JPS58142912A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition that consists of a specific polymaleimide, an aminosulfonamide and an epoxide, thus being suitable for use over a wide range of application, because of its high heat resistance, good operability and high storage stability. CONSTITUTION:(A) A polymaleminde of formulaI(R<1> is n-valent organic group; X<1>, X<2> are H, halogen, organic group; n is 2 or more), (B) an aminosulfonamide of formula II (R<2> is H, halogen, organic group) such as p-aminobenzenesulfonamide and (C) an epoxide having at least 2 epoxy groups such as bisphenol-A type epoxy resin are made to react in the absence or presence of a solvent such as methylcellosolve with heat for a few minutes to several hours at 80-220 deg.C to give the objective thermosetting resin compostion.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a thermosetting resin composition that has good heat resistance, workability, and excellent storage stability.

[Technical background of the invention and its problems]

Conventionally, maleimide resins, such as polymaleimide and polymaleimide/polyamine resins, are well known as heat-resistant thermosetting resins.

Although these are generally satisfactory in terms of heat resistance, they have high melting points and viscosity, and they dissolve only in special dipolar solvents such as N, dimethylformamide, and N-methyl-2-pyrrolidone, and they do not harden. Due to its slow speed, it has poor workability compared to general-purpose resins such as epoxy resins and unsaturated polyester resins, which is a major hindrance, and its uses have been limited.

In order to improve this, it has also been proposed to use it in combination with an epoxy resin. However, among maleimide resins, particularly polymaleimide, has poor compatibility with epoxy resins, so high temperatures are required to make them compatible in a solvent-free system, which has the disadvantage of shortening pot life.

On the other hand, the compatibility of polymaleimide/polyamine resin (adduct obtained by reacting polymer/imide with polyamine in advance) and epoxy resin is extremely good, but since it is thermosetting itself, it cannot be mixed with epoxy resin. It is difficult to obtain resins suitable for That is, this is because the resin tends to harden during production, and has disadvantages such as poor fluidity due to increased viscosity.

[Purpose of the invention]

An object of the present invention is to provide a thermosetting resin composition that has excellent storage stability, despite the disadvantages of the prior art described above.

[Summary of the invention]

In order to achieve the above object, the present invention provides the following methods: (wherein R1 is an n-valent organic group, Xi and X2 are hydrogen atoms), the same or different monovalent atoms or groups selected from , n represents an integer of 2 or more), aminosulfonamides (n represents a group selected from organic groups), and epoxy compounds having at least two epoxy groups. It is a thermosetting resin composition consisting of.

Polymaleimides as component Q used in the present invention include, for example, ethylene bismaleimide, hexamethylene bismaleimide, m- or p-phenylene bismaleimide,
4.4'-')yenylmethane bismaleimito, 4,4
'-Cyphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 4,4'-dicyclohexylmethane bismaleimide, m- or p-xylylene bismaleimide, 4,4'-diphenylcyclohexane bismaleimide, 4 .4'-diphenylenebismaleimide, poly(phenylmethylene)polymaleimide, etc.

In addition, if necessary, KN-
Monomaleimides such as N-4-nitrophermaleimide and N-4-nitrophermaleimide can also be used in combination.

However, the component aminosulfonamides include p-aminobenzenesulfonamide, 2-aminotoluene-5-
sulfonamide, 2-aminephenol-4-sulfonamide, 2-amino-6-chlorotoluene-5-sulfonamide, etc.

Epoxy compounds having at least two epoxy groups as oral components include bisphenol A epoxy resins, bisphenol F epoxy resins, novolac epoxy resins, polyglycidyl esters of polycarboxylic acids, polyglycidyl ethers of polyols, and urethane-modified epoxy resins. , aliphatic or alicyclic polyepoxides made by epoxidizing unsaturated compounds, epoxy resins having a complex at-containing compound, epoxy resins having a heterozygous compound, epoxy resins containing glycidylated amines, etc., all of which contain one type or two or more types. It can also be used in a mixed system.

The reaction conditions for obtaining a thermosetting resin composition by heat-reacting the three components of the present invention, @, and O, are in the range of 80 to 220°C for several minutes to several 1θ hours without solvent or with methyl cellosolve or cellosolve acetate. , heat reaction in a solvent such as dioxane. Polymaleimides and ingredients (6)
The molar ratio of the aminosulfonamides is IA, 2 to 1/
It is desirable to mix at a ratio of 2. component) is 0.
If it is less than 2 moles, the curability will be poor and the cured product will become brittle.

If the amount exceeds 2 moles, the heat resistance of the cured product will decrease. The blending amount of the epoxy resin in the component part is preferably 5 to 70% by weight based on the total amount of the component (ω), 0. If component 0 is less than 5% by weight, the curability will be poor, and if it exceeds 70% by weight, the heat resistance of the cured product will decrease. The heating reaction procedure for obtaining the resin composition of the present invention includes component (4),
C') t-A heating reaction may be carried out at the same time, or the component (A
) and (g) may be reacted and then component 0 is added, or component 01 may be added and further reacted.

The effects of the present invention can also be achieved by a method in which component (g) and 0 are reacted, a component is added, and the reaction is carried out by heating.

The resin composition of the present invention thus obtained is thermosetting and hardens by heating. The heating temperature is generally preferably 130 to 250°C. To accelerate the curing of the composition, for example, tertiary amines, imidazoles, quaternary
Cured products such as class ammonium salts, boron trifluoride amine complex salts, caripole salts, peroxides, and organic acids can be added.

The composition of the present invention contains Merck, alumina, and silica, quartz glass powder, fillers such as glass fiber, colorants such as carbon black and red iron, coupling agents such as glycidoxyprobyltriethoxysilane, and stearic acid. A mold release agent such as , carnaupawa, or sous can also be added as appropriate.

The composition of the present invention has excellent heat resistance, workability, and storage stability, and can be used in a wide range of applications such as lamination, molding, adhesion, and impregnation.

[Embodiments of the invention]

Next, the present invention will be explained in detail. In the following, "parts" refer to "parts by weight" unless otherwise specified.

Example 1 4.4'-diphenylmethane bismaleimide 179 f
(corresponding to 1 equivalent of maleimide group) and p-aminobenzenesulfonamide 51.61 (0.3 mol) were mixed and 15
After reacting at 0°C for 30 minutes, bisphenol A type epoxy resin (epoxy equivalent: 190) 165.2 f f
The mixture was added and uniformly mixed and dissolved to obtain a red transparent resin. 100 parts of this resin was mixed with 0.1 part of 2-ethyl-4-methylimidazole.
A resin solution was obtained by dissolving the resin together with methyl selonlupe-MEK (7-3).

Next, this resin solution was poured into a glass film treated with aminosilane.
The prepreg was impregnated with water (250×250×O, 1811!1) and dried at 120 to 150° C. for 10 minutes to obtain a prepreg. Nine sheets of this prepreg were stacked and press-molded at a temperature of 160 to 180° C. and a pressure of 40° C. for 120 minutes to obtain a laminate having a thickness of 1.6 mm. The glass transition point of the laminate is 235°C, and the bending strength (according to JIS-C-6481) measured at 1 is 60KQ/d at room temperature, 20
Excellent values of 48 to 9/d were obtained at 0 °C and 500 at 250 °C.
Even after heating for hours, the value was still excellent at 55 KQ/-.

Furthermore, the resin solution remained stable with no change in viscosity even after one month at room temperature.

Comparative Example 1 4.4'-diphenylmethane bismaleimide 179I and 4,4'-diaminodiphenylmethane 49.51 (0
, 25 mol) and reacted at 100° C. for 30 minutes to obtain a red transparent resin. This resin was dissolved in N-methyl-2-pyrrolidone to obtain a resin solution.

Next, a laminate was obtained in the same manner as in Example 1, but long-term after-curing at a temperature of 200°C or higher was required to keep the bending strength at 200°C from 30% or less relative to room temperature. . Further, the resin solution became unusable after one month at room temperature due to significant thickening.

Comparative Example 2 67 parts of bisphenol A type epoxy resin (epoxy equivalent: 190) were added to 100 parts of the resin of Comparative Example 1 and dissolved in N=methyl-2-pyrrolidone to obtain a resin solution.

Next, a laminate was obtained in the same manner as in Example 1. The glass transition point of this laminate is 218°C, and the bending strength was measured to be 55 to 9/++d at room temperature and 37 to 9/d at 200°C.
- after heating at 250℃ for 500 hours, the value was 46 to 9.
It was /-. Further, the resin solution significantly thickened after one month at room temperature and could not be used.

Example 2 4.4'-enylmethane bismaleimi)'179f
and p-aminebenzenesulfonamide 68.8 F (
0.4 mol) and reacted at 150°C for 30 minutes, then added 106.29 f of enol novolac type epoxy resin (epoxy equivalent: 180), mixed and dissolved uniformly, and then held at 130°C for another 10 minutes to turn red and transparent. of resin was obtained. 100 parts of this resin and 3 parts of benzyldimethylamine,
120°C using a mixing roll with 3 parts of stearic acid and 150 parts of quartz glass powder (passed through 325 mesh).
The mixture was kneaded for 10 minutes, cooled, and then ground to obtain a molded powder.

Next, using this molding powder, 200'C, 3 minutes, 60KV
Transfer molding was performed using C- to obtain a molded product. This molded product has a glass transition point of 212°C and bending strength (JI
S-C-6481K
sd.

It was 9.5 kg/- at 200°C.

Example 3 4.4′-cyphenylmethane bismaleimi)”179f
and p-amine benzene sulfate (7mm)'86m1 (0
, 5 mol) thornicidyl ester type epoxy resin (epoxy equivalent: 190) mixed with 106F at 130°C
-t" Reaction was carried out for 20 minutes to obtain a red transparent resin. 0.5 part of this resin was mixed with Methylseron Lupu MEK (7-3).
A resin solution was obtained.

Next, the resin solution was applied to both sides of a 50 μm thick polyimide film using a coating device and dried at 130 to 150° C. for 10 minutes. This was placed between two t-100x25x1al mild steel plates with a 10al overlap and heated and pressed at 180°C with a pressure of 10KQ/d for 30 minutes using a hot plate press, followed by after-curing at 200°C for 3 hours. .

The tensile shear strength of the obtained substrate was measured at a rate of t 1 at/min and was 168 to 9/d at room temperature, 200
Excellent values of 9/cd were obtained at 128 °C and 50 at 220 °C.
Even after heating for 0 hours, it showed an excellent value of 9/cIM at 156.

Patent applicant: Toshiba Chemical Corporation

Claims (1)

[Claims] 1 General formula (wherein R1 is an n-valent organic group, zl and X2 are the same or different monovalent atoms or groups selected from hydrogen atoms, halogen atoms, or organic groups, and n is Each represents an integer of 2 or more.) or a group selected from organic groups. ) Aminosulfone “
A thermosetting resin composition comprising an amide and (b) an epoxy compound having at least two epoxy groups. 2 Component ■: The molar ratio of acid component 2) is 1:0.2 to 1:2
The thermosetting resin composition according to claim 1. 3 Component C) is the component), ■, 5 to 70 for the sum of O
The thermosetting resin composition according to claim 1, which has a weight of 1 tlb.