JPH0364551B2 - - Google Patents

Description

[Detailed description of the invention]

[Object of the Invention] (Industrial Application Field) The present invention relates to a polyimide-based heat-resistant resin composition with excellent moisture resistance. (Prior Art) Addition reaction polyimide resins are utilized for their excellent processability in laminated products, molded products, adhesives, and the like. The first of these is the unsaturated dicarboxylic acid N,
Products made by reacting N'-bisimide with diamines are suitable for use in laminates, but on the other hand, they have the property of being difficult to dissolve in solvents, such as
It has the property of being difficult to dissolve except in a polar solvent with a high boiling point such as DMF (dimethylformamide), which has the disadvantage of difficulty in processability and short life of the resin solution. Secondly, there is also one in which N,N'-bisimide of an unsaturated dicarboxylic acid and aminophenol are used as reaction components. This resin exhibits well-balanced properties for use in laminates, is soluble in low-boiling point solvents, and has good processability, but its moisture resistance is difficult, making it difficult to store the resulting copper-clad laminates for long periods of time. Particular attention must be paid to moisture absorption. Furthermore, N,N′- of the third unsaturated dicarboxylic acid
Using bisimide and aminobenzoic acid as reaction components is also suitable for laminated boards, but it has poor solubility in low-boiling point solvents, so care must be taken to preserve the resin solution before making prepregs such as glass cloth. It has disadvantages such as having to be used. (Problems to be Solved by the Invention) The present invention has been made to improve the above-mentioned drawbacks of conventional polyimide resins, and has significantly improved not only heat resistance but also moisture resistance, and a low boiling point solvent. The object of the present invention is to provide a heat-resistant resin composition that has good solubility in polyimide, and as a result can exhibit excellent practicality in a wide range of fields such as laminates, molded products, and adhesives. [Structure of the invention] (Means and effects for solving the problems) The present invention provides (A) (a) General formula (In the formula, R ¹ represents a divalent group having at least 2 carbon atoms, R ² represents a divalent group containing a double bond between carbon atoms.) ′-bisimide compound and (b) general formula (In the formula, R ³ represents a hydrogen atom, a halogen atom, or an alkyl group) and (c) the general formula (In the formula, R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group, a halogen atom, a group such as -COH ₃ , -OC ₂ H ₅ , etc., and do not contain active hydrogen). A heat-resistant resin composition comprising a reaction product and (B) an epoxy compound having two or more epoxy groups in the molecule as essential components, [component (b) + component (c)] is 0.1 to 1.0 mole per mole of component (a), and component (B) is 0.2 to 2.0 equivalent per mole of component (a), and [2 (b) component + (c) component] mole It is preferable to mix it in an amount equivalent to or more. The present invention will be explained in more detail below. [] Regarding essential components: N,N'-bisimide compound of unsaturated dicarboxylic acid: Use one having the following general formula. However, in the formula, R ¹ represents a divalent group having at least two carbon atoms, and R ² represents a divalent group containing a double bond between carbon atoms. That is, R ¹ is a linear or branched alkylene group, 5 to 6 carbon atoms.
including a cycloalkylene group having 3 rings, a heterocyclic group containing at least one of oxygen, nitrogen, or sulfur atoms, a benzene group, or a polycyclic aromatic group.
NHCO−, NR ⁶ −, −SiR ⁶ R ⁷ − or −SO ₂ −
(However, R ⁶ , R ⁷
represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having a ring having 5 to 6 carbon atoms, and a benzene group). Examples of the latter R ² , that is, a divalent group containing a double bond between carbon atoms, include maleic acid residues, citraconic acid residues, and tetrahydrophthalic acid residues. Therefore, R ¹ mentioned above
Specifically, the N,N'-bisimide compounds of unsaturated dicarboxylic acids that satisfy the conditions of R2 and ^R2 include the following, and each of these may be used alone or in a mixed system of two or more. is possible. Maleic acid N,N'-4,4'-diphenylmethane bisimide, Maleic acid N,N'-4,4'-diphenyl ether bisimide, Maleic acid N,N'-
Paraphenylene bisimide, maleic acid N,
N'-benzidine bisimide, maleic acid N,
N'-metaxylene bisimide, maleic acid N,
N'-1,5-naphthalene-bisimide, maleic acid N,N'-4,4'-diphenylsulfone-bisimide, maleic acid N,N'-2,2'-4,4'-dimethylene-cyclohexane- Bisimide, N,N'-4,4'-dicyclohexyl maleate-methane bisimide, N,N'-4,4'-diphenylcyclohexane-bisimide maleate, N,N'-4,4'-maleate diphenyl-phenylamine-
Bisimide, N,N'-4,4'-diphenyl maleate-diphenylsilane-bisimide, N,N'-4,4'-diphenyl sulfur maleate-bisimide, N,N'-2,2'-( 4,4'-diphenyl)-propane-bisimide, maleic acid N,
Examples include N'-metaphenylene bisimide and maleic acid N,N'-3,3'-(N,N'-metaphenylene bisbenzamide) bisimide. ○ Aminophenol: Use one having the following general formula. general formula However, in the formula, R ³ represents a hydrogen atom, a halogen atom, or an alkyl group. Specific compounds include the following, which may be used singly or as a mixture of two or more. o-aminophenol,
m-aminophenol, p-aminophenol,
Examples include 2-amino-4-chlorophenol and 2-amino-4-methylphenol. ○ Aniline or aniline derivative: Use one having the following general formula. general formula However, in the formula, R ⁴ and R ⁵ are hydrogen atoms, alkyl groups,
Halogen atom, −OCH ₃ , −OC ₂ H ₅ , −COOCH ₃ , −
It is represented by a group such as COOC ₂ H ₅ that does not contain active hydrogen, and specific examples include aniline, o-chloroaniline, m-toluidine, methyl-p-aminobenzoic acid ester, etc. In short, it is a nuclear substituent of aniline. Any material can be used as long as it does not contain active hydrogen. Epoxy compound: A low molecular weight compound or a high molecular weight compound having at least two epoxy groups in the molecule. For example, Epikot 828 (manufactured by Ciel Chemical Co., Ltd., trade name), an Epibis-type compound based on bisphenol A, etc., Epiklon 800, an alkyl-modified type, Epicuron
Glycidyl ester compounds such as 4050 (manufactured by Dainippon Ink & Chemicals Co., Ltd., trade name), Cyodyne (manufactured by Showa Denko Co., Ltd., trade name), Araldite CY-183 (manufactured by Ciba Chemical Co., Ltd., trade name), Novolac-type Epicote 154 (manufactured by Ciel Chemical Co., Ltd., product name), DEN431,
DEN438 (manufactured by Dow Chemical Company, trade name), cresol novolak type ECN1280, ECN1235 (manufactured by Ciba Chemical Company, trade name), urethane modified type EPU-6,
Examples include EPU-10 (product name, manufactured by Asahi Denka Kogyo Co., Ltd.). Furthermore, epoxy resins represented by the following formulas (1) to (3) can also be used. In addition to the epoxy resins mentioned above, various epoxy resins can be used, and in short, all kinds of epoxy resins can be used if conditions are appropriately selected. [] About the manufacturing method of the heat-resistant resin composition To manufacture the heat-resistant resin composition of the present invention, aminophenol and aniline or an aniline derivative are added to the N,N'-bisimide compound of the unsaturated dicarboxylic acid mentioned above. It is produced by reacting without a solvent or in an inert solvent, and then adding and reacting an epoxy compound. The molar ratio of the above four components is such that the total of aminophenol and aniline or aniline derivative is 0.1 to 1.0 mole to 1 mole of N,N'-bisimide compound of unsaturated dicarboxylic acid, and the epoxy compound is 0.2 to 2.0 equivalent. It is preferable that The reason for this is that when the total of aminophenol and aniline or aniline derivative exceeds 1.0 mol, an epoxy compound corresponding to the excess must be added, and as a result, the heat resistance This is because their sexuality is impaired. Further, if it is less than 0.1 mole, the softening temperature is high and the solubility is poor, making it impossible to dissolve in a low boiling point solvent, which is not preferable. If the amount of epoxy compound is less than 0.2 equivalent, moisture resistance will deteriorate, and if it exceeds 2.0 equivalent, heat resistance (high temperature) will deteriorate.
This is because the bending strength and hardness at 200°C are impaired. The reason for the above limitation can be explained as follows. According to the present invention, aminophenol and/or aniline or aniline derivative is added to the bisimide compound. Reaction products as shown in equations (4) and (5) above are produced. Therefore, by selecting substituents that do not contain active hydrogen for R ⁴ and R ⁵ , the amount of epoxy compound to be reacted can be reduced compared to reacting a bisimide compound with aminophenol alone, which improves heat resistance. Moisture resistance can be improved without impairing. That is, from the experimental results, active hydrogen (-
It was confirmed that moisture resistance can be improved by sufficiently reacting hydrogen atoms (such as NH- and -OH) with epoxy groups. In the present invention, the order of blending the four components, the reaction temperature, and the solvent can be appropriately selected and are not particularly limited. Hereinafter, typical manufacturing processes applied to laminates, molding, and adhesives will be explained as examples. In a reaction vessel, the aforementioned N,N'-bisimide compound of unsaturated dicarboxylic acid, aminophenol, and aniline or aniline derivative are charged in a predetermined ratio. After raising the temperature of the reaction system to 100 to 200 °C to melt the contents and proceeding with the reaction until it shows a predetermined viscosity, the temperature is lowered to 80 to 150 °C, and a predetermined amount of epoxy compound is added. Continue the reaction at this temperature while stirring. As the reaction progresses, the reaction system gradually becomes viscous, so the cure time is measured and the reaction is allowed to proceed until an appropriate point. By dissolving this reactant in a solvent such as acetone, methyl ethyl ketone, dioxane, or tetrahydrofuran, a resin solution suitable for use in laminates or adhesives can be obtained. Furthermore, by pulverizing the solid content of the reactant, a powder suitable for molding can be obtained. On the other hand, when preparing a resin solution for laminates or adhesives, a solvent can also be used from the beginning. For example, in a reaction vessel, the aforementioned N,N'-bisimide compound of unsaturated dicarboxylic acid, aminophenol, and aniline or aniline derivative are charged together with dioxane, and the reaction is allowed to proceed while refluxing the dioxane until a predetermined viscosity is achieved. After that, a predetermined amount of epoxy compound is added. By continuing the reaction while refluxing dioxane until a suitable cure time is reached, a resin solution for use in laminates or adhesives can be obtained. The resin composition thus prepared can be blended with various additives and fillers depending on the intended use. For example, in order to obtain a composition suitable for molding, a curing agent for epoxy resins such as amines and imidazole is added to the resin composition to adjust the curing speed. Further, in order to obtain a composition suitable for use in laminates or adhesives, fillers such as tackifiers and flame retardants may be appropriately blended in addition to the above-mentioned curing agent. (Example) An example of the present invention will be described. Example 1 36.03 g of N,N'-4,4'-diphenyl ether bisimide maleate and 6.0 g of p-aminophenol were placed in a flask equipped with a stirrer and a thermometer.
Prepare 4.15g of aniline and 26g of dioxane,
The reaction proceeded while refluxing dioxane. The reaction was allowed to proceed for 12 hours until the temperature reached 62 seconds/50°C using a bubble viscometer. The temperature was lowered to 80° C., 29.45 g of Epicote 828 (manufactured by Ciel Chemical Co., Ltd., trade name) and 51.17 g of dioxane were added, and the mixture was heated and stirred for an additional 30 minutes, followed by cooling. In this solution, Nipole 1072 (manufactured by Nippon Zeon Co., Ltd.,
Methyl ethyl ketone solution containing 15% by weight of product name)
67g and 2-ethyl-4-methyl-imidazole
An adhesive was prepared by adding 0.3 g and a solution of 1.2 g of 4,4'-diaminodiphenylsulfone dissolved in 5 g of methyl ethyl ketone. The adhesive strength of this adhesive was measured using the Strucker method and was found to be 53 kg/mm ² . Next, 125 μm Nomex paper (manufactured by Dupont, polyamide paper)
Approximately 50 μm of adhesive was applied to the
10 min at 80°C, 10 min at 105°C, 30 min at 170°C
After drying for several minutes, after-curing was performed at 200°C for 15 hours. Place the dried Nomex with adhesive in vacuum degassed silicone oil.
A deterioration test was conducted at 220℃ for 300 hours, but the adhesive strength was 80.
%, and no deterioration of the silicone oil was observed, demonstrating excellent heat resistance. Example 2 35.83 g of maleic acid N,N'-4,4'-diphenylmethane bisimide and 1.64 g of o-aminophenol
g and 0.83 g of p-aminobenzoic acid ethyl ester were added and heated with occasional stirring. Contents are approx.
Melted at 130℃. Stir this liquid substance vigorously,
After raising the temperature to 150°C and proceeding with the reaction for about 15 minutes, lowering the temperature to 120°C and proceeding with the reaction for another 15 minutes, and when the temperature was lowered to 80°C, epoxy resin (Epicote 1001, manufactured by Ciel Chemical Co., Ltd., trade name ) Add 20g,
Heating and stirring were continued for an additional hour. Next, 0.08g of 2-ethyl-4-methylimidazole and graphite
After adding 23 g and uniformly dispersing the contents, the contents were poured into an enameled vat, cooled, and pulverized with a mixer. This powder is placed in a mold and heated to 200°C.
Compression molding was performed at a pressure of 50 kg/cm ² for 30 minutes to obtain a molded product. After curing this molded product at 200℃ for 15 hours, we measured its bending strength.
It was 9.0Kg/mm ² and 8.5Kg/mm ² at 200°C. Furthermore, after heating the molded article at 230° C. for 200 hours, the bending strength at room temperature was measured and found to be 8.8 Kg/mm ² . Furthermore, the load for the same molded product is 100Kg,
The friction coefficient was calculated at a linear velocity of 1 m/sec.
It was 0.03. Although the temperature of the friction surface rose to 220°C, almost no wear deterioration was observed and excellent heat resistance was exhibited. Example 3 358.0 g of maleic acid N,N'-4,4'-diphenylmethane-bisimide, 72.31 g of 2-amino-4-chlorophenol, and 27.03 g of m-toluidine were mixed, and when the temperature exceeded 100°C with stirring, It gradually begins to dissolve and becomes a brown liquid. This liquid is heated to 120℃
and stirred for 1 hour. In this way, the complete addition reaction of aminophenol and aniline derivatives to bismaleimide was dissolved in dioxane.
A 50% solution was prepared, and 24.5 g of epoxy novolak resin (DEN438, manufactured by Dow Chemical Company, trade name) was added to 100 g (50 g of resin). Further, 0.25 g of dimethylbenzylamine was added and stirred to obtain a uniform mixture. A prepreg was prepared by dipping a glass cloth treated with aminosilane, air drying for 30 minutes, then drying in a dryer kept at 100°C for 10 minutes, and then at 150°C for 7 minutes. By stacking several sheets of this prepreg, the pressure is 40Kg/cm ² ,
A laminate was formed by heating and pressing at a temperature of 170°C for 1 hour. A copper-clad board was also created in the same way by laminating it with copper foil (35 μm). After curing this laminate at 200℃ for 1 hour, the bending strength was measured at 25℃ and was 55Kg/mm ² .
Bending strength in atmosphere is 25Kg/mm ² and at 200℃
The surface hardness is Barcol hardness (934-1 type).
It was 62. Regarding copper clad laminates (thickness 0.5mm,
Copper foil 35μm) 300℃ after boiling as an accelerated test for hygroscopicity
I tested it by floating it in solder, but no abnormality occurred for 2 minutes even 6 hours after boiling. In addition, there was no abnormality in the measling test (immersion in solder at 260°C for 20 seconds after boiling) even after 8 hours of boiling. Examples 4 to 6, Comparative Examples 1 to 2 Resin compositions were prepared using the compositions shown in Table 1 in the same manner as in Example 3, and the properties were measured and shown in Table 1.

〔Effect of the invention〕

According to the present invention, active hydrogen in the reaction product of the bisimide compound and aminophenol and/or aniline or aniline derivative can be sufficiently reacted with the epoxy compound, thereby reducing heat resistance. moisture resistance can be improved. Further, since the addition reaction does not involve a dehydration condensation reaction, complicated operations such as defoaming are not required in the molding operation of the composition of the present invention, which is a great advantage. Furthermore, since it has good solubility in low-boiling point solvents, it has the advantage that B-stage formation can be easily achieved when used for laminates and adhesives. It also has good thermal, mechanical, and electrical properties, and has great practical effects.

Claims (1)

[Claims] 1 (A) (a) General formula (In the formula, R ¹ represents a divalent group having at least 2 carbon atoms, R ² represents a divalent group containing a double bond between carbon atoms.) ′-bisimide compound and (b) general formula (In the formula, R ³ represents a hydrogen atom, a halogen atom, or an alkyl group) and (c) the general formula (In the formula, R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group, a halogen atom, a group such as -OCH ₃ , -OC ₂ H ₅ and the like, which do not contain active hydrogen.) A heat-resistant resin composition comprising as essential components a reaction product and (B) an epoxy compound having two or more epoxy groups in the molecule. 2. The heat-resistant resin composition according to claim 1, wherein 0.1 to 1.0 mol of [(b)+(c)] is blended per 1 mol of (a). 3. The heat-resistant resin composition according to claim 1 or 2, which contains 0.2 to 2.0 equivalents of (B) per mole of (a). 4. The heat-resistant resin composition according to claims 1 to 3, wherein (B) is blended in an amount equivalent or more to [2(b)+(c)] moles.