JPS608696B2 - Manufacturing method of heat-resistant resin material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel heat-resistant resin material with excellent heat resistance and mechanical properties. , relates to a heat-resistant resin material containing an imidocarbamate bond and a triazine ring.

In recent years, as the performance of electrical equipment has improved, the need for heat-resistant resins with excellent heat resistance and mechanical properties has increased.

As conventional thermosetting resins with excellent heat resistance, for example, epoxy resins, silicone resins, polyimide resins, etc. are well-known. However, when the epoxy resin is exposed to a high temperature of 180 qo or more for a long time, it cannot maintain sufficient heat resistance. Furthermore, although polyimide resin exhibits excellent heat resistance, it is difficult to use this resin without solvents, and it is difficult to use, and the cured product is hard but brittle. . Furthermore, silicone resins have poor mechanical strength and are expensive. As described above, each of the conventional heat-resistant resins has its own drawbacks, but the inventors of the present invention have attempted to improve these drawbacks.As a result of intensive research, the present invention has been completed. That is, an object of the present invention is to provide a heat-resistant resin material with excellent heat resistance and mechanical properties.

Moreover, the gist of the present invention is obtained by the reaction of a polyfunctional acid anhydride and a polyfunctional cyanate compound, and is represented by the following formula '1
} contains one or more triazine rings and an imidocarbamate bond connecting them as repeating units. (In the formula, R represents a residue of a polyfunctional acid anhydride, R represents a residue of a polyfunctional cyanate compound, and n
and m represents an integer of 1 or more. ) As described above, the heat-resistant resin material of the present invention contains an imidocarbamate bond and a triazine ring in the molecular chain.

Polymers containing such heterocycles are generally said to have excellent heat resistance, and in fact, the polymer of the present invention also has very excellent heat resistance. The polymer of the present invention also has very excellent mechanical properties, which are the result of realizing appropriate combinations and repetitions of these heterocycles in the molecule. The polyfunctional cyanate compound used in the present invention has the general formula is an organic group bonded by

n represents an integer of 2 or more. ).

Typical polyfunctional cyanate compounds suitably used in the present invention are illustrated below. These polyfunctional cyanate compounds can be easily obtained by reacting corresponding phenols with halogen cyanides.

(References Anhoko w. Chem. 79, (1967) 2
19) Furthermore, as these polyfunctional cyanate compounds, cyanate trimers obtained by applying a catalyst to monofunctional or polyfunctional cyanate compounds can also be used. Among the above polyfunctional cyanate compounds, bisphenol A dicyanate and novolac polycyanate are good in reactivity and properties of cured products.

Moreover, as the polyfunctional acid anhydride used in the present invention, etc. are mentioned as representative ones.

In the present invention, the blending ratio of the polyfunctional acid anhydride and the polyfunctional cyanate compound is not particularly limited;
It is preferable to blend the polyfunctional cyanate in an amount of 1 equivalent or more, preferably 2 to 6 equivalents, based on the equivalent amount.

The reason why the polyfunctional cyanate compound is added in excess of the polyfunctional acid anhydride is that the polyfunctional cyanate compound is consumed by the self-trimerization reaction that occurs simultaneously with the reaction between the cyanate group and the acid anhydride group. The polymer according to the present invention uses a tertiary amine catalyst such as triethylamine and initially has a
Heat at 13,000 for 0.5-5 hours, then at 150-1
It is obtained by heating one to four dishes at a temperature of 8,000 °C or higher.

Further, heating at a temperature of 20,000 or higher is also performed as appropriate. By heating in two stages in this manner, trimerization of the polyfunctional cyanate compound mainly proceeds during the initial heating to form a triazine ring. This is expressed in a formal drama. (In the formula, R' represents a cyanate residue.) Thereafter, by heating at an elevated temperature, the acid anhydride group and the cyanate group react to form an imidocarbamate bond, resulting in the final cured product.

This is expressed by the formula {state. The thus obtained cured heat-resistant resin material containing the imidocarbamate bond and the triazine ring is considered to be crosslinked and bonded three-dimensionally.

Furthermore, in order to obtain the polymer of the present invention, it goes without saying that the raw composition can be used in a non-solvent form, but it can also be used in a solvent form, for example, by applying it to a substrate such as glass or mica. It can also be applied and used as laminates, prepregs, etc.

It may also be used in powder form with a thermosetting resin such as a solid epoxy resin. Furthermore, it goes without saying that various fillers, diluents, modifiers, pigments, extenders, softeners, etc. can be appropriately added to the above-mentioned raw composition as needed. Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

The bending strength in the examples was measured in accordance with JIS standard K-69.
This was done based on 11. Example 12 2-bis (4-
For 100 parts by weight of cyanatophenol)propane,
40 parts by weight of pyromellitic anhydride and 0.1 part by weight of triethylamine as a catalyst were mixed and heated at 11,000 for 1 hour to obtain a homogeneous solution.

Looking at the IR spectrum of this thing, it is 1775 cm-I
There is no change in the absorption of acid anhydrides at 1,855 cm-1, but the absorption due to cyanate groups at 2,300 cm-1 is greatly reduced, and instead, at 1,575 cm-1.
Absorption due to the triazine ring appeared at 1 and 1380 cm-1. This shows that at this stage, a reaction to form a triazine ring mainly occurs through self-trimerization of the polyfunctional cyanate compound. Furthermore, when we measured the IR spectrum after heating this material at 18,000 for 8 hours, we found that instead of absorption at 1775 cm-1 and 1855 cm-1 due to acid anhydride, 1735 skin-1 due to imidocarbamate bonding
Three new absorptions appeared: , 1785c-1, and 1825 skin-1. This shows that at this stage, the formation reaction of imidocarbamate bonds mainly occurs through the reaction between acid anhydride and cyanate. (Heating in two stages is very important in order to form a polymer containing triazine rings and imidocarbamate bonds in the polymer structure, which is the essence of the present invention.) Examples 2 A sample having the formulation used in Example 1 was heated at 12,000 for 3 hours, then heated and cured at 18,000 for 8 hours and 20,000 for 4 hours.The properties of the sample were as follows.

Bending strength (room temperature) 8.5k9/ground (22000, after 20 days) 7.7k
g/crap heating loss (〃) 0.8
5% heat softening temperature 30000
Example 32. 100 parts by weight of 2-bis(4-cyanatophenyl)propane, 50 parts by weight of ethylene glycol ditrimellitate (EGIM) and 0.1 part by weight of triethylamine as a catalyst were mixed and heated at 11,000 ℃. A homogeneous solution was obtained.

This product was heated under the same conditions as in Example 2, and the properties of the cured product were as follows. Bending strength (room temperature)
9.6k9′ land〃 (22000, 20
Days later) 9.0k9/masu heating loss (〃
, 〃 ) 1.05% heat softening temperature
250oo Example 4 EGTM was added to 100 parts by weight of a cyanate compound obtained from novolak type phenol having an average molecular weight of about 600.
5 parts by weight and 0.1 part by weight of triethylamine as a catalyst were mixed and heated at 11,000 to obtain a homogeneous solution.

This product was heated under the same conditions as in Example 2, and the properties of the cured product were as follows. Bending strength (room temperature)
8.8kg′ association〃 (22000, 20
(days later) 8.1k9'm heating loss (〃
, 〃 ) 0.91% heat softening temperature
280q○ Example 5 40 parts of glycerin tritrimellitate (GTM) was added to 100 parts by weight of 2-bis(4-cyanatophenyl)propane.
0.05 parts by weight of triethylamine as a catalyst was dissolved in a mixed solvent of solvent naphtha and dimethylformamide.

This product was applied to a silicon steel plate and heated at 13,000 for half an hour and then at 200 to 30,000 for 5 minutes to obtain a uniform, dark brown, strong coating. Comparative Example 1 Novolak-based epoxy resin with an epoxy equivalent of 175
00 parts by weight was used, and 85 parts by weight of methylendomethylenetetrahydrophthalic anhydride and 0.5 parts by weight of penzyldimethylamine were blended therein, mixed uniformly, and heated at 150oO for 8 hours and then heated at 17000C for 6 hours. A cured product was obtained.

The properties of this cured product were as follows. Bending strength (room temperature)
8.2kg/grandchild〃 (220o
o, after 20 days) 3.5k9/Sun heating weight loss (
〃 , 〃 ) 10.0% heat softening temperature
16000 comparative example 22
42-bis(4-cyanatophenyl)p.

To 10 parts by weight of bread, 9.2 parts by weight of cyclobentanetetracarboxylic dianhydride and 0.1 part by weight of trethylamine as a catalyst were mixed and heated at 110°C to obtain a homogeneous solution. This product was heated under the same conditions as in Example 2 to obtain a cured product. Although this product had almost the same heat resistance as that of the example, it showed a decrease in mechanical properties, especially brittleness, compared to the above example. The compounding ratio in this example was equivalent to 1 part acid anhydride to 8 parts cyanate compound, which is thought to result in the formation of many triazine rings with a high crosslinking density, resulting in a decrease in mechanical properties.
As described above, it can be seen that the heat-resistant resin material according to the present invention has excellent heat resistance and mechanical properties when compared with epoxy resin, which is the most widely used heat-resistant thermosetting resin material.

In the resin cured products of Examples 3 and 4 explained above, IR
When absorption spectra were measured, the presence of a triazine ring and an imidocarbamate bond was observed in all cases.

As described above, the heat-resistant resin material of the present invention contains triazine rings and imidocarbamate bonds as repeating units in its polymer, and therefore, the cured product has excellent heat resistance and mechanical properties.
It is extremely useful industrially.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, as repeating units in the molecular chain, which consists of heating a polyfunctional acid anhydride and an equivalent amount of polyfunctional cyanate compound in excess of a tertiary amine catalyst in the presence of a tertiary amine catalyst.
There are chemical formulas, tables, etc. ▼ (In the formula, R represents the residue of a polyfunctional acid anhydride, R' represents the residue of a polyfunctional cyanate compound, and n and m represent integers of 1 or more.) A method for producing a cured heat-resistant resin material containing a carbamate bond and a triazine ring. 2. The method for producing a heat-resistant resin material according to claim 1, wherein the residue of the polyfunctional acid anhydride is a residue of a difunctional acid anhydride. 3. The method for producing a heat-resistant resin material according to claim 1 or 2, wherein the residue of the polyfunctional cyanate compound is a residue of a difunctional cyanate compound. 4. The method for producing a heat-resistant resin material according to claim 1 or 2, wherein the residue of the polyfunctional cyanate compound is a novolac polycyanate residue. 5 The residue of the bifunctional cyanate compound is bisphenol A
4. The method for producing a heat-resistant resin material according to claim 3, wherein the dicyanate residue is a dicyanate residue.