JP2001031784A - Prepreg and manufacture of printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a prepreg having a low moisture absorption by bringing a sheet of a resin composition containing an epoxy resin, a curing agent, and a phenolic-hydroxyl-containg polyamide resin and/or a phenolic-hydroxyl- containing polyamide-polybutadiene-acrylonitrile copolymer into tight contact with a substrate to be thermally fused and impregnated. SOLUTION: The resin composition comprises an epoxy resin (A) such as a polyfunctional epoxy resin, a curing agent (B) selected from among acid anhydrides, amines, phenols, etc., and a phenolic-hydroxyl-containing polyamide resin (C), and/or a phenolic-hydroxyl-containing polyamide-polybutadiene- acrylonitrile copolymer (D). The equivalent ratio of ingredient B to epoxy groups of ingredient A is 0.3 to 2.0, and the sum of ingredients C and D accounts for 10 to 90 wt.% of the composition. A sheet formed of the composition is brought into contact with one or both side, of a substrate such as a woven or nonwoven aramid fabric to be thermally fused and impregnated, thus giving a prepreg.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a prepreg and a printed wiring board, and more particularly, to a method for manufacturing a prepreg and a printed wiring board.
The present invention relates to a semiconductor mounting wiring board, a prepreg used as a material for forming an insulating layer of a printed wiring board, and a method of manufacturing a printed wiring board used for various electronic devices.

[0002]

2. Description of the Related Art A prepreg used as a material for forming an insulating layer of a printed wiring board and a semiconductor mounting wiring board is made by impregnating a varnish mainly composed of a conventional epoxy resin and a curing agent into a glass woven fabric or an aramid nonwoven fabric. Obtained by drying

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to develop a novel method for producing a prepreg.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, completed a method of manufacturing a prepreg and a printed wiring board having excellent productivity. That is, the present invention provides (1) an epoxy resin (a), a curing agent (b), and a phenolic hydroxyl group-containing polyamide resin (c) and / or a phenolic hydroxyl group-containing polyamide.
A sheet of an epoxy resin composition containing a polybutadiene-acrylonitrile copolymer (d) is adhered to a substrate,
Then, a method for producing a prepreg, which is characterized by being heat-sealed and impregnated. (2) The substrate is selected from the group consisting of glass woven fabric, glass nonwoven fabric, wholly aromatic polyester nonwoven fabric, aramid woven fabric, and aramid nonwoven fabric The method for producing a prepreg according to (1), which is at least one of the following:

(3) The method for producing a prepreg according to (1), wherein the base material is at least one selected from the group consisting of aramid woven fabric and aramid nonwoven fabric.
A method of manufacturing a printed wiring board, comprising: a step of thermocompression bonding a metal foil to at least one surface of the prepreg according to any one of (3) to (3); and a step of forming a circuit pattern. 5) Epoxy resin (a), curing agent (b), and phenolic hydroxyl group-containing polyamide resin (c) and / or phenolic hydroxyl group-containing polyamide
A sheet of an epoxy resin composition containing the polybutadiene-acrylonitrile copolymer (d).

[0006]

DETAILED DESCRIPTION OF THE INVENTION The epoxy resin composition used in the present invention comprises an epoxy resin (a), a curing agent (b), and a phenolic hydroxyl group-containing polyamide resin (c) and / or a phenolic hydroxyl group-containing polyamide-polybutadiene. It contains an acrylonitrile copolymer (d). The epoxy resin composition must be impregnated into the interior of the prepreg base material after being melted, and must not have tackiness when formed into a sheet, so that it has an appropriate softening point (for example, 80 to 130).
C).

The epoxy resin (a) used in the present invention
Are, for example, a polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound, a polyfunctional epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester-based epoxy resin, and glycidylamine. Examples include, but are not limited to, epoxy resins and epoxy resins obtained by glycidylation of halogenated phenols. Here, the polyfunctional epoxy resin is an epoxy resin having two or more glycidyl groups.

Examples of polyfunctional epoxy resins which are glycidyl etherified compounds of polyphenols include bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, and tetramethylbisphenol F. , Dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1 , 1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,
2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-
Methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenol And polyfunctional epoxy resins which are glycidyl etherified products of polyphenol compounds such as polybutadiene.

Examples of polyfunctional epoxy resins which are glycidyl etherified compounds of various novolak resins include, for example, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A,
Novolak resins, phenol novolak resins containing a xylylene skeleton, phenol novolak resins containing a dicyclopentadiene skeleton, phenol novolak resins containing a biphenyl skeleton, phenol novolak resins containing a fluorene skeleton, etc. made from various phenols such as bisphenol F, bisphenol S, and naphthols. Examples include glycidyl etherified products of various novolak resins.

Examples of the alicyclic epoxy resin include an alicyclic epoxy resin having an aliphatic skeleton such as cyclohexane. Examples of the aliphatic epoxy resin include 1,4-butanediol and 1,6-hexane. Diol,
Glycidyl ethers of polyhydric alcohols such as polyethylene glycol and pentaerythritol are mentioned.

The heterocyclic epoxy resin includes, for example, a heterocyclic epoxy resin having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring. The glycidyl ester-based epoxy resin includes, for example, hexahydrophthalic acid diglycidyl ester and the like. Examples of the epoxy resin include carboxylic acids. Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylation of amines such as aniline and toluidine.

Examples of epoxy resins obtained by glycidylation of halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, chlorinated bisphenol S, and chlorinated bisphenol. An epoxy resin obtained by glycidylation of a halogenated phenol such as A is exemplified.

[0013] Of these epoxy resins, which epoxy resin to use is appropriately selected depending on the required characteristics. However, bisphenol A, bisphenol F, bisphenol S, tetramethyl-4,4'-biphenol,
-(4-hydroxyphenyl) -2- [4- (1,1-
Bis- (4-hydroxyphenyl) ethyl) phenyl]
Propane, resorcinol, glycidyl etherified product of 1,1-di-4-hydroxyphenylfluorene, phenol, cresols, bisphenol A, bisphenol F, bisphenol S, a novolak resin made from naphthols, a phenol novolak resin containing a xylylene skeleton, Glycidyl etherified products of various novolak resins such as a phenol novolak resin containing a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, and a phenol novolak resin containing a fluorene skeleton; an alicyclic epoxy resin having a cyclohexane ring;
Hexanediol, glycidyl ethers of polyethylene glycol, triglycidyl isocyanurate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, N, N-diglycidylaniline, N, N-diglycidyl toluidine, brominated bisphenol A And glycidyl brominated phenol novolak and brominated cresol novolak are preferred. If necessary, other epoxy resins can be mixed and used.

The curing agent (b) used in the present invention includes, for example, acid anhydrides, amines, phenols, imidazoles, dihydrazines, Lewis acids, Bronsted acid salts, polymercaptons, isocyanates, And block isocyanates.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol trimellitic anhydride, biphenyltetracarboxylic anhydride and the like. Aromatic carboxylic acid anhydrides, azelaic acid, sebacic acid, anhydrides of aliphatic carboxylic acids such as dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic acid anhydride, heptic anhydride, Alicyclic carboxylic acid anhydrides such as hymic acid anhydrides are exemplified.

Examples of the amines include diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-
Aromatic amines such as diaminonaphthalene and m-xylylenediamine; aliphatic amines such as ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane and polyetherdiamine; dicyandiamide; guanidines such as (o-tolyl) biguanide;

Examples of phenols include bisphenol A, bisphenol F, bisphenol S, 4,
4′-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,
4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-
Methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone,
Pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenolated polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, Novolak resin, phenol novolak resin containing a xylylene skeleton, phenol novolak resin containing a dicyclopentadiene skeleton, phenol novolak resin containing a biphenyl skeleton, phenol novolak containing a fluorene skeleton, made of various phenols such as bisphenol A, bisphenol F, bisphenol S, and naphthols Various novolak resins such as resin, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated bisphenol A Nord novolac, brominated cresol novolak, chlorinated bisphenol S, halogenated phenols such as chlorinated bisphenol A and the like.

Examples of imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole,
2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2 -Undecyl imidazole,
2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, , 4-Diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine Isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-
Various imidazoles of 5-methylimidazole and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and those imidazoles and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene Salts with polycarboxylic acids such as dicarboxylic acid, maleic acid and oxalic acid are mentioned.

Among these curing agents, which curing agent is used is appropriately selected according to the properties required for the adhesive, but phenols are preferred.

The amount of the curing agent (b) used is in the range of 0.3 to 2.0, preferably 0.4 to 1.6 in terms of the equivalent ratio of the curing agent to the epoxy group of the epoxy resin (a). It is used in the range, more preferably in the range of 0.5 to 1.3. The above curing agents can be used as a mixture of two or more kinds.

In the present invention, a phenolic hydroxyl group-containing polyamide resin (c) and / or a phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer (d) are used. These are necessary for maintaining the shape of the sheet, and when added, impart sufficient strength and flexibility to the sheet. The combined use ratio of (c) and (d) is 10 to 9 in the entire epoxy resin composition.
0% by weight, preferably about 20 to 70% by weight.

The phenolic hydroxyl group-containing polyamide resin (c) can be synthesized, for example, by the following method. That is, an excess amount of diamine is added to a dicarboxylic acid having a phenolic hydroxyl group and a dicarboxylic acid not having a phenolic hydroxyl group, and these are added, for example, in the presence of a phosphite and a pyridine derivative to N-methyl-2- It can be obtained by heating and stirring in an organic solvent represented by pyrrolidone under an inert atmosphere such as nitrogen.

Also, a phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer (d)
Can be synthesized, for example, by the following method. That is, an excess amount of diamine is added to a dicarboxylic acid component containing a dicarboxylic acid having a phenolic hydroxyl group, for example,
Using a condensing agent in the presence of a phosphite and a pyridine derivative, heating and stirring and performing a condensation reaction in an organic solvent represented by N-methyl-2-pyrrolidone under an inert atmosphere such as nitrogen. To form a polyamide oligomer containing phenolic hydroxyl groups. As a result, it can be obtained by adding a polybutadiene-acrylonitrile copolymer having a carboxyl group at both ends to the obtained phenolic hydroxyl group-containing polyamide oligomer solution having amino groups at both ends and subjecting the solution to polycondensation. Further, the dicarboxylic acid was added to the diamine in excess to synthesize the polyamide in which both ends became a carboxylic acid group, and the both ends were blocked using a polybutadiene-acrylonitrile copolymer having amino groups at both ends. It can also be converted. Further, the polyamide or polybutadiene-
It is also possible to modify the terminal of the acrylonitrile copolymer into a functional group that can be blocked. Other combinations of functional groups include vinyl groups and -NH groups or-
A combination with an SH group and the like can be mentioned. In order to contain a phenolic hydroxyl group in the polyamide portion of the block copolymer synthesized in this manner, a dicarboxylic acid containing a phenolic hydroxyl group or a diamine containing a phenolic hydroxyl group is contained in the dicarboxylic acid or diamine. This is possible by conducting the above-mentioned condensation polymerization.

The dicarboxylic acid having a phenolic hydroxyl group used in (c) and (d) includes, for example, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid,
2-hydroxyphthalic acid, 3-hydroxyphthalic acid, 2
-Hydroxyterephthalic acid, dicarboxylic acids having no phenolic hydroxyl group include phthalic acid, isophthalic acid,
Terephthalic acid, dicarboxylic naphthalene, succinic acid,
Fumaric acid, glutaric acid, adipic acid, 1,3-cyclohexanedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'-methylene dibenzoic acid and the like.

As the diamine component, 3,3'-diamine-diamine containing a phenolic hydroxyl group is used.
4,4'-dihydroxyphenylmethane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) difluoromethane, 3,4-diamino -1,5
-Benzenediol, 3,3'-dihydroxy-4,
4'-diaminobisphenyl, 3,3'-diamino-
4,4'-dihydroxybiphenyl, 2,2-bis (3
-Amino-4-hydroxyphenyl) ketone, 2,2-
Bis (3-amino-4-hydroxyphenyl) sulfide, 2,2-bis (3-amino-4-hydroxyphenyl) ether, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone, 2,2 -Bis (3-amino-
4-hydroxyphenyl) propane, 2,2-bis (3
-Hydroxy-4-aminophenyl) propane, 2,2
As a diamine containing no phenolic hydroxyl group, such as -bis (3-hydroxy-4-aminophenyl) methane,
3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, diaminonaphthalene, piperazine, hexanetylenediamine, tetramethylenediamine, m-xylenediamine, 4,4 ' -Diaminodiphenylmethane, 4,4'-diaminobenzophenone, 2,2'-bis (4-aminophenyl) propane, 3,3'-diaminodiphenylsulfone, 3,3 '
-Diaminodiphenyl and the like, but the present invention is not limited to these.

Also, polybutadiene-acrylonitrile copolymers having various functional groups at both ends are commercially available as Hycar CTBN from Goodrich and used to block them with the above-mentioned phenolic hydroxyl group-containing polyamide. be able to.

In the epoxy resin composition of the present invention, a curing accelerator can be used if necessary. Examples of the curing accelerator include phosphorus compounds such as triphenylphosphine, for example, triethylamine, tetraethanolamine, 1,8-diaza-bicyclo [5.4.0]-.
7-undecene (DBU), N, N-dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2
Tertiary amine compounds such as -ethyl-4-methylimidazole and N-methylpiperazine, for example, boron compounds such as 1,8-diaza-bicyclo [5.4.0] -7-undecenium tetraphenylborate Is raised.

Other additives can be added to the epoxy resin composition of the present invention, if necessary. For example, plasticizers such as natural waxes, synthetic waxes and metal salts of long-chain aliphatic acids, release agents such as acid amides, esters and paraffins, stress relievers such as nitrile rubber and butadiene rubber, and trioxide Inorganic flame retardants such as antimony, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate, tetrabromobisphenol A, tetrabromo anhydride Brominated flame retardants such as phthalic acid, hexabromobenzene, brominated phenol novolak, coupling agents such as silane coupling agents, titanate coupling agents, aluminum coupling agents, fused silica, crystalline silica, low α Line silica, glass flake, glass beads, glass balloon,
Talc, alumina, calcium silicate, aluminum hydroxide, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt,
Metal powders such as gold, silver, nickel, copper, lead, iron powder, iron oxide, iron sand, etc .; inorganic fillers such as graphite, carbon, red iron oxide, and graphite; or conductive particles; coloring agents such as dyes and pigments; Carbon fiber,
Inorganic fibers such as glass fiber, boron fiber, silicon carbide fiber, alumina fiber, silica-alumina fiber, etc., organic fibers such as aramid fiber, polyester fiber, cellulose fiber, carbon fiber, oxidation stabilizer, light stabilizer, moisture resistance An improver, a thixotropy-imparting agent, a diluent, an antifoaming agent, other various resins, a tackifier, an antistatic agent, a lubricant, an ultraviolet absorber and the like can also be blended.

The sheet of the epoxy resin composition of the present invention is formed on a film serving as a support. Examples of the forming method include a method of applying the above-described epoxy resin composition as a varnish on a film, drying a solvent, and a method of applying the epoxy resin composition on a film by hot melt, but are not limited thereto. The thickness of the sheet is appropriately determined according to the thickness of the prepreg to be produced.
When the prepreg is manufactured, the thickness is preferably about 30 to 50 μm. As a film to be a support, since heat is transferred through the support in the step of heat-sealing and impregnating the sheet to the prepreg base material, it is necessary that the film has heat resistance to withstand the heat. is there. Polyethylene terephthalate (P
ET) film and the like.

The epoxy resin varnish comprises an epoxy resin (a), a curing agent (b), a phenolic hydroxyl group-containing polyamide resin (c) and / or a phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer (d). In this case, the composition can be obtained by uniformly mixing a curing accelerator and other additives in a solvent or without a solvent. As the solvent, for example, toluene, ethanol, cellosolve, tetrahydrofuran, N-methyl-2
-Organic solvents such as pyrrolidone and dimethylformamide. The hot melt is an epoxy resin (a);
Curing agent (b), phenolic hydroxyl group-containing polyamide resin (c) and / or phenolic hydroxyl group-containing polyamide
It can be obtained by melt-kneading the polybutadiene-acrylonitrile copolymer (d), if necessary, a curing accelerator and other additives with a biaxial roll, a pressure kneader, an extruder or the like.

In order to carry out the method for producing a prepreg of the present invention, for example, a sheet of the epoxy resin composition formed on the film is brought into close contact with one or both sides of a substrate, and the sheet is heat-sealed and impregnated. Good. In order to uniformly impregnate the inside of the base material with the epoxy resin composition, it is preferable to impregnate the base material from both sides of the base material. As a method for heat fusion and impregnation, a hot press, a hot roll, or the like is preferable. Optimal conditions for heat fusion and impregnation are empirically determined by the softening point of the epoxy resin composition and the viscosity during melting.
It is appropriate that the set temperature of the heat roll is generally 130 to 200C. The impregnation amount of the epoxy resin composition may be the same as that of the conventional prepreg, but is generally 50 to 60% by weight based on the total weight of the prepreg.

As the substrate, a conventionally used substrate can be used, and is preferably selected from the group consisting of glass woven fabric, glass nonwoven fabric, wholly aromatic polyester nonwoven fabric, aramid woven fabric, and aramid nonwoven fabric. Of these, aramid woven fabric and aramid nonwoven fabric are preferable from the viewpoint of low dielectric constant and weight reduction.

The printed wiring board of the present invention has at least one insulating layer formed from the prepreg of the present invention, and a circuit pattern formed on at least one surface of the insulating layer. The circuit pattern is usually formed by metal foil or metal plating, but may be formed from a conductive paste. The metal forming the circuit pattern is preferably at least one selected from the group consisting of copper, gold, silver, nickel and solder. The metal foil is preferably a commonly used copper foil. The circuit pattern can be formed in the same manner as in the case of a conventional printed wiring board.

[0034]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples,% and parts are by weight unless otherwise specified.

Synthesis Example 1 Synthesis of polyamide A (phenolic hydroxyl group-containing aromatic polyamide-polybutadiene / acrylonitrile block copolymer). 19.93 g (120 mmol) of isophthalic acid, 3,
30.63 g (153 mmol) of 4'-oxydianiline, 3.64 g (20 mmol) of 5-hydroxyisophthalic acid, 3.9 g of lithium chloride, calcium chloride 1
2.1 g, 240 ml of N-methyl-2-pyrrolidone and 54 ml of pyridine were placed in a 1-liter four-necked round-bottomed flask and dissolved by stirring.
g was added and reacted at 90 ° C. for 4 hours to produce a phenolic hydroxyl group-containing aromatic polyamide oligomer. Polybutadiene / acrylonitrile copolymers with carboxyl groups at both ends (Hycar CTBN, BF Goodr
Made by ich. The acrylonitrile component contained in the polybutadiene acrylonitrile part is 17 mol% and the molecular weight is about 36.
00) A solution obtained by dissolving 48 g in 240 ml of N-methyl-2-pyrrolidone was added, and the reaction was further carried out for 4 hours. After cooling to room temperature, the reaction solution was poured into 20 liters of methanol to prepare the polybutadiene used in the present invention. An aromatic polyamide-polybutadiene / acrylonitrile block copolymer containing about 14 mol% of a phenolic hydroxyl group having a content of the acrylonitrile copolymer part of 50 wt% was precipitated. The precipitated polymer was further purified by washing with methanol and refluxing methanol. The intrinsic viscosity of this polymer was 0.85 dl / g (dimethylacetamide, 30 ° C.). When the infrared spectrum of the polymer powder was measured by the diffuse reflection method, the absorption was based on the amide carbonyl group at 1,674 cm -1, the absorption based on the C-H bond of the butadiene portion at 2,856-2975 cm -1, and the nitrile group at 2,245 cm -1. Absorption was observed.

Synthesis Example 2 Synthesis of Polyamide B (Phenolic Hydroxyl-Containing Polyamide Resin) 20 g (120 mmol) of isophthalic acid, 26.4 g (132 mmol) of 3,4'-oxydianiline, 3.7 g of 5-hydroxyisophthalic acid (20 mmol), 3.9 g of lithium chloride, 12.1 g of calcium chloride, 240 ml of N-methyl-2-pyrrolidone, and 54 ml of pyridine were placed in a 1-liter four-necked round-bottomed flask, stirred and dissolved. Add 74 g of triphenyl phosphate and add 90 g
The reaction was performed at 4 ° C. for 4 hours to obtain a solution of a phenolic hydroxyl group-containing aromatic polyamide oligomer. The reaction solution was poured into 20 liters of methanol to precipitate a phenolic hydroxyl group-containing polyamide resin used in the present invention. The precipitated polyamide resin was further purified by refluxing methanol. The intrinsic viscosity of the obtained polyamide resin is 0.85 dl / g (dimethylacetamide solution, 30
° C).

Example 1 A resin having the following composition was dissolved in a mixed solvent of 1 part by weight of MEK with respect to 3 parts by weight of N-methyl-2-pyrrolidone (NMP) to prepare a 60% by weight resin solution. The compounding amount of the curing agent was 1.0 in equivalent ratio. This resin solution was applied to a PET film using an applicator to prepare a sheet having a thickness of 50 μm. This sheet had sufficient strength and flexibility without cracking, chipping, or peeling even when the PET film as the support was curved. The sheet was overlaid on both sides of an aramid nonwoven fabric (Technola manufactured by Teijin Limited), laminated with a laminator, and then heat-sealed and impregnated with a hot press to obtain a prepreg of the present invention. At this time, the temperature of the hot press was 150 ° C., the press time was 5 seconds, and the press pressure was 55 kgf / cm ² . The resin impregnation amount was 50% based on the total weight of the prepreg. When the cross section was observed with a microscope, the resin was impregnated into the inside of the aramid nonwoven fabric.

Table 1 Resin composition of Example 1: NC-7000 100.0 parts (naphthol-modified epoxy resin; Nippon Kayaku Co., Ltd .; epoxy equivalent: 235) Kayahard NHN 60.9 parts (naphthol-modified novolak resin) Manufactured by Nippon Kayaku Co., Ltd .; hydroxyl equivalent: 143) triphenylphosphine 1.0 part polyamide A 161.9 parts

Example 2 A resin having the following composition was dissolved in 1 part by weight of MEK with respect to 3 parts by weight of N-methyl-2-pyrrolidone (NMP) to prepare a 60% by weight resin solution. The compounding amount of the curing agent was 1.0 in equivalent ratio. This resin solution was applied to a PET film using an applicator to prepare a sheet having a thickness of 50 μm. This sheet had sufficient strength and flexibility without cracking, chipping, or peeling even when the PET film as the support was curved. The sheet was overlaid on both sides of an aramid nonwoven fabric (Technola manufactured by Teijin Limited), laminated with a laminator, and then heat-sealed and impregnated with a hot press to obtain a prepreg of the present invention. At this time, the temperature of the hot press was 150 ° C., the press time was 5 seconds, and the press pressure was 55 kgf / cm ² . The resin impregnation amount was 50% based on the total weight of the prepreg. When the cross section was observed with a microscope, the resin was impregnated into the inside of the aramid nonwoven fabric.

Table 2 Resin composition of Example 2: NC-7000 100.0 parts Kayahard NHN 60.9 parts Triphenylphosphine 1.0 parts Polyamide B 161.9 parts

Comparative Example 1 A resin having the following composition was dissolved in MEK to prepare a 60% by weight resin solution. The amount of the curing agent is 1.0 in equivalent ratio.
And This resin solution was applied to a PET film using an applicator to prepare a sheet having a thickness of 50 μm. This sheet breaks when the film that is the support is curved,
The desired prepreg could not be produced because of chipping and peeling.

Table 3 Resin composition of Comparative Example 1: NC-7000 100.0 parts Kayahard NHN 60.9 parts Triphenylphosphine 1.0 part

Comparative Example 2 A resin having the same composition as in Comparative Example 1 was dissolved in MEK to prepare
Was prepared. The amount of the curing agent is 1.
0 was set. This resin solution was impregnated into an aramid nonwoven fabric (Technola manufactured by Teijin Limited) and dried at 140 ° C. to prepare a prepreg. The resin impregnation amount was 50% based on the total weight of the prepreg.

Measurement of Moisture Absorption The prepregs produced in Examples 1 and 2 and Comparative Example 2
The composition was cured at 0 ° C. for 1 hour, cut into 3 × 10 cm, and used as a test piece for measuring moisture absorption. After the test piece was dried at 120 ° C. for 2-3 hours, its initial weight was measured. Next, this test piece was placed in an environmental bath at 85 ° C. and 85% RH, taken out after a predetermined time, and its weight was measured. The difference between this weight and the initial weight was divided by the initial weight to determine the moisture absorption. Table 4 shows these results.
Shown in

Table 4 Sample Moisture absorption rate (after 24 hours) Moisture absorption rate (after 48 hours) Example 1 0.44% 0.44% Example 2 0.66% 0.66% Comparative example 2 0.72% 0 .72%

Measurement of Peeling Strength The prepregs produced in Examples 1 and 2 and Comparative Example 2 were sandwiched between roughened copper foils and heated and pressed by a vacuum hot press at 200 ° C. and 55 kg / cm ² for 1 hour. This was cut into a strip having a width of 1 cm to obtain a test piece. Table 5 shows the results obtained by chucking the copper foil and peeling it at 90 ° to measure the strength.

Table 5 Sample 90 ° peeling strength Example 1 14.4 N / cm Example 2 5.8 N / cm Comparative Example 2 4.4 N / cm

Example 3 A polyethylene terephthalate (PET) film was laminated on both sides of a prepreg prepared in the same procedure as in Example 1. Next, a predetermined portion of the prepreg was processed with a via using a carbon dioxide gas laser, and the via was filled with a conductive paste. The conductive paste used here consisted of copper powder (85%) having an average particle size of 2 μm as a conductive substance and solventless epoxy resin (remainder) as a binder resin, and three pieces of copper powder and binder resin were used. It is prepared by kneading with a roll. After peeling PET from both sides of the prepreg filled with the conductive paste, sandwich the prepreg with copper foil,
After heating and pressurizing with a vacuum hot press at 200 ° C. and 55 kg / cm ² for 1 hour, an inner layer circuit pattern was formed by etching to form a double-sided board. A prepreg filled with conductive paste in vias created in the same way as above,
A copper foil is laminated on both surfaces of the double-sided board and copper foil is further laminated on the outer surfaces of both prepregs. After thermocompression bonding under the same conditions as above, a circuit pattern for an outer layer is formed by etching to obtain a printed wiring board having a four-layer structure. Was. Note that a printed wiring board having an arbitrary number of layers can be obtained by repeating the above series of steps.

Example 4 A printed wiring board having a four-layer structure was prepared in the same manner as in Example 3, except that a prepreg prepared in the same procedure as in Example 2 was used.

Comparative Example 3 A printed wiring board having a four-layer structure was prepared in the same manner as in Example 3, except that a prepreg prepared in the same procedure as in Comparative Example 2 was used.

Measurement of Moisture Absorption Rate The moisture absorption rate when the printed wiring boards having the four-layer structure manufactured in Examples 3, 4 and Comparative Example 3 were held at 85 ° C. and 85% RH was measured in the same manner as the prepreg. Table 6 shows these results.
Shown in

Table 6 Samples Moisture absorption rate (after 24 hours) Moisture absorption rate (after 48 hours) Example 3 0.66% 0.66% Example 4 1.20% 1.20% Comparative Example 3 1.30% 1 .30%

Consider the results shown in Tables 4 to 6 obtained for Examples 1 to 4 and Comparative Examples 1 to 3 above. Table 4
From the results shown in the above, comparing the prepregs of Examples 1 and 2 and Comparative Example 2, when the phenolic hydroxyl group-containing polyamide resin was added, the moisture absorption decreased slightly, and when the phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer was added. The moisture absorption rate has dropped significantly. It is known that the relationship between the moisture absorption and the dielectric constant is a linear relationship,
It can be said that a prepreg having a low moisture absorption has excellent dielectric properties. The results for the printed circuit boards shown in Table 6 also had the same tendency as the prepregs in Table 4.

From the results shown in Table 5, when the prepregs of Examples 1 and 2 and Comparative Example 2 are compared, the 90 ° peeling strength when the roughened copper foil is press-cured and cured on the prepreg has a phenolic hydroxyl group-containing polyamide resin. Was slightly increased, and increased significantly when a phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer was added.

[0055]

According to the method for producing a prepreg and a printed wiring board of the present invention, the production efficiency can be improved and the production equipment can be greatly simplified as compared with the conventional varnish impregnation method.
The obtained prepreg also has a low hygroscopic property and excellent dielectric properties, and as a result, a printed wiring board with low hygroscopic property and excellent dielectric properties can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F072 AB06 AB09 AB28 AB29 AD02 AD03 AD23 AD44 AE01 AG03 AH12 AH21 AJ04 AK05 AL13 4J002 AC07Y BG10Y CD00W CL00X CL06X FA04X FD146 GQ00

Claims (5)

[Claims] An epoxy resin (a), a curing agent (b), and a phenolic hydroxyl group-containing polyamide resin (c) and / or
Alternatively, a method for producing a prepreg, comprising: adhering a sheet of an epoxy resin composition containing a phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer (d) to a substrate, followed by heat fusion and impregnation. . 2. The method for producing a prepreg according to claim 1, wherein the substrate is at least one selected from the group consisting of glass woven fabric, glass nonwoven fabric, wholly aromatic polyester nonwoven fabric, aramid woven fabric, and aramid nonwoven fabric. 3. The method for producing a prepreg according to claim 1, wherein the substrate is at least one selected from the group consisting of aramid woven fabric and aramid nonwoven fabric. 4. A printed wiring comprising a step of thermocompression bonding a metal foil to at least one surface of the prepreg according to any one of claims 1 to 3, and a step of forming a circuit pattern. Substrate manufacturing method. 5. An epoxy resin (a), a curing agent (b), and a phenolic hydroxyl group-containing polyamide resin (c) and / or
Or a sheet of an epoxy resin composition containing a phenolic hydroxyl group-containing polyamide-polybutadiene-acrylonitrile copolymer (d).