JPH07116286B2 - Resin containing triazine ring - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a thermosetting resin, and more specifically to a thermosetting resin having excellent processability and heat resistance.

<Prior Art> Thermosetting resins are used as various electrical insulating materials, structural materials, etc. as casting, impregnating, laminating, and molding materials. In recent years, the usage conditions of materials have tended to be severe in each of these applications, and the heat resistance of materials has become an important characteristic.

Conventionally, a thermosetting polyimide resin has been used for this purpose, but in terms of workability, heating at a high temperature for a long time is required.

Further, although the epoxy resin having improved heat resistance is excellent in processability, its high heat resistance such as mechanical properties at high temperature, electrical properties, and long-term heat deterioration resistance is insufficient.

One of the alternative materials is, for example, Japanese Patent Publication Sho 58-
27806, Japanese Patent Publication No. 59-15126, etc., a thermosetting resin containing a monomer having a double bond and a maleimide compound has been proposed. However, in these cases, since the above-mentioned monomers have low molecular weights, it was necessary to pre-polymerize them before heat curing. This is because when the resin is directly heat-cured without being made into a prepolymer, a part of the monomer evaporates during the curing. Further, for a monomer having only one double bond in the molecule,
There was a limit to the crosslink density in the cured product, and the heat resistance was insufficient.

As other materials, for example, a thermosetting mixture containing polyimide and alkenylphenol and / or alkenylphenol ether (JP-A-52-994), a maleimide compound, a polyallylated phenol compound and an epoxy resin are used as a heat-resistant resin composition. Thing (JP-A-58-
134099) etc. have been proposed. However, the polyallylated phenolic compound used here is either a polyallyl ether compound that has undergone the Claisen transition, or has a structure in which a phenolic hydroxyl group is produced by the Claisen transition during heat curing. Has a problem that the cured product has a high dielectric constant and poor water resistance.Furthermore, in the case of a novolac type, especially after curing, the nucleus-substituted allyl group and the hydroxyl group or ether group are located in the ortho position of the same aromatic ring. However, it is likely to remain unreacted, and there was a problem with the cured physical properties at high temperatures.

<Problems to be Solved by the Invention> The inventor has already proposed in Japanese Patent Application No. 60-249600 for a material that solves such problems, but the present inventor has further excellent heat resistance, As a result of an investigation to improve processability and workability especially when a solvent is not used while maintaining water resistance and electrical characteristics, it was found that a specific resin containing an alkenyl group and a triazine ring was suitable for the purpose of the previous term. Heading The present invention has been completed.

<Means for Solving Problems> That is, the present invention is represented by the following general formula (1), and n
Provides a resin containing 20% or more of one or more components.

[In the formula, n is 0 to 15, -OAr ₁ is a monovalent phenol residue substituted with an alkenyl group, -OAr ₂ O- is a divalent phenol residue, Y is -OAr ₁ or another substituent. Represent. ] Here, for the alkenyl group substituted for Ar ₁ , CH ₂ = CH-, CH ₂ = CHCH ₂ − One or more of CH ₃ CH = CH- and the like are exemplified. Ar ₁ may be substituted with a substituent other than an alkenyl group. Further, Y may be the above-OAr ₁ , other alkyl group, alkoxy group, halogen atom, alkyl group-substituted or unsubstituted amino group, aryl group, aryloxy group, hydroxyl group, CH ₂ = CHCH ₂ O- and the like may be used.

Preferred examples include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and CH ₂ ═CHCH ₂ O—, but when particularly high heat resistance is required, Y is most preferably —OAr _1. preferable.

On the other hand, -OAr ₂ O- is a divalent phenol residue. And the like, and other substituents may be substituted on the aromatic ring.

Regarding the method for producing a resin containing an alkenyl group and a triazine ring of the present invention, when Y in the general formula (1) is —OAr ₁ , cyanuric chloride (n + 1) is represented by the following reaction formula (2).
It is obtained by reacting n moles of bisphenol and alkenylphenol (n + 3) moles.

The reaction temperature is preferably 0 to 100 ° C., and it is preferable that a base is present in the reaction system.

For the base, sodium hydroxide, potassium hydroxide,
Examples include sodium carbonate, potassium carbonate, sodium methylate, sodium ethylate, triethylamine, diethylaniline, pyridine and the like. The bisphenol and the alkenylphenol may be reacted in either order, and there is no problem if they are reacted at the same time.

When Y is an alkyl group, an alkoxy group or an aryloxy group, a substituted dichlorotriazine represented by the following general formula (3) is obtained, and as shown in the following reaction formula (4), this (n + 1) mol is It is preferable to react n moles of bisphenol and 2 moles of alkenylphenol. Regarding the reaction conditions, the same conditions as in the reaction represented by the formula (2) can be exemplified.

The compound represented by the formula (3) can be obtained by reacting Grignard reagents corresponding to cyanuric chloride when X is an alkyl group or an aryl group. A mixture of X as an alkoxy group or an aryloxy group can be obtained by reacting alcohols or phenols corresponding to cyanuric chloride in the presence of a base.

As described above, having the alkenyl group and the triazine ring of the present invention,
Although the resin manufacturing method has been described, the present invention is not limited to this.

The resin having an alkenyl group and a triazine ring of the present invention is represented by the general formula (1) as described above, but the component in which n in the formula (1) is 1 or more is at least 20%.
is necessary. When the amount of n = 0 is large, it becomes crystalline, and it is necessary to maintain the temperature at 100 ° C. or higher in order to impart fluidity. As a result, the resin and other solid components cannot be kneaded at a low temperature, and excellent workability and workability cannot be obtained when the solvent is not used, which is the effect of the present invention.

Regarding the use of the resin of the present invention, it can be thermoset alone, but it can also be thermoset in combination with another compound or resin having an unsaturated group. For example, a bismaleimide or polymaleimide having two or more maleimide groups in the molecule, an unsaturated polyester resin, a diallyl phthalate resin, an epoxy acrylate resin, or a resin other than the resin of the present invention has two or more alkenyl groups in the molecule. Examples thereof include compounds and resins, but the invention is not limited thereto. When particularly high heat resistance is required, it is preferably used in combination with bismaleimide or polymaleimide.

Regarding the method of heat curing, it is possible to easily perform heat curing without a catalyst, and it is also possible to perform heat curing using a radical polymerization initiator such as an organic peroxide or an azo compound in combination. Examples of such radical polymerization initiators include benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl hydroperoxide. , Azobisisobutyronitrile and the like. Other tertiary amines such as tributylamine, triethylamine and triamylamine, benzyltriethylammonium chloride,
It is also possible to use a quaternary aluminum salt such as benzyltrimethylammonium hydroxide, an imidazole, a boron trifluoride complex, a transition metal acetylacetonate, etc. in combination. The curing temperature is preferably 50 to 300 ° C.

Also, a known polymerization inhibitor may be used in combination in order to adjust the curing speed. For example, 2,6-di-t-
Butyl-4-methylphenol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-
Methylenebis (2,6-di-t-butylphenol), 4,
Phenols such as 4′-thiobis (3-methyl-6-t-butylphenol) and hydroquinone monomethyl ether, hydroquinone, catechol, pt-butylcatechol, 2,5-di-t-butylhydroquinone, methylhydroquinone, t -Polyhydric phenols such as butylhydroquinone pyrogallol, phenothiazine compounds such as phenothiazine, benzophenothiazine and acetamidophenothiazine, N-nitrosodiphenylamine, N
There are N-nitrosamine compounds such as nitrosodimethylamine.

If necessary, the resin of the present invention or the composition comprising the resin may be used in combination with a filler, a filler, a reinforcing agent, a pigment or the like. For example, silica, calcium carbonate, antimony trioxide, kaolin, titanium dioxide, zinc oxide, mica, barite, carbon black, polyethylene powder, polypropylene powder, aluminum powder, iron powder, copper powder, glass fiber, carbon fiber, alumina fiber, asbestos. Fibers and the like are used and provided for molding, lamination, adhesives, composite materials and the like. Other known thermosetting resins depending on the purpose, for example, an alkenyl group-containing resin or a triazine group-containing resin other than the present invention,
Unsaturated polyester resin, epoxy resin, silicone resin, phenol resin, etc. may be added.

<Effects of the Invention> Thus, the resin of the present invention has processability, heat resistance, mechanical properties,
Exhibits excellent electrical characteristics.

Further, since the resin of the present invention is an amorphous material having no melting point and has fluidity at 100 ° C. or lower, it can be kneaded with other solid components at a low temperature. As a result, the resin composition of the present invention has excellent workability and workability as compared with the crystalline compound, and the effect is great particularly when a solvent is not used.

<Example> The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 23.6 g (0.4 mol) of 2-propenylphenol and 36.8 g of cyanuric chloride were placed in a flask equipped with a stirrer and a thermometer.
(0.2 mol), resorcin 11.0 g (0.1 mol) and acetone 173 g are charged and dissolved. Thereafter, the temperature was maintained at 20 to 30 ° C., 252.0 g (0.63 mol) of 10% NaOH was added dropwise over 1 hour, and after the addition, the temperature was kept for 2 hours to complete the reaction. After the reaction, charged with methyl isobutyl ketone and washed with water to produce Na as a by-product.
Cl was removed and the solvent was distilled off to obtain a resin having a softening point of 58 ° C.

When the molecular weight distribution was examined by GPC (solvent tetrahydrofuran, detector RI, column Toyo Soda achieved G3000-HXL, 2000-HXL, 1000HXL), 62% of the components of n in the general formula (1) were 1 or more.

Example 2 Example 1 was repeated except that 11.0 g (0.1 mol) of resorcin was replaced with 25.0 g (0.1 mol) of bisphenol S in Example 1.
The same operation as above was performed to obtain a resin having a softening point of 89 ° C. GPC
80% of the components in which n was 1 or more were analyzed.

Example 3 A flask equipped with a stirrer and a thermometer was charged with 45.0 g (0.25 mol) of 2-methoxy-4,6-dichloro-S-triazine,
26.8 g (0.2 mol) of 2-allylphenol, 34.2 g (0.15 mol) of bisphenol A and 187 g of dioxane were charged and dissolved. Then keep the temperature at 40-50 ° C and 10% NaOH 210g
(0.525 mol) was added dropwise over 1 hour, and the reaction was terminated by keeping the temperature for 2 hours after the addition. After the reaction, the same operation as in Example 1 was performed to obtain a resin having a softening point of 78 ° C. N in GPC analysis
The percentage of components having a value of 1 or more was 83%.

For the method of synthesizing 2-methoxy-4,6-dichloro-S-triazine, see J. Amer. Chem. Soc. 73P2986 (195).
1) Following JT Thuroton et al., The synthesis was carried out using cyanuric chloride, methanol and sodium hydrogen carbonate as raw materials.

Example 4 45.2 g (0.2 mol) of 2-phenyl-4,6-dichloro-S-triazine in a flask equipped with a stirrer and a thermometer,
2-Isopropenylphenol 26.8 g (0.2 mol) resorcin 11.0 g (0.1 mol) and acetone 160 g are charged and dissolved. After that, keep the temperature at 40-50 ° C and 10% NaOH 168.0g
(0.42 mol) was added dropwise over 1 hour, and after the addition, the temperature was kept for 2 hours to complete the reaction. After the reaction, the same operation as in Example 1 was performed to obtain a resin having a softening point of 54 ° C. In GPC analysis, 56% of the components had n of 1 or more.

Regarding the method for synthesizing 2-phenyl-4,6-dichloro-S-triazine, see Helv. Chem. Acta 33P1365 (195).
0) According to R. Hirt et al., 1 mol of cyanuric chloride and 1 mol of phenylmagnesium bromide were used as starting materials for the synthesis.

Continuation of front page (56) References JP-A-50-44298 (JP, A) JP-A-55-131023 (JP, A) JP-A-50-84586 (JP, A) JP-A-54-159494 (JP , A) JP-A-56-24423 (JP, A) JP-A-53-47496 (JP, A)

Claims (2)

[Claims] 1. A compound represented by the following general formula (1), wherein n is 1
Triazine ring-containing resin containing 20% or more of the above components. [In the formula, n is 0 to 15, -OAr ₁ is a monovalent phenol residue substituted with an alkenyl group, -OAr ₂ O- is a divalent phenol residue, Y is -OAr ₁ or another substituent. Represent. ] 2. The triazine ring-containing resin according to claim 1, wherein the alkenyl group is a propenyl group, an isopropenyl group or an allyl group.