JP3253119B2 - Method for manufacturing printed circuit board using polyisoimide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a printed circuit board useful as a heat-resistant composite material, and more particularly to a method for producing a printed circuit board having a strong adhesive force without requiring a high temperature in the bonding step. The present invention relates to a method for manufacturing a printed circuit board using polyisoimide.

[0002]

2. Description of the Related Art Various resin systems such as polyimide, silicone, epoxy, phenol, acrylate, polyamide imide, and polybenzimidazole have been known as structural adhesives composed of high molecular compounds or prepregs for laminated molded articles. I have. However, among these, epoxy resin-based resins and the like have disadvantages in that they have poor heat resistance and must be stored at a low temperature. Conversely, a polyimide resin system having excellent heat resistance has a drawback that heat resistance is excellent but melt fluidity is poor. Some polyimides and the like exhibit high heat resistance and high adhesive strength, but they still have problems such as requiring a high temperature of 300 ° C. or more in the bonding step.

[0003]

SUMMARY OF THE INVENTION The present inventor has obtained a novel printed circuit board using a polyisoimide resin composition having excellent heat resistance and exhibiting excellent adhesive strength without requiring high temperatures in the bonding step. As a result of extensive research, the present invention has been accomplished.

[0004]

SUMMARY OF THE INVENTION According to the present invention, an aromatic tetracarboxylic dianhydride component and an aromatic diamine component are polymerized in an excess of a diamine component, and then both ends are dicarboxylic anhydride and / or dicarboxylic acid. Or a polyisoimide solution obtained by isoimidizing a polyamic acid sealed with a derivative thereof,
This is a method for producing a printed circuit board in which a fibrous reinforcing material is impregnated, a solvent is removed at a temperature of 150 ° C. or less, a prepreg is obtained, and then a prepreg is laminated with a conductive foil and heated and pressed. In addition, the polyisoimide solution is composed of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as BTDA). BPDA) (BTDA: BP)
DA) of 70:30 to 10:90, an aromatic tetracarboxylic dianhydride component, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP) and 1,3 -Bis (3-
An aromatic diamine component having a molar ratio (BAPP: APB) of 10:90 to 90:10 with (aminophenoxy) benzene (hereinafter abbreviated as APB) is polymerized in a diamine component excess state. Is a method for producing a printed circuit board obtained by isoimidizing a polyamic acid obtained by encapsulating a polyamic acid with a dicarboxylic anhydride and / or a derivative thereof.

[0005]

In the present invention, the reaction is usually carried out in an organic polar solvent which does not react with tetracarboxylic dianhydride or diamine. In addition to being inert to the reaction system and being a good solvent for the product, the organic polar solvent must be a good solvent for at least one of the reaction components, preferably both. Typical solvents of this type include tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfone, dimethylsulfoxide, N-methyl-2-pyrrolidone, etc. They can be used in combination. In addition, non-polar solvents such as benzene, dioxane, xylene, toluene and cyclohexane may be used in combination as a solvent, such as a dispersion medium of a raw material, a reaction regulator or a volatilization regulator from a product, a film smoothing agent, and the like. Used as

It is generally preferred that the reaction be carried out under anhydrous conditions. This is because the tetracarboxylic dianhydride may be ring-opened by water, inactivated, and stop the reaction. Therefore, it is necessary to remove both the water in the raw materials and the water in the solvent. But on the other hand, it regulates the progress of the reaction,
Water is also added to control the degree of polymerization of the resin. The reaction is preferably performed in an inert gas atmosphere. This is to prevent oxidation of diamines. Dry nitrogen gas is generally used as the inert gas.

Examples of the acid dianhydride used in the present invention include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3 '-Benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, naphthalene-2,3,
6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-
Tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7 -Tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8
-Dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,
6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic Acid dianhydride, 2,3,
6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7
-Tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3 ' , 4'-Diphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3" -p-terphenyltetracarboxylic acid Dianhydride, 2,3,3 ", 4" -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl)
-Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl)
Methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane Dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10- Tetracarboxylic dianhydride,
Perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride , Phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride Anhydride, pyrazine-
2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,
4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-
Examples thereof include, but are not limited to, tetracarboxylic dianhydride and 4,4′-oxydiphthalic dianhydride.

[0008] Examples of the diamine component used in the present invention include 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,6-dimethyl-m-phenylenediamine, and 2,5-dimethyl-p-phenylene. Diamine, 2,4-diaminomesitylene,
4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-
Xylidine, 4,4'-methylene-2,6-diethylaniline, 2,
4-toluenediamine, m-phenylene-diamine, p-phenylene-diamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'-diamino-diphenylethane, 3,3 '-Diamino-diphenylethane, 4,4'-diamino-diphenylmethane, 3,3'-diamino-
Diphenylmethane, 4,4'-diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether , 3,3'-
Diamino-diphenyl ether, benzidine, 3,3'-diamino-biphenyl, 3,3'-dimethyl-4,4'-diamino-biphenyl, 3,3'-dimethoxy-benzidine, 4,4 "-diamino-
p-terphenyl, 3,3 "-diamino-p-terphenyl, bis
(p-amino-cyclohexyl) methane, bis (p-β-amino-
t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-amino-pentyl) benzene, p-bis (1,1-dimethyl-5- (Amino-pentyl) benzene, 1,5-diamino-naphthalene, 2,6-diamino-naphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diamino-toluene, m-xylene- 2,5-diamine, p-xylene-2,5-diamine, m-xylylene-diamine, p-xylylene-diamine, 2,6-diamino-pyridine,
2,5-diamino-pyridine, 2,5-diamino-1,3,4-oxadiazole, 1,4-diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine, 2,2- Dimethyl-propylene-diamine, tetramethylene-diamine, pentamethylene-diamine, hexamethylene-diamine, 2,5-dimethyl-hexamethylene
-Diamine, 3-methoxy-hexamethylene-diamine, heptamethylene-diamine, 2,5-dimethyl-heptamethylene
-Diamine, 3-methyl-heptamethylene-diamine, 4,4-
Dimethyl-heptamethylene-diamine, octamethylene-
Diamine, nonamethylene-diamine, 5-methyl-nonamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, 1,10-diamino-1,10-dimethyl-decane, 2,11-diamino-dodecane, 1,12-diamino
-Octadecane, 2,12-diamino-octadecane, 2,17-diamino-eicosane, 1,3'-bis (3-aminophenoxy) benzene, and the like.

The reaction of the tetracarboxylic dianhydride component, the diamine component and the acid anhydride component is carried out by the following formula: acid dianhydride component / diamine component / acid anhydride component (molar ratio) = 0.9 / 1.0 / 0.1-0.9.
It is preferably performed at 9 / 1.0 / 0.01. Acid dianhydride component is 0.
If it is lower than 90, the degree of polymerization does not increase, and the film properties after curing are poor. If it is larger than 1.00, gas is generated at the time of curing, and a smooth film cannot be obtained.

As the dicarboxylic anhydride, maleic anhydride, phthalic anhydride, naphthalenedicarboxylic anhydride and the like are generally used. The timing of adding the dicarboxylic acid is preferably after the generation of the polyamic acid. This is for eliminating the amine at the terminal of the polyamic acid reacted in excess of the diamine component. If the amino group remains at the terminal
When a dehydrating ring-closing agent such as N, N'-dicyclohexylcarbodiimide is added, an addition reaction of an amino group occurs, which is not preferable.

In particular, the resin composition used in the present invention includes an aromatic tetracarboxylic dianhydride component having a molar ratio of BTDA to BPDA of 70:30 to 10:90;
After polymerizing an aromatic diamine component having a molar ratio of 10:90 to 90:10 with APB in an excess of the diamine component, both ends are sealed with a dicarboxylic anhydride and / or a derivative thereof. Polyisoimide obtained by isoimidizing the obtained polyamic acid is preferable.

As dehydrating agents for isoimidization, N,
N'-dicyclohexylcarbodiimide, acetic anhydride, thionyl chloride and the like are generally used. However, these dehydrating agents have different formation ratios of the isoimide ring and the imide ring depending on the type of the solvent and the type of the catalyst. In addition, as long as the physical properties are not significantly affected in the polyisoimide thus obtained, an imide ring and an uncyclized amic acid portion may remain.

Typical examples of the fibrous reinforcing material include carbon fiber, glass fiber, and aromatic polyamide fiber. As the conductor foil, a foil of copper, aluminum, stainless steel or the like is used. As the impregnation method, it is general that the fibrous reinforcing material is immersed in a polyisoimide solution for impregnation. The heating and drying temperature is about the boiling point of the solvent, and
50 ° C. The resin content to be impregnated is preferably in the range of 20 to 80% by weight of the whole printed circuit board.

The polyisoimide of the present invention is superior in melt flowability as compared with polyimide, and is suitable as a material for printed circuit boards. In heating and pressing, the adherend which match stick and a pressure of 1 to 100 kg / cm ^2, 10
By performing pressure bonding at a temperature of 0 to 250 ° C., the adherend can be strongly bonded. The imidization of polyisoimide is
The heating and pressurization may be performed at the same time as the pressing by appropriately selecting the temperature and time, or may be performed by after-baking after the pressing.

[0015]

EXAMPLES Example 1 A four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with APB as a diamine component.
146.2 g (0.5 mol) and 205.3 g (0.5 mol) of BAPP were added, and tetrahydrofuran (hereinafter abbreviated as THF) was further added.
3000 g was added, and the mixture was stirred well until the diamine was dissolved. After the diamine component is dissolved, the solution is cooled to 15 ° C or less,
223.6 g (0.76 mol) of BPDA, 61.2 g (0.19 mol) of BTDA
l) was gradually added so that the temperature in the system did not exceed 15 ° C, and after the addition was completed, stirring was performed at 15 ° C for 3 hours. continue,
14.8 g of phthalic anhydride to seal the terminal amine
(0.1 mol) was added, and the reaction was further performed at 15 ° C. for 3 hours. Next, 412.6 g of N, N'-dicyclohexylcarbodiimide dissolved in 600 g of a THF solution was slowly added dropwise over 8 hours. After completion of the dropwise addition, the mixture was stirred at 20 ° C. for 24 hours. After completion of the stirring, the reaction mixture was filtered to remove dicyclohexylurea, thereby obtaining a polyisoimide solution.

Example 2 AP was added as a diamine component to a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser.
204.6 g (0.7 mol) of B and 123.2 g (0.3 mol) of BAPP were added, and 3000 g of NMP was further added, followed by sufficient stirring until the diamine was dissolved. After the diamine component has dissolved, the solution is
Cooled to below ℃, 195.6 g (0.66 mol) of BPDA, BT
93.4 g (0.29 mol) of DA was gradually added so that the temperature in the system did not exceed 15 ° C, and after the addition was completed, stirring was performed at 15 ° C for 3 hours. Subsequently, in order to seal the terminal amine, 14.8 g (0.1 mol) of phthalic anhydride was added, and the reaction was further performed at 15 ° C. for 3 hours. Next, 412.6 g of N, N'-dicyclohexylcarbodiimide dissolved in 600 g of NMP solution was added to 8
It was dripped slowly over time. After dropping, 24 ° C at 20 ° C
Stirring was performed for hours. After completion of the stirring, the reaction mixture was filtered,
Dicyclohexylurea was removed. The obtained solution was precipitated in methanol to obtain a yellow polyisoimide powder. Dissolve 50 g of this powder in 200 g of 1,4-dioxane,
A polyisoimide solution was used.

Comparative Example 1 AP was added as a diamine component to a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser.
233.9 g (0.8 mol) of B and 64.4 g (0.2 mol) of BAPP were added, and 3000 g of NMP was further added, followed by sufficient stirring until the diamine was dissolved. After the diamine component has dissolved, the solution is
BPDA 223.6 g (0.76 mol), BT
61.2 g (0.19 mol) of DA was gradually added so that the temperature in the system did not exceed 15 ° C, and after the addition was completed, stirring was performed at 15 ° C for 3 hours. Subsequently, in order to seal the terminal amine, 14.8 g (0.1 mol) of phthalic anhydride was added, and the reaction was further performed at 15 ° C. for 3 hours.

As described above, the glass fibers were impregnated with the polyisoimide solutions synthesized in Examples 1 and 2 and Comparative Example 1, and were heated at 60 ° C. for 1 hour, at 100 ° C. for 2 hours (Comparative Example 1 was used to complete thermal imidization. At 350 ° C. for 3 hours). Insert the resulting printed circuit board between the two copper foils, 200
℃, 40kg / cm ^2, 30 minutes heating was carried out crimping. The value obtained by measuring the peel strength of the obtained test piece was 2.5 k in Example 1.
gf / cm, and 2.4 kgf / cm in Example 2. In contrast, in Comparative Example 1, no isoimidization was performed,
Since it did not melt at 200 ° C, the peel strength was as low as 0.1 kgf / cm, and almost no peel strength was obtained.

[0019]

According to the present invention, there is provided a printed circuit board which does not require a high temperature in the heating and pressurizing step, and has the same heat resistance as ordinary polyimide because the isoimide ring is rearranged to the imide ring after heat curing. It is possible to get.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) H05K 3/38 C08J 5/24

Claims (2)

(57) [Claims] 1. A polyamic polymer in which an aromatic tetracarboxylic dianhydride component and an aromatic diamine component are polymerized in an excess of a diamine component, and both ends are sealed with a dicarboxylic anhydride and / or a derivative thereof. The polyisoimide solution obtained by isoimidizing the acid is impregnated into the fibrous reinforcing material, and
A method for producing a printed circuit board, comprising: removing a solvent at a temperature of 0 ° C. or lower to obtain a prepreg; 2. A polyisoimide solution comprising 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (Hereinafter abbreviated as BPDA) (BTDA: BP)
DA) of 70:30 to 10:90, an aromatic tetracarboxylic dianhydride component, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP) and 1,3 -Bis (3-
An aromatic diamine component having a molar ratio (BAPP: APB) of 10:90 to 90:10 with (aminophenoxy) benzene (hereinafter abbreviated as APB) is polymerized in a diamine component excess state. 3. The method for producing a printed circuit board according to claim 1, wherein polyamic acid obtained by sealing with a dicarboxylic acid anhydride and / or a derivative thereof is isoimidized.