as a solvent. A Bayer product) 8% in 143 parts A resin composition was prepared by mixing 0.2 part of zinc octylate, 0.1 part of catechol, and 0.075 part of 2-ethyl-4-methylimidazole. After impregnating a plain weave glass cloth with the resin composition, the solvent was removed. This was air-dried at room temperature until there was no tack, and then dried at 125-140°C for 7 minutes to B-stage the impregnated resin. The obtained prepreg and copper foil were layered and heated at 180℃ for 2 hours.
The copper-clad laminate was then cured using a hot press at 190° C. for 2 hours to obtain a copper-clad laminate. Table 1 shows the properties of the obtained laminate. Comparative Example 2 100 parts of Sumiepoxy ESCN-220L (cresol novolak type epoxy resin, trade name of Sumitomo Chemical Co., Ltd.) was dissolved in 43 parts of methyl ethyl ketone, and then Sumikiure-M (4,4'-diaminodiphenylmethane, trade name of Sumitomo Chemical Co., Ltd.) was dissolved. ) was added and uniformly dissolved to prepare a resin composition. Thereafter, a laminate was obtained in the same manner as in Comparative Example 2. Table 1 shows the properties of the obtained laminate. Example 2 Compound A obtained in Reference Example 1 was left in an atmosphere of 40°C and 100% relative humidity for one week, and then
A laminate was produced in the same manner as in Example 1. The properties of the obtained laminate are shown in Table 1, and the properties are almost the same as in Example 1, and even when Compound A was stored under high humidity as described above, no effect was observed. Ta. Comparative Example 3 KU-6573 (described above) was left in an atmosphere of 40° C. and 100% relative humidity for one week, and then a laminate was prepared in the same manner as in Comparative Example 1. The properties of the obtained laminate are shown in Table 1, and the properties were extremely poor, and the influence of humidity during storage of the raw resin was very large. Example 3 After mixing 50 parts of m-isopropenyl phenyl glycidyl ether with 50 parts of the compound A obtained in Reference Example 1,
It was heated to 120°C to uniformly dissolve it. After lowering the temperature to 80°C, 2 parts of 2-ethyl-4-methylimidazole and 45 parts of methylnadic anhydride are added,
The mixture was thoroughly stirred to obtain a resin composition. This resin composition was injected into a casting mold made by sandwiching a 3 mm thick silicone rubber spacer between two glass plates, and held at 120°C for 2 hours, 150°C for 1 hour, and 180°C for 1 hour to stage cure. I did it. The properties of the obtained cast plate are shown in Table 2. Comparative Example 4 2 parts of 2-ethyl-4-methylimidazole and 90 parts of methylnadic anhydride were added to 100 parts of Sumiepoxy ELA-128 (bisphenol-based epoxy resin, manufactured by Sumitomo Chemical Co., Ltd.), and the mixture was stirred well at 80°C to form a resin. A composition was obtained. A cast plate was made using the resin composition in the same manner as in Example 3. The properties of the obtained cast plate are shown in Table 2. Example 4 50 parts of the compound A obtained in Reference Example 1, 10 parts of m-isopropenyl phenyl glycidyl ether, 20 parts of Sumiepoxy ESA-014 (bisphenol solid epoxy resin, softening point 95-104°C, Sumitomo Chemical Co., Ltd.) ,
Sumiepoxy ESA-017 (bisphenol solid epoxy resin, softening point 122-131℃, Sumitomo Chemical Co., Ltd. product) 20 parts, dicyandiamide 2 parts, 2-ethyl-
After roll mixing 2 parts of 4-methylimidazole, 50 parts of titanium oxide and 1 part of Erosil, 150μ
It was ground to the following particle size. Powder coating using this powder (-70KV charging)
The film was baked at 150°C for 1 hour and then at 1180°C for an additional 1 hour. Table 3 shows the performance of the resulting coating film. Comparative Example 5 Powder coating was carried out in exactly the same manner as in Example 4, except that Sumiepoxy ESA-014 was used instead of Compound A. The performance of the obtained coating film is shown below.
Shown in 3.

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Claims (1)

[Claims] 1. A polymerizable unsaturated compound obtained by reacting m-isopropenylphenol and s-triazine trihalide in the presence of a base at a molar ratio of 3:0.8 to 1.2 and a curing catalyst. A curable resin composition containing. 2 A polymerizable unsaturated compound and m-isopropenyl phenyl glycidyl ether obtained by reacting m-isopropenylphenol and s-triazine trihalide in the presence of a base at a molar ratio of 3:0.8 to 1.2. and a curable resin composition containing a curing catalyst. 3 Polymerizable unsaturated compound and m-isopropenyl phenyl glycidyl ether obtained by reacting m-isopropenylphenol and s-triazine trihalide in the presence of a base at a molar ratio of 3:0.8 to 1.2. A curable resin composition containing an epoxy compound having two or more epoxy groups in the molecule and a curing catalyst.