JPS635423B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a laminate. Conventionally, polyimide resins have been used for printed circuit boards and multilayer printed circuit boards in fields that require severe heat resistance and environmental resistance. but,
Polyimide resins are only soluble in special high-boiling point solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide, which makes them extremely difficult to work with, and solvents remain in prepregs and copper-clad laminates. For boiling water absorption, measling resistance,
This had an adverse effect on properties such as flame retardancy. The present invention has been made in view of these points, and provides a copper-clad laminate that has excellent workability because it dissolves in low-boiling point organic solvents, and also has excellent heat resistance and is free from the adverse effects of residual solvent after molding. This invention relates to a method for producing imide-based prepolymers that can be produced. The method for producing the imide-based prepolymer of the present invention is as follows: (A) General formula (In the formula, R ₁ represents a divalent organic group having a carbon-carbon double bond, and R ₂ represents a divalent organic group having at least 2 carbon atoms.) A diamine of H ₂ N-R ₃ -NH ₂ (in the formula, R ₃ represents a divalent organic group having at least 2 carbon atoms) is prepared in an organic solvent with a boiling point (760 mmHg) of 100°C to 170°C. After the heating reaction, (C) an epoxy compound having at least two epoxy groups is added to the reaction solution, and the reaction is further heated. In the present invention, first, bisimide (A) and diamine (B) are reacted in a low boiling point, general-purpose solvent such as 2-methoxyethanol at a temperature of 110°C to 170°C for 5 to 120 minutes, and then Add epoxy compound (C) and further
The reaction is carried out for 5 to 120 minutes at a temperature ranging from 70°C to 140°C to produce a red and transparent varnish containing a prepolymer consisting of bisimide, diamine and epoxy compounds. The reaction between bisimide (A) and diamine (B) is allowed to proceed until the average molecular weight reaches 400-800. If the average molecular weight is less than 400, a large amount of unreacted bismaleimide (A) remains, and if it is more than 800, the reactants of (A) and (B) will become too polymeric, so methyl ethyl ketone is This is because it becomes difficult to dissolve in acetone, etc. The epoxy compound (C) is added to the reaction solution of the bisimide (A) and the diamine (B), and the reaction is further heated until at least 20% by weight of the epoxy compound is reacted. The resulting imide prepolymer consisting of bisimide (A)-diamine (B)-epoxy compound (C) is
Because it is used as a varnish for impregnating base materials,
It is necessary that the gel time at 160°C is 120 seconds or more. In the present invention, bisimide (A), diamine (B), and epoxy compound (C) have a boiling point (760 mmHg) of 100°C to 170°C.
One of the characteristics is that the reaction is carried out by heating in an organic solvent. As the organic solvent, 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol, and 2-isoproxyethanol are best, and in addition, N,N'-formamide and the like are also effective. The molar ratio of the bisimide (A) and diamine (B) is preferably in the range of 1:0.1 to 1:1. If the amount of diamine (B) is less than 0.1 mole per mole of bismaleimide (A), the solubility, which is a feature of the present invention, tends to deteriorate, and conversely, per mole of (A), (B) When is more than 1 mole, the reaction is too fast,
It tends to be difficult to obtain the desired prepolymer. Further, the amount of the epoxy compound (C) is preferably 15 to 70% by weight based on the sum of (A), (B), and (C). If the epoxy compound (C) is less than 15% by weight, the solubility, which is a feature of the present invention, tends to deteriorate, and if the content of (C) is more than 70% by weight, the heat resistance is poor and the flame retardance is poor. It tends to be difficult to roll a 1. Bisimide (A) in the present invention has the general formula It is expressed as In the formula, R ₁ represents a divalent organic group having a carbon-carbon double bond, R ₂ represents a divalent organic group having at least 2 carbon atoms, and the formula It is derived from the ethylenic dicarboxylic anhydride represented by Examples of such unsaturated bisimides include N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, and N,N'-P-phenylene bismaleimide. Bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N'-methylenebis(3-chloro-P-phenylene)bismaleimide , N,N'-4,4'-diphenylsulfon bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-α,α'-
Examples include 4,4'-dimethylenecyclohexane bismuth maleimide, N,N'-m-methaxylene bismaleimide, and N,N'-4,4'-diphenylcyclohexane bismaleimide. Also, diamine (B)
is represented by the general formula H ₂ N—R ₃ —NH ₂ , where R ₃ represents a divalent organic group having at least 2 carbon atoms, such as a straight chain or branched alkylene group. , a cyclic alkylene group consisting of 5 to 6 carbon atoms, a multi-ring group containing at least one of oxygen, nitrogen, and sulfur atoms, a phenylene group, a polycyclic aromatic group, or -COO-, Those having a skeleton of a plurality of arylene groups connected by at least one group of -SO ₂ -, -O-, and -N=N- are used. Specific examples include 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane,
2,6-diaminopyridine, m-phenylenediamine, P-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-bis(4-aminophenyl)propane, benzidine, 4,4'-diamino Phenyl oxide, 4,4'-diaminodiphenylsulfone, bis(4-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)phenylphosphine oxide, bis(4-aminophenyl)methylamine, 1,5- Diaminonaphthalene, m-xylylenediamine, 1,1-
Bis(P-aminophenyl)furatane, P-xylylene diamine, hexamethylene diamine, 6,
6'-diamine-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-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-oxadiazole), 4,4'-diaminodiphenyl ether, 4,
4'-bis(P-aminophenyl)-2,2'-dithiazole, m-bis(4-P-aminophenyl-
2-thiazolyl)benzene, 4,4-diaminobenzanilide, 4,4'-diaminophenylbenzoate, N,N'-bis(4-aminobenzyl)
-P-phenylenediamine, 4,4'-methylenebis(2-chloroaniline), etc., and at least one of these or a mixture thereof is used. The epoxy compound (C) having at least two epoxy groups in the present invention includes, for example, diglycidyl ether of bisphenol A, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4' -(1,2-epoxyethyl)biphenyl, 4,4'-di(1,2
-Epoxyethyl)diphenyl ether, resorcin diglycidyl ether, bis(2,3-epoxycyclopentyl)ether, N,N'-m-
Bifunctional epoxy compounds such as phenylene bis(4,5′-epoxy-1,2-cyclohexanedicarboximide), triglycidyl compounds of P-aminophenol, 1,3,5-tri(1,2-epoxyethyl)benzene , tetraglycidoxytetraphenylethane, and polyglycidyl ether of phenol formaldehyde novolak resin. In addition, epoxy compounds having a hydantoin skeleton, epoxy compounds containing halogen, and the like are also included. The imide prepolymer produced in the present invention dissolves well when a low boiling point organic solvent such as methyl ethyl ketone or acetone is used as a diluting solvent, improving workability and making it suitable for producing general epoxy prepregs and copper-clad laminates. You can do almost the same work as . Therefore, when a special solvent with a high boiling point such as N-methyl-2-pyrrolidone is used, there is no varnish dripping during coating, and there is no volatilization remaining in the manufactured prepregs and copper-clad laminates. The amount can also be drastically reduced by the present invention. In addition,
Methyl ethyl ketone, acetone, etc. used as diluents can be added during varnish production, but this may impair the formation of the prepolymer.
If possible, it is preferable to add it after cooling the prepolymer or just before coating. Furthermore, when dicyandiamide is used as a common curing agent for bisimide and epoxy compounds in the impregnating varnish using the imide prepolymer of the present invention, the curing property becomes extremely good and moldability can be improved. Example 1 50 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide 10 parts by weight of 4,4'-diaminodiphenylmethane in 60 parts by weight of 2-methoxyethanol,
The heating reaction was carried out at 120-130°C for 30 minutes. After this, cresol novolac type epoxy resin EOCN-102S (epoxy equivalent: 222) manufactured by Nippon Kayaku Co., Ltd. was applied.
After adding 40 parts by weight and further reacting at 90 to 100°C for 30 minutes, it was cooled to room temperature, and 1.2 parts by weight of dicyandiamide and 40 parts by weight of methyl ethyl ketone were added to prepare a varnish with a solid content of 50% by weight. A 0.18 mm thick glass cloth coated with aminosilane was impregnated with this varnish and dried at 130 to 150°C for 10 minutes to produce a prepreg with a resin content of 41%. Using 8 pieces of the above prepreg, 35μ thick on top and bottom.
TAI treated copper foil (manufactured by Furukawa Circuit Oil Co., Ltd.)
Then, lamination and adhesion were performed at 170° C. for 80 minutes under a pressure of 40 kg/cm ² to obtain a copper-clad laminate with a thickness of 1.6 mm. Comparative Example 1 160 parts by weight of Rhone Poulenc's kerimid 60, EOCN, which is an aminobismaleimide prepolymer made from N,N'-4,4'-diphenylmethane bismaleimide and 4,4'-diaminodiphenylmethane, -102S 40 parts by weight, dicyandiamide 1.2 parts by weight N-methyl-2-pyrrolindone 100
A varnish was prepared by dissolving parts by weight. Next, the same glass cloth as in Example 1 was impregnated with the above varnish and dried at 140 to 160°C to produce a prepreg with a solid content of 41%. Next, a copper-clad laminate having a thickness of 1.6 mm was produced in the same manner as in Example 1. Example 2 47 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide 13 parts by weight of 4,4'-diaminodiphenylmethane in 60 parts by weight of 2-ethoxyethanol,
After reacting at 120 to 130°C for 30 minutes, 40 parts by weight of bisphenol A type epoxy Epicoat 828 (epoxy equivalent: 188) manufactured by Ciel Chemical Co., Ltd. was added, and further 85 to 95 parts by weight was added.
The reaction was allowed to take place at ℃ for 30 minutes. Next, after cooling to room temperature, 1.5 parts by weight of dicyandiamide and 40 parts by weight of methyl ethyl ketone were added to prepare a varnish with a solid content of 50% by weight. Thereafter, prepregs and copper-clad laminates were created in the same manner as in Example 1. Comparative Example 2 60 parts by weight of kerimid 601, 40 parts by weight of Epicote 828, and 1.5 parts by weight of dicyandiamide were dissolved in 100 parts by weight of N,N'-dimethylformamide to prepare a varnish with a solid content of 50% by weight. Thereafter, prepregs and copper-clad laminates were created in the same manner as in Comparative Example 1. Example 3 N,N'-4,4'-diphenylmethane bismaleimide 55 parts by weight 4,4'-methylenebis(2-chloroaniline)
10 parts by weight of 4,4'-diaminodiphenylmethane in 60 parts by weight of 2-methoxyethanol,
After reacting at 110 to 120°C for 30 minutes, 35 parts by weight of cresol novolak type epoxy resin (epoxy equivalent: approximately 210) manufactured by Ciba-Geigi was added, and the mixture was further heated to 85 to 120°C.
The reaction was carried out at 95°C for 30 minutes. Thereafter, it was cooled to room temperature, and 50 parts by weight of methyl ethyl ketone was added to prepare a varnish with a solid content of 50% by weight. Next, a prepreg and a copper-clad laminate were produced in exactly the same manner as in Example 1. Comparative Example 3 A varnish was created in exactly the same manner as in Example 3, except that N-methyl-2-pyrolindone was used as the solvent, and then a prepreg and a copper-clad laminate were created in the same manner as in Comparative Example 1. . Example 4 50 parts by weight of N,N'-methylenebis(3-chloro-P-phenylene)bismaleimide 10 parts by weight of 4,4'-diaminodiphenylmethane in 60 parts by weight of 2-methoxyethanol,
After reacting at 120-130℃ for 40 minutes, Dow Chemical's phenol novolak type epoxy resin DEN
-Add 40 parts by weight of 438 (epoxy equivalent: approximately 180) to 85
The reaction was carried out at ~95°C for 30 minutes. Thereafter, 1.0 parts by weight of dicyandiamide was added, then cooled to room temperature, and 40 parts by weight of methyl ethyl ketone was added to prepare a varnish with a solid content of 50% by weight. Thereafter, prepregs and copper-clad laminates were created in the same manner as in Example 1. Comparative Example 4 A varnish was prepared in exactly the same manner as in Example 4 except that N,N-dimethylformamide was used as the solvent. Next, using this varnish, Comparative Example 1
Prepreg and copper-clad laminates were produced in the same manner as above. First, Table 1 shows the characteristics of the prepregs of Examples and Comparative Examples. The prepreg of the present invention has extremely low volatile content and is almost the same as ordinary epoxy prepreg.

[Table] Next, regarding the 1.6 mm thick copper-clad laminate, 300
Table 2 shows the measurement results of solder heat resistance and flame resistance tests at 320°C, 320°C, and 340°C. In addition, the temperature characteristics of bending strength and thermal deterioration characteristics were examined, and there was no difference at all between the examples and comparative examples, and they satisfied the heat resistance grade H class.

Observe the presence or absence of [Table] ○ if both are absent, × otherwise
rated it as.
Anti-inflammatory properties: Measured using the UL-94 vertical method.

Claims (1)

[Claims] 1 (A) General formula (In the formula, R ₁ represents a divalent organic group having a carbon-carbon double bond, and R ₂ represents a divalent organic group having at least 2 carbon atoms.) General formula of bisimide (B) A diamine of H ₂ N―R ₃ -NH ₂ (in the formula, R ₃ represents a divalent organic group having at least 2 carbon atoms) in an organic solvent with a boiling point (760 mmHg) of 100 to 170°C. After the heating reaction, (C) an epoxy compound having at least two epoxy groups is added to the reaction solution, and a curing agent and a low boiling point organic A method for manufacturing a laminate, which comprises: adding a diluted solvent to form a varnish; impregnating a glass base material with the varnish; drying to obtain a prepreg; stacking the required number of prepreg sheets and heating and pressurizing them.