JPH05295111A - Maleimide resin composition - Google Patents

Abstract

PURPOSE:To obtain a maleimide resin composition having a low melting point, good solvent solubility, good adhesion to various substrates, low water absorption, and high toughness without impairing heat resistance by reacting a polyamine with a maleimide resin modified with an aromatic hydrocarbon. CONSTITUTION:A diamine or polyamine is reacted with a maleimide resin modified with an aromatic hydrocarbon. The resin is obtained by bonding an unsaturated bisimide compound (a) to a product of the acid-catalyzed reaction of an aromatic hydrocarbon with formaldehyde, wherein the compound (a) is one derived from both an aromatic diamine or polyamine and an ethylenic carboxylic acid or a reactive derivative thereof. Thus, a maleimide resin composition can be obtained which has a low melting point, good solvent solubility, good adhesion to various substrates, low water absorption, and high toughness, without impairing the heat resistance inherent in bismaleimide polymers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a maleimide resin composition which is excellent in workability such as low melting point and high solvent solubility and is excellent in adhesion to a substrate, toughness, heat resistance and water absorption resistance.

[0002]

2. Description of the Related Art Conventionally, bismaleimide, amine-modified bismaleimide and the like have been widely known as thermosetting and heat resistant resins. Although bismaleimide has excellent heat resistance, it has a high melting point, and the melt viscosity at the melting point or higher is too low,
In addition, it has a drawback that it is poor in solvent solubility, and it is very difficult to use because it has many restrictions when used as various binders. In addition, the cured product is extremely hard and brittle, and has the drawback of poor adhesion to various base materials.

Therefore, it is generally used as an amine-modified bismaleimide by reacting it with a diamine, but although it can lower the melting point, optimize the melt viscosity, and improve the adhesiveness to various substrates, it can be dissolved in a solvent. The improvement is insufficient, and there is a disadvantage in that it is disadvantageous in terms of cost because a two-step synthetic route that once passes through bismaleimide has to be taken.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a low melting point, solvent solubility, improved adhesion to various substrates, low water absorption and toughness without impairing the heat resistance inherent to bismaleimide. As a result of earnest research for the purpose of reacting an aromatic hydrocarbon-modified maleimide resin with an aromatic hydrocarbon group introduced into a maleimide resin and a diamine or a polyamine compound, without lowering the heat resistance, a low melting point, good It was found that a maleimide resin composition having excellent solvent solubility, adhesion to various substrates, low water absorption, and high toughness can be obtained. In addition, in the case of passing through an aromatic hydrocarbon-modified maleimide resin, it was found that, unlike the case of passing through a bismaleimide, it can be produced by a one-step synthetic route without taking out once in the state of an aromatic hydrocarbon-modified maleimide. It was Further, based on this knowledge, various researches have been advanced to complete the present invention.

[0005]

The present invention provides an unsaturated bisimide compound (a) derived from an aromatic diamine or polyamine compound and a dicarboxylic acid having an ethylene type carbon-carbon double bond or a reactive derivative thereof. ), An aromatic hydrocarbon and formaldehyde are reacted in the presence of an acid catalyst to obtain an aromatic hydrocarbon formaldehyde reaction product.
The present invention relates to a maleimide resin composition obtained by reacting an aromatic hydrocarbon-modified maleimide resin compound (A) with (b) with a diamine or a polyamine compound (B).

The ratio of the diamine or polyamine compound to the aromatic hydrocarbon-modified maleimide resin compound in the present invention is preferably 50% by weight or less, more preferably 10% by weight or more and 40% by weight or less. The ratio of the diamine or polyamine compound to the aromatic hydrocarbon-modified maleimide resin compound is 5
When it is 0% by weight or more, the melting point is largely lowered, the heat resistance is also lowered, and it may not be cured. On the other hand, when it is 10% by weight or less, the adhesion to various base materials becomes insufficient, and sufficient strength may not be exhibited. In order to produce such a maleimide resin composition, an aromatic diamine or polyamine compound and an aromatic hydrocarbon formaldehyde resin, a dimethylolated aromatic hydrocarbon, a dimethoxymethylated aromatic hydrocarbon, a dihalogenomethylated aromatic are used. Nucleophilic reaction of a hydrocarbon or the like in the presence of an acid catalyst to give an aromatic hydrocarbon-modified polyamine, and further reaction with a dicarboxylic acid anhydride having an ethylene-type carbon-carbon double bond by an ordinary method to produce an aromatic hydrocarbon It is a modified maleimide compound. Under further melting,
The desired maleimide resin composition can be obtained by reacting a diamine or a polyamine compound.

As the aromatic hydrocarbon for obtaining the aromatic hydrocarbon formaldehyde reaction product, which is a modifier for the aromatic hydrocarbon-modified maleimide resin compound, which is the above-mentioned intermediate raw material, benzene, toluene, xylene, ethylbenzene, diethylbenzene are used. , Lower alkylbenzenes such as mesitylene, chlorobenzene, dichlorobenzene, bromobenzene, dibromobenzene, chlorotoluene, chloroxylene, bromoxylene, dibromoxylene, and other halogenated benzenes or halogenated lower alkylbenzenes.

As the aromatic diamine or polyamine used here, metaphenylenediamine, paraphenylenediamine, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylmethane, 1,
3,5-triaminobenzene, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) methylphosphine oxide, bis (3-aminophenyl) methylphosphine oxide, bis (4-aminophenyl) phenyl Phosphine oxide, bis (4
-Aminophenyl) phenylamine, metaxylylenediamine, paraxylylenediamine, 1,1-bis (p-
Aminophenyl) phthalane, 6,6′-diamino-2,
2'-dipyridyl, 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-oxadiazol, 2,5-bis (p-aminophenyl) -1,3
4-oxadiazol, 2,5-bis (m-aminophenyl) thiazolo (4,5-α) thiazole, 5,5′-
Bis (m-aminophenyl) -2,2'-bis (1,
3,4-oxadiazolyl) diphenyl sulfide,
4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 2,6-diaminopyridine, tris (4
-Aminophenyl) phosphine oxide, bis (4-aminophenyl) -N-methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 2,5
-Diamino-1,3,4-oxadiazol, 2,4-
Bis (β-amino-tert-butyl) toluene, bis (p-β-amino-tert-butylphenyl) ether, bis (p-β-methyl-α-aminophenyl) benzene, bis-p- (1 , 1-Dimethyl-5-aminopentyl) benzene, 1-isopropyl-2,4-m-phenyldiamine, 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'-dibenzanilide, 4,4'-diaminophenylbenzoate, N, N'-bis (4-aminobenzyl) -p-phenylenediamine, 3,5-bis (m-aminophenyl)- 4-phenyl-1,2,4-
Triazole etc. are mentioned. Further, the aromatic amine compound of the present invention also includes triazine ring compounds such as melamine, cyclohexanecarboguanamine, acetoguanamine and benzoguanamine. In addition, these may be used alone or as a mixture of two or more kinds.

As the diamine and polyamine compounds,
In addition to the aromatic diamine or polyamine, an aliphatic, cycloaliphatic, or heterodiamine or polyamine compound can be used, and a silicone compound such as diaminodimethylsiloxane can also be used. The aromatic hydrocarbon formaldehyde reaction product used here is a reaction product of an aromatic hydrocarbon and formaldehyde in the presence of an acid catalyst, which is then neutralized and washed, and diallylmethanes and other Those produced by removing low-boiling fractions are preferable, and it is preferable that non-reactive binuclear components such as diallylmethane having an oxygen content of 8% or more are not present as much as possible.

As the acid catalyst, organic acids such as oxalic acid, paratoluenesulfonic acid, xylenesulfonic acid and phenolsulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid can be used. Examples of unsaturated dicarboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, pyrocinconic anhydride, dichloromaleic anhydride, and the like. Examples thereof include a Diels-Alder reaction product of β-unsaturated dicarboxylic acid anhydride or one of these anhydrides with an acyclic, alicyclic or heterocyclic diene such as cyclopentadiene.

The maleimide resin composition obtained as described above is a vinyl compound, an allyl compound, an epoxy resin, a phenol resin, a melamine resin, a polyamide, a polycarbonate, a polysulfone, a polyethersulfone,
It may be reacted or mixed with polyether ether ketone, polyphenylene oxide, polyphenylene sulfide, polyetherimide, organic silicone compound, organic fluorine compound and the like. Further, as a curing accelerator, for example, radical polymerization initiators such as azo compounds and organic peroxides, tertiary amines, quaternary ammonium salts, phosphonium compounds, imidazoles, boron trifluoride compounds, amine salts and other ions May be added. If necessary, organic or inorganic additives and fillers other than these may be added. Further, the addition and mixing of these components may be simply pulverization mixing, solution mixing or melt mixing, and the resin composition may take any form of powder, solid and liquid.

[0012]

EXAMPLES The present invention will be described in detail below with reference to examples.
All "parts" and "%" described herein indicate "parts by weight" and "% by weight". << Production Example 1 >>4,4'-diaminodiphenylmethane 3000
Part, 300 parts of Mitsubishi Gas Chemical's xylene formaldehyde resin nicanol G (oxygen content 15%) was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer, and the internal temperature was heated to 110 ° C. When 4'-diaminodiphenylmethane was completely dissolved, 40 parts of p-toluenesulfonic acid was added, and the mixture was further reacted under a temperature-rising reflux for 2 hours. Furthermore, the reaction is carried out for 2 hours under atmospheric pressure dehydration, and while cooling, methylcellosolve 10
00 parts was added to obtain 4250 parts of an aromatic polyamine solution. The viscosity of this product at 25 ° C. was 0.2 Pa · s, and the nonvolatile content after 1 hour at 135 ° C. was 72%.

Example 1 1925 parts of acetone was placed in the same reactor as in Preparation Example 1, 600 parts of maleic anhydride was added and completely dissolved, and the aromatic polyamine obtained in Preparation Example 1 was maintained at 40 ° C. or lower. 825 parts of the solution was added dropwise over 90 minutes, and after completion of the addition, the temperature was maintained for 1 hour. Then triethylamine
165 parts and nickel acetate tetrahydrate 19.5 parts were added, acetic anhydride 800 parts was further added, and it was made to react at reflux temperature for 2 hours. After the reaction was completed, the solvent was quickly distilled off under vacuum, and warm water at 70 ° C was added to 1500
Parts were added and mixed with stirring for 10 minutes. Then, the mixture was allowed to stand and the supernatant aqueous layer was removed. Furthermore, while stirring at the same temperature, 90 ℃
1,500 parts of warm water was added, and the mixture was stirred and mixed at 90 ° C. for 10 minutes and then left standing to remove the supernatant aqueous layer. Then, repeat this operation 2
Repeat 500 times, add 500 parts of methanol and
After stirring for 1 minute, the supernatant was removed, and the internal temperature was raised to 120 ° C while dehydrating and removing the solvent under reduced pressure. At this point 4,4'-
195 parts of diaminodiphenylmethane (corresponding to 16.6%) was added, and the mixture was reacted with stirring at the same temperature for 20 minutes to obtain 1175 parts of a solid resin. The melting point of this product was 76 ° C.

Example 2 Same as Example 1 except that 195 parts (corresponding to 16.6%) of 4,4′-diaminodiphenylmethane was changed to 390 parts (corresponding to 28.6%) of 4,4′-diaminodiphenylmethane. Then, 1370 parts of a solid resin was obtained. The melting point of this product was 74 ° C. Example 3 195 parts of 4,4′-diaminodiphenylmethane
(Corresponding to 16.6%) 4,4'-diaminodiphenylmethane 5
The same procedure as in Example 1 was carried out except that the amount was changed to 90 parts (corresponding to 37.5%) to obtain 1570 parts of a solid resin. The melting point of this product is 64
It was ℃.

Comparative Example 1 Same as Example 1 except that 195 parts (corresponding to 16.6%) of 4,4′-diaminodiphenylmethane was changed to 50 parts (corresponding to 5%) of 4,4′-diaminodiphenylmethane. Then, 1030 parts of a solid resin was obtained. The melting point of this product was 72 ° C. << Comparative Example 2 >> 195 parts of 4,4'-diaminodiphenylmethane
(Corresponding to 16.6%) 4,4'-diaminodiphenylmethane 1
The same procedure as in Example 1 was carried out except that the amount was changed to 200 parts (corresponding to 55%) to obtain 2180 parts of a solid resin. The melting point of this product is 52
It was ℃. << Comparative Example 3 >> 195 parts of 4,4'-diaminodiphenylmethane
(Corresponding to 16.6%) is 4,4'-diaminodiphenylmethane 2
The same procedure as in Example 1 was carried out except that the amount was changed to 290 parts (corresponding to 70%) to obtain 3270 parts of a solid resin. This was a sticky solid at room temperature and its melting point could not be measured.

Using the solid resins obtained in Examples 1 to 3 and Comparative Examples 1 to 3, compounding, molding and post-curing were carried out to prepare test pieces, and the heat resistance of the molded products was evaluated. .. The results are shown in Tables 1 and 2. (Molding for moldings) Resins obtained in Examples and Comparative Examples 15 parts Glass fiber (3 mm chop) 6 parts Calcium carbonate 65 parts (molding) Temperature: 180 ° C., pressure: 200 kg / cm ² , time: 10 minutes ( Post-curing) 170 ° C. for 6 hours, 200 ° C. for 4 hours, and 250 ° C. for 3 hours

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

The maleimide resin composition according to the present invention is
It has a low melting point and good solvent solubility, and therefore has excellent workability. For example, molding material, organic fiber binder, rubber compounding agent, grindstone binder, inorganic fiber binder, electronic A product having excellent heat resistance and toughness can be obtained by using it as a coating agent for electric parts, a resin for laminated plates, a binder for friction materials, a binder for sliding members, and the like.

Claims (2)

[Claims] 1. An unsaturated bisimide compound (a) derived from an aromatic diamine or polyamine compound and a dicarboxylic acid having an ethylene-type carbon-carbon double bond or a reactive derivative thereof, and an aromatic hydrocarbon. Aromatic hydrocarbon-modified maleimide resin compound (A) obtained by reacting formaldehyde with an aromatic hydrocarbon formaldehyde reaction product (b) obtained in the presence of an acid catalyst is combined with a diamine or polyamine compound (B). A maleimide resin composition characterized by reacting with. 2. The ratio of the diamine or polyamine compound to the aromatic hydrocarbon-modified maleimide resin compound is 5
The maleimide resin composition according to claim 1, which is 0% by weight or less.