JPH0155301B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a resin composition having excellent heat resistance, and more specifically, a resin composition formed by reaction-blending bismaleide, an aromatic polyamine, and an epoxy resin. The composition of the present invention can be used in the electrical/electronic field, the automobile field,
Used as a heat-resistant insulating material in the mechanical and aircraft fields. For example, in recent years, electronic circuits have become increasingly compact, and as a result, the amount of heat generated between conductors has increased, and the need for heat-resistant insulating materials as resins for circuit boards has increased. In response to this demand, epoxy resins and polymaleimides were investigated. However, although epoxy resins are generally said to have many excellent properties such as heat resistance, electrical/mechanical properties, chemical resistance, and adhesive properties, they cannot meet the high requirements mentioned above. In addition, it is not sufficient,
It had drawbacks such as poor dimensional stability, poor drilling performance, and smearing. Further, although polybismaleimide has good heat resistance, it is brittle and has the disadvantage of poor adhesion when bonding copper foil to a circuit board such as a copper-clad laminate. Therefore, a method for producing a cured epoxy resin has been proposed that solves the problems of heat resistance and brittleness (Special Publication No. 47
−42160). The present invention further improves heat resistance,
The object of the present invention is to provide a heat-resistant resin composition suitable for the various uses mentioned above. That is, the present invention provides a composition in which (d) an aromatic polyamine is further added to a pre-reacted product obtained by reacting (a) bismaleimide, (b) an aromatic polyamine, and (c) an epoxy resin. A heat-resistant resin composition that satisfies the conditions. The ratio of the total number of primary amino groups possessed by the aromatic polyamines (b) and (d) to the number of double bonds possessed by the bismaleimide (a) is 0.1 to 1.0. (b) Number of primary amino groups in aromatic polyamine and
(a) The ratio to the number of bismaleimide double bonds is 0.05
~0.85. (a) bismaleimide, (b) aromatic polyamine and
(c) The blending ratio of the epoxy resin (a+(b))/(c) (weight ratio) is 0.3 to 3.0. The number of primary amino groups in component (d) is 10 of the total number of primary amino groups in aromatic polyamine (b) and (d).
% or more. The main points are as follows. Regarding the present invention, bismaleimide as component a has the general formula It is expressed as R means N, N-direct bond or two bonds. Divalent bonds include aliphatic, alicyclic,
Any group that can bond nitrogen atoms together, such as an aromatic group, a heterocyclic group, or a combination thereof, may be used, but an aromatic group is particularly preferable. Examples of dimaleimide having specific compounds are as follows. In addition, although the above general formula is the essence, the hydrogen of the maleimide ring is alkyl, aryl,
It may be substituted with a group that does not adversely affect the reaction, such as a halogen or cyano group. N, N'-ethylene dimaleimide, N, N'-hexamethylene dimaleimide, N, N'-decamethylene dimaleimide, N,
N'-oxydipropylene dimaleimide, ethylenedioxybis(N-propylmaleimide), N,
N'-methylene (di-1,4-cyclohexylene)
dimaleimide, N,N'-isopropylidene (di-1,4-cyclohexylene) dimaleimide,
2,6-xylylene dimaleimide, 2,5-oxadiazole dimaleimide, N,N'-paraphenylene (dimethylene) dimaleimide, N,
N′-2-methyl paratoluylene dimaleimide,
N,N'-thio(diphenylene)dicitraconimide, N,N'-methylene(diparaphenylene)
In addition to bis(chlormaleimide), N,N'-hexamethylenebis(cyanmethylmaleimide), particularly preferably N,N'-metaphenylene dimaleimide, N,N'-paraphenylene dimaleimide,
N,N'-oxy(diparaphenylene) dimaleimide, N,N'-methylene(diparaphenylene)
Examples include dimaleimide, N,N'-ethylene (diparaphenylene) dimaleimide, N,N'-sulfo(diparaphenylene) dimaleimide, N,N'-metaphenylenebis(paraoxyphenylene) dimaleimide, and the like. Specific examples of the aromatic polyamine of component (b) include m-phenylenediamine, p-phenylenediamine, 2,2-bis(4-aminophenyl)propane, benzidine, 4,4'-diaminodiphenyls. Rufide, bis(4-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)phenylphosphine oxide, bis(4-aminophenyl)methylamine, 1,5-diaminonaphthalene, 1,1-bis(p- Aminophenyl) phthalane, 4,4'-diaminobenzophenone, 4,4'-diaminoazobenzene, bis(4-
Aminophenyl) phenylmethane, 1,1'-bis(4-aminophenyl)cyclohexane, 1,1
-Bis(4-amino-3-methylphenyl)cyclohexane, 2,5-bis(m-aminophenyl)-1,3,4-oxadiazole, 2,5-
Bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis(m-aminophenyl)thiazolo(4,5-d)thiazole, 5,
5'-di(m-aminophenyl)-(2,2')-bis(1,3,4-oxadiazolyl), 4,4'-
Bis(p-aminophenyl)-2,2'-dithiazole, m-bis(4-p-aminophenyl-2-
thiazolyl)benzene, 2,2'-bis(m-aminophenyl)-5,5'-dibenzimidazole,
4,4'-diaminobenzanilide, 4,4'-diaminophenylbenzoate, N,N'-bis(4
-aminobenzyl)-p-phenylenediamine and 3,5-bis(m-aminophenyl)-4-
Phenyl-1,2,4-triazole is mentioned. In addition, as a particularly preferable example, the general formula

[Formula] (X represents CH ₂ , SO ₂ , O, S); for example, 4, 4'-
Typical examples include diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl ether. The epoxy resin of component (c) is, for example, a compound having a 1,2-epoxypropyl group at the end, and compounds in which a 1,2-epoxyethyl group is bonded to an oxygen, nitrogen, or sulfur atom are particularly preferred. . Examples of such epoxy resins include polyglycidyl ethers, which are compounds having at least two free alcoholic and/or phenolic hydroxyl groups in the molecule, e.g. and epichlorohydrin or glycerol dichlorohydrin. The ethers include ethylene glycol, diethylene glycol, triethylene glycol, higher polyoxyethylene glycol, propane-1,2-diol, polyoxypropylene glycol, propane-1,3-diol, butane-1,4-diol, and polyoxybutylene. Glycol, pentane-1,5-diol, hexane-1,6-diol, hexane-
2,4,6-triol, glycerol, 1,
Acyclic alcohols such as 1,1-trimethylolpropane, pentaerythritol, poly(epichlorohydrin); resorcitol, quinitol, bis(4-hydroxycyclohexyl)-methane, 2,2-bis(4- Cycloaliphatic alcohols such as hydroxycyclohexyl)propane, 1,1-bis(hydroxymethyl)cyclohexene-3; N,N-bis(2-hydroxyethyl)aniline, 4,4'-bis(2-hydroxyethylamino) ) It can be obtained from alcohols with aromatic nuclei such as diphenylmethane. Alternatively, mononuclear phenols such as resorcinol and hydroquinone, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)sulfone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A
), 2,2-bis (3,5-
Polynuclear phenols such as dibromo-4-hydroxyphenyl)propane, aldehydes and phenols such as formaldehyde, acetaldehyde, chloral, furfuraldehyde, 4-chlorophenol, 2-methylphenol, 4-tertiarybutylphenol, etc. It can also be obtained from novolacs obtained from phenols. Some poly(N-glycidyl) compounds include, for example, epichlorohydrin and aniline, n-butylamine, bis(4-aminophenyl)methane,
Amines containing at least two amino hydrogen atoms such as bis(4-methylaminophenyl)methane, triglycidyl isocyanurate, and cyclic ureas such as ethylene urea, 1,3-propylene urea, 5,5- Also included are those obtained by dihydrochlorination with reaction products of hydantoins, such as dimethylhydantoin, with N,N'-diglycidyl derivatives. Examples of poly(S-glycidyl) compounds include:
Examples include di-S-glycidyl derivatives of dithiols such as ethane-1,2-dithiol and bis(4-mercaptoethyl phenyl) ether. Also included are polyglycidyl esters obtained by reacting a compound having two or more carboxyl groups in one molecule with epichlorohydrin or glycerol dichlorohydrin in the presence of an alkali. Such polyglycidyl esters are
oxalic acid, acetic acid, glutaric acid, adipic acid, pinelic acid, suberic acid,
Aliphatic polycarboxylic acids such as azelaic acid, sebacic acid, dimerized or trimerized linoleic acid; alicyclic acids such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid Formula polycarboxylic acid;
It can be obtained from aromatic carboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. Epoxy resins in which the terminal 1,2-epoxide groups are bonded to various hetero elements can also be used. Examples of these include N,N,O-triglycidyl derivatives of p-aminophenol or glycidyl ether-glycidyl esters of salicylic acid or phenolphthalein. You may use a mixture of epoxy resins. In the present invention, glycidyl ether of novolak obtained by reacting phenol or cresol with formaldehyde is particularly preferred because of its good heat resistance. The epoxy equivalent is preferably 100-300. The pre-reacted product obtained by reacting (a), (b), and (c) of the present invention is obtained by reacting (a) and (b) to synthesize a prepolymer in advance. The pre-reactant obtained by reacting and (c) is most preferred.
When synthesizing the prepolymer of (a) and (b) above, the ratio of components (a) and (b) to be used is usually determined based on the number of primary amino groups possessed by (b) the aromatic polyamine and (a) The ratio to the number of double bonds in bismaleimide is preferably
It is used in a ratio of 0.05 to 0.85, more preferably 0.05 to 0.6. If a large amount of aromatic polyamine (b) is used at this stage, the heat resistance will be poor when the composition of the present invention is cured, and if too little component (b) is used, the cured product will become brittle, which is undesirable. When this prepolymer and (c) epoxy resin are reacted,
The amount of component (c) used is usually ((a) + (b)) / (c) (weight ratio)
is set to be 0.3 to 3, preferably 0.5 to 2.5. (c) If the epoxy resin component is small, the adhesion, for example, when making a laminate using the composition of the present invention as a matrix, the adhesion between the laminates or between the laminate and copper foil will deteriorate, and the water absorption of the cured product will deteriorate. becomes large, which is not desirable. Moreover, if the epoxy resin component (c) is too large, the heat resistance tends to decrease, which is not preferable. The reaction conditions can be selected within a wide range.
Generally, the reaction time is preferably controlled at a temperature of 80 to 150°C, so that the gelation time of the preliminary reactant is approximately 5 to 30 minutes at 150 to 170°C. To give examples of preferred specific conditions, when synthesizing a prepolymer by reacting (a) and (b), the temperature is 110 to 150°C for 5 minutes to 1 hour, and when reacting the prepolymer with (c), 80~150℃
It takes about 10 minutes to 1 hour. The reaction of the present invention is performed using dimethylformamide (D.
MF), N-methylpyrrolidone, or dimethylacetamide. Solvents are advantageously used if the application of the produced polymer requires the use of solutions. This is because it becomes possible to directly obtain solutions with a very high solids content. The preparation can also be carried out in bulk by heating the reactants, which have previously been thoroughly mixed. Depending on the physical state of the reactants, conventional methods can be used to mix the finely divided solids, or solutions or dispersions of one reactant into the other. It can also be made by keeping it in a liquid state. In the present invention, (d) aromatic polyamine is further blended into the preliminary reaction product obtained as described above. this
(d) The aromatic polyamine can be the same as the above (b) aromatic polyamine, and among them, the general formula

Diamine represented by [Formula] (X represents CH ₂ , SO ₂ , O, S),
For example, 4,4'-diaminophenyl sulfone, 3,
Preferred are 3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and the like. Of course, (b) and (d) may be exactly the same or different. (d) Aromatic polyamine is determined by the total number of primary amino groups present in the total amount of aromatic polyamine ((b) + (d)) used in the composition and (a) the number of double bonds possessed by bismaleimide. They are blended so that the number ratio (number of primary amino groups in (b)+(d))/number of double bonds in (a)) is 0.1 to 1.0, preferably 0.2 to 0.8. In addition, the amount of component (d) to be blended is such that the number of primary amino groups in component (d) is 10% or more of the total number of primary amino groups in component (b) and component (d). It is preferable to blend component d). It is more preferable if it is 15% or more. If too little component (d) is added, heat resistance will be poor;
Even with the combination of component (d), the heat resistance of the cured product is still poor. The resin composition thus obtained is used after being cured in a desired state such as a solution, suspension, or powder. Curing can be carried out by heating at a temperature of 150 to 250°C, if desired under pressure. If desired, fillers and other conventional additives can also be used. The composition of the present invention has heat resistance, dimensional stability, lightness,
It has excellent soundproofing properties, mechanical/electrical properties, chemical resistance, etc., and can be used as printed circuit boards for computers, insulating materials for vehicle motors, circuit boards for watches, electromagnetic switch parts, metal substitutes for automobile engine parts, timing gears, Thrust washers, pistons,
Shift hooks, synchronizing cones, sliding parts (contains Teflon, graphite powder, molybdenum disulfide, etc.), copy machine parts, compressor sealing materials, binders for diamond grinding wheels, flowmeter rotors, aircraft wings (glass fibers) , carbon fiber, Kevlar fiber, etc.), block card doors, engine shroud materials, and many other uses. Example 1 40.9 parts by weight of N,N'-4,4'-diphenylmethane bismaleide and 9.1 parts by weight of 4,4'-diaminodiphenylmethane were mixed in 80 parts by weight of dimethyl formamide at 130°C. A prepolymer was synthesized by performing a heating reaction for 15 minutes. After this, cresol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd.
50 parts by weight of EOCN102S (epoxy equivalent: 225) was added, and the mixture was further reacted at 100°C for 25 minutes, and then cooled to room temperature to obtain a preliminary reaction product. Further, 6 parts by weight of 3,3'-diaminodiphenylsulfone was added. The gel time of this solution was 8 minutes and 30 seconds at 160°C.
Glass cloth treated with epoxy silane manufactured by Nittobo Co., Ltd. using the varnish prepared in this way
WE18K-BZ2 was impregnated with resin and dried at 120°C for 5 minutes to produce a prepreg with a solid content of 45% by weight. Nine sheets of this prepreg are stacked together under a pressure of 40Kg/ ^cm2.
Lamination molding was carried out at 160°C for 60 minutes. Then 200℃
Heat treatment was carried out for 8 hours. Comparative Example 1 This example is the same as Example 1 without adding component (d). That is, 40.9 parts by weight of N,N'-4,4'-diphenylmethane bismaleide and 9.1 parts by weight of 4,4'-diaminodiphenylmethane were reacted in dimethyl formamide, and then 50 parts by weight of EOCN102S was added. The cooled varnish (the gel time of this varnish was 12 minutes and 30 seconds at 160°C) was laminated in the same manner as in Example 1, and then heated at 200°C for 8 hours to obtain a laminate. Ta. Example 2 39.2 parts by weight of N,N'-4,4'-diphenylmethane bismaleide and 10.8 parts by weight of 4,4'-diaminodiphenyl ether were fused to silica (Tatsumori Products Fuzurex RD-8). Temperature with 50 parts by weight
A melt reaction was performed for 15 minutes using a heating roll at 130°C.
A prepolymer was synthesized. After this, 50 parts by weight of phenol novolac type epoxy resin EPPN201 (epoxy equivalent: 185) manufactured by Nippon Kayaku Co., Ltd. was added and heated to 50% at 120°C.
A preliminary reaction product was obtained by reacting for a minute. Then 4, 4'-
Add 5 parts by weight of diaminodiphenyl ether to 120
Melt mixed for 2 minutes at °C. After that, add 5 parts by weight of 4,4'-diaminodiphenyl ether and heat at 120℃ for 2 hours.
Melt mixed for minutes. Thereafter, it was cooled with dry ice and subjected to impact pulverization to obtain a fine powder. This fine powder
20 at 200℃ using an 80mm x 10mm x 4mm square bar mold.
Compression molding was performed for a minute to obtain a bending test piece. After that, heat treatment was performed at 220°C for 3 hours. Comparative Example 2 This example is an example in which the entire amount of (b) + (d) in Example 2 was reacted with bismaleimide at the stage of synthesizing the prepolymer. That is, N, N'-4,
39.2 parts by weight of 4'-diphenylmethane bismaleimide and 4,4'-diaminodiphenyl ether
15.8 parts by weight was heated and reacted with 50 parts by weight of fused silica at 130° C. for 15 minutes using a heating roll. Furthermore
After adding 50 parts by weight of EPPN201 and reacting at 120°C for 5 minutes, a bending test piece was obtained in the same manner as in Example 2. After that, heat treatment was further performed at 220°C for 3 hours. Comparative Example 3 This example is an example in which dicyandiamide was used instead of (d) aromatic amine. That is, N, N'-4,
47.6 parts by weight of 4'-diphenylmethane bismaleimide, 2.4 parts by weight of 4,4'-diaminodiphenylmethane, and 50 parts by weight of EOCN-102S were dissolved in 60 parts by weight of dimethylformamide, and heated at 140°C for 20 minutes. After that, it was cooled. Furthermore, 1.5 parts by weight of dicyandiamide was added to these reactants as a curing aid. Example 1 The varnish obtained in this way
Laminate molding was carried out according to the following. Comparative Example 4 This example is an example in which a large amount of component (d) was added and the total amount of components (b)+(d) became extremely large. That is, 40.9 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide, 9.1 parts by weight of 4,4'-diaminodiphenylmethane, and 50 parts by weight of fused silica were mixed into 130 parts by weight of
A prepolymer was synthesized by melting reaction using a heating roll at ℃ for 15 minutes. After this, another 50 parts by weight of orthocresol type epoxy resin EOCN102S was added,
A preliminary reaction product was obtained by reacting at 120°C for 5 minutes. Thereafter, 45.3 parts by weight of 4,4'-diaminodiphenyl ether was added and melt-mixed at 120°C for 2 minutes. below,
A test piece was prepared in the same manner as in Example 2 and subjected to testing. Table 1 shows the results of tests conducted on the test pieces obtained above.

【table】

Claims (1)

[Claims] 1. A composition in which (d) an aromatic polyamine is further added to a preliminary reaction product obtained by reacting (a) bismaleimide, (b) an aromatic polyamine, and (c) an epoxy resin. A heat-resistant resin composition that satisfies the following conditions. The ratio of the total number of primary amino groups possessed by the aromatic polyamines (b) and (d) to the number of double bonds possessed by the bismaleimide (a) is 0.1 to 1.0. (b) Number of primary amino groups in aromatic polyamine and
(a) The ratio to the number of bismaleimide double bonds is 0.05
~0.85. (a) bismaleimide, (b) aromatic polyamine and
(c) The blending ratio of the epoxy resin ((a)+(b))/(c) (weight ratio) is 0.3 to 3.0. The number of primary amino groups in component (d) is 10 of the total number of primary amino groups in aromatic polyamine (b) and (d).
% or more. 2 Claims in which the preliminary reaction product is obtained by reacting a prepolymer obtained by reacting (a) bismaleimide and (b) aromatic polyamine in advance with (c) an epoxy resin. 2. The heat-resistant resin composition according to item 1.