JPH043428B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a thermosetting resin composition having excellent heat resistance, processability, and mechanical properties.

[Technical background of the invention and its problems] Polyimide resins have excellent heat resistance and chemical resistance, so they have traditionally been used in films that are used at high temperatures.
It is used in a variety of applications such as electrical coatings, laminates, paints, adhesives, and molded products.

Among these, polymers of bismaleimide and aminobenzoic acid, homopolymers of bismaleimide, and copolymers of bismaleimide and monomaleimide have very excellent thermal properties, but their molecular structure clearly shows that mechanical strength is not sufficient.

Therefore, it is used by copolymerizing it with other materials, sacrificing some of its thermal properties and improving its mechanical strength. In addition, bismaleimide is
Many materials have a melting point of 150°C or higher, making it difficult to process them by heating and kneading them, and furthermore, radical chain polymerization at temperatures above that melting point is extremely fast, resulting in narrow molding tolerances and even more rapid hardening. Cured molded products tend to become distorted due to the heat generated by bismaleimide, and resins made of bismaleimide alone or copolymerized with monomaleimide are difficult to put into practical use. On the other hand, polyetherimide, represented by Ultem (trade name manufactured by GE), has excellent mechanical and thermal properties, but because it is thermoplastic, it undergoes dimensional changes at high temperatures of 160°C or higher.
It had the disadvantage of large thermal deformation.

[Object of the Invention] The object of the present invention was to solve the above-mentioned drawbacks, and is made of a heat-resistant material with good mechanical properties.
Another object of the present invention is to provide a thermosetting resin composition that has excellent processability and can be widely used for lamination or as a molding material.

[Summary of the Invention] As a result of intensive research to achieve the above object, the present invention provides that the above object can be achieved by adding polyetherimide to an addition reaction product of bismaleimide and aminobenzoic acid. This is what I found.

That is, the present invention provides (A) bismaleimide represented by the general formula ();
(b) an addition reaction product obtained by subjecting aminobenzoic acid to a heating reaction; (In the formula, R ¹ is a hydrogen atom or an alkyl group, R ²
is -O-, _-CH2- , _-SO2- or -S-S-
, R ³ represents a hydrogen atom, an alkyl group, or a chlorine atom) (B) Polyetherimide represented by the general formula () (In the formula, n represents a positive integer.) A thermosetting resin composition characterized by having as an essential component.

(a) Bismaleimide used in the present invention is a condensation reaction product of maleic acid and its derivatives with diamine, and specifically, 4,4'-methylenebis(N-phenylmaleimide), 4,4'-oxybis( N-phenylenemaleimide), 4,4'-sulfone bis(N
-phenylmaleimide), 4,4'-dithiobis(N-phenylmaleimide), and the like, and these may be used alone or in combination of two or more.

Examples of the aminobenzoic acid (b) used in the present invention include p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, etc., and these may be used alone or in combination of two or more. Aminobenzoic acid can be addition-polymerized to bismaleimide in any amount, but in order to obtain appropriate curing time and moldability, aminobenzoic acid should be added in an amount of 0.2 to 1.0 mol, especially 0.4 to 0.8 mol, per 1 mol of bismaleimide.
Preference is given to using moles. Addition polymerization of bismaleimide and aminobenzoic acid is carried out by a heating reaction in the melt, but dioxane, N,
The reaction can also be carried out by heating in a solvent such as N'-dimethylacetamide, dimethylformamide, or N-methyl-2-pyrrolidone. In a heating reaction in a solvent, when bismaleimide and aminobenzoic acid are stirred and raised in temperature, they melt at around 100℃, and
If kept at a temperature of 150℃, an addition polymerization reaction will occur,
A solid or viscous addition reaction product can be obtained by cooling to room temperature.

The addition reaction product (A) is desirably contained in an amount of 15 to 85% by weight based on the resin composition. If it is less than 15% by weight, the desired workability cannot be obtained, and if it exceeds 85% by weight, although workability improves, mechanical strength decreases, which is not preferable.

(B) is one component of the thermosetting resin composition of the present invention.
Examples of polyetherimide include Ultem (trade name, manufactured by GE). The resin composition of the present invention is usually dissolved in a single or mixed solvent such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dioxane, methyl cellosolve, ethyl cellosolve, etc., and is used for laminated products such as glass cloth. The resin solution is applied to the base material by impregnation coating. Next, the prepregs obtained by volatilizing the solvent are superimposed, heated, and pressure-molded to obtain a laminate having excellent heat resistance, electrical properties, and mechanical properties. When applied to molding materials, a powder material that can be molded at 180 to 200°C can be obtained by pouring the resin solution into a large excess of water and separating and drying only the resin component. Similarly, by dry blending the powders of (A) and (B),
A powder molding material that can be molded at ~250°C is obtained.
These molding materials make it possible to obtain molded articles with excellent mechanical properties and thermal properties.

[Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 1 mole of 4,4'-methylenebis(N-phenylmaleimide) (molecular weight 358) was mixed with 0.6 mole of p-aminobenzoic acid (molecular weight 137), and the mixture was heated to 100% while stirring.
The temperature was raised to ℃ to form a uniformly dissolved liquid. This liquid was heated to 130°C, held for 30 minutes, and cooled to room temperature to obtain a solid addition reaction product. crushed addition reactant
200 g of N-methyl-2-pyrrolidone was added, and then a solution of 60 g of Ultem (a polyetherimide trade name manufactured by GE) dissolved in a mixed solvent of 300 g of dimethylformamide and 300 g of N-methyl-2-pyrrolidone was added. The mixture was heated and stirred at 90°C for 1 hour to obtain a uniform resin composition. The thermal decomposition curve of the resin composition is shown in FIG.

This solution was applied to a satin type glass cloth treated with γ-aminopropyltriethoxysilane,
A prepreg was obtained by drying at 110°C for 5 minutes, 150°C for 10 minutes, and 170°C for 5 minutes. Next, multiple sheets of this prepreg are stacked together and preformed in a press heated to 200℃ while degassing twice.
After maintaining the pressure at 60 Kgf/cm ² for 60 minutes, the pressure was removed to obtain a laminate. The obtained laminate was heated at 230℃.
After being kept for 15 hours and then cured, the bending strength was measured to be 57Kgf/mm ² at room temperature and 50Kgf/mm 2 at 200℃.
It maintained a strength of 52 Kgf/ ^{mm 2} even after deterioration at 230°C for 20 days.

Example 2 1 mol of 4,4'-oxybis(N-phenylmaleimide) (molecular weight 360) and 0.4 mol of p-aminobenzoic acid (molecular weight 137) were mixed and mixed with stirring.
Heat to 110°C to uniformly dissolve and form a liquid. This liquid was heated to 140°C, held for 30 minutes, and then cooled to room temperature to obtain an addition reaction product. crushed addition reactant
40% by weight, 10% by weight of Ultem (polyetherimide trade name manufactured by GE), 25% by weight of silica powder, and 25% by weight of aminosilane-treated glass chops, kneaded at 140°C for 10 minutes, and cooled.
It was crushed to obtain a molding material. This molding material is heated to 240℃.
Placed in a mold heated ^to
After press molding for a few minutes, a molded product with a good appearance could be obtained. After the molded product was kept at 250℃ for 5 hours and cured, the tensile strength (according to JIS-K6911) was tested and found to be 11.7Kgf/mm ² at room temperature, 250
It had a strength of 10.2Kgf/mm ² even at 250°C, and maintained a strength of 8.6Kgf/mm ² (measured at room temperature) even after being deteriorated by heating at 250°C for 20 days. The thermal decomposition curve before filler kneading is shown in FIG.

Example 3 179 g of 4,4'-methylenebis(N-phenylmaleimide) (molecular weight 358) and o-aminobenzoic acid
25g and dissolved in 90g of dimethylacetamide,
After reacting at 110℃ for 14 hours and cooling to 60℃, 90g of Ultem (trade name of polyetherimide manufactured by GE) was added to 300g of
g of N-methyl-2-pyrrolidone and stirred at 60° C. for 30 minutes to obtain a uniform resin composition solution. The obtained solution was applied to the edge of a 1.5 x 25 x 100 mm mild steel plate approximately 10 mm wide to a thickness of 30 μm, and heated at 110°C for 5 minutes, 150°C for 10 minutes, and 180°C.
The sample was dried with hot air for 5 minutes. After that, two mild steel plates were set with a width of about 10 mm overlapping, and heated to 200℃.
After heating and pressing with a hot plate press for 30 minutes at 10Kg/cm ² ,
After being kept at 250°C for 5 hours, it was cured and the bending strength was measured. 24Kgf/cm ² at room temperature, 22Kgf/cm ² at 200℃
It has a strength of 21Kg even after heating at 250℃ for 200 hours.
The strength was maintained at f/cm ² (measured at room temperature).

[Effects of the Invention] As is clear from the above description and drawings, the resin composition of the present invention overcomes the conventional drawbacks by blending polyetherimide into the addition reaction product with bismaleimide aminobenzoic acid. The resin composition was obtained as a resin composition with excellent heat resistance, processability, and mechanical properties, and is suitable for lamination and molding materials.

[Brief explanation of drawings]

FIG. 1 is a curve diagram showing the thermal decomposition temperature of the thermosetting resin composition according to the present invention.

Claims (1)

[Scope of Claims] 1 (A) An addition reaction product obtained by thermally reacting (a) bismaleimide and (b) aminobenzoic acid represented by the general formula (); (In the formula, R ¹ is a hydrogen atom or an alkyl group, R ²
is -O-, _-CH2- , _-SO2- or -S-S-
, R ³ represents a hydrogen atom, an alkyl group, or a chlorine atom) (B) Polyetherimide represented by the general formula () (In the formula, n represents a positive integer.) A thermosetting resin composition characterized by having as an essential component. 2. The thermosetting resin composition according to claim 1, which contains 15 to 85% by weight of the addition reaction product (A) and 85 to 15% by weight of the polyetherimide (B). . 3. Claims 1 or 2, characterized in that the addition reaction product (A) is made by reacting 0.2 to 1 mol of aminobenzoic acid (b) with 1 mol of bismaleimide (a). The thermosetting resin composition described.