JP2003266595A - Manufacturing method for heat-resistant film substrate- containing b-stage resin composition sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an adhesive sheet used for manufacturing a build-up printed wiring board excellent in copper adhesive strength, heat resistance, elastic modulus and reliability by a substractive method and an additive method. <P>SOLUTION: In a heat-resistant film substrate-containing B-stage resin composition sheet wherein B-stage resin composition layers are bonded to both surfaces of a heat-resistant film substrate material, the respective B-stage resin composition layers are bonded to a metal foil (c) or a release film (e) to be manufactured separately and the B-stage resin composition layers (b) and (d) are arranged on both surfaces of a heat-resistant film (a) to be laminate-bonded and integrated under pressure and heating to manufacture the heat-resistant film substrate-containing B-stage resin composition sheet with the metal film or the release film. <P>COPYRIGHT: (C)2003,JPO

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 B-stage resin composition sheet containing a heat-resistant film and having a B-stage resin composition layer adhered on both sides of the heat-resistant film. It is possible to produce a multi-layer printed wiring board, especially a high-density multi-layer printed wiring board excellent in copper adhesion, heat resistance, reliability, etc., by mounting a semiconductor chip as a high-density small printed wiring board,
It is mainly used for new lightweight semiconductor plastic packages.

[0002]

2. Description of the Related Art In recent years, high density multilayer printed wiring boards have come to be used in electronic devices that are becoming smaller, thinner and lighter. This multilayer printed wiring board is becoming thinner and thinner, and a multilayer printed wiring board in which an insulating interlayer distance between copper foils is 20 to 40 μm has been manufactured. Conventionally, glass fiber woven fabrics, non-woven fabrics, or organic fiber woven fabrics and non-woven fabrics have been used as the base material, but there is a limit to making a thin base material, and a resin layer is sufficiently formed on the front and back of this base material. Since the base material contacts the inner copper foil and the outer copper foil after lamination molding, it is inferior in migration resistance in the Z direction, solder heat resistance after moisture absorption, etc., and is highly reliable as a high-density multilayer printed wiring board. There was a problem.

Further, in the case of producing a high-density multilayer printed wiring board, there is a method of producing a multilayer printed wiring board by an additive method as a method of forming a fine circuit. However, a large amount of rubber is added to a conventional epoxy resin. Additive multilayer printed wiring boards that use an adhesive sheet with no base material reinforcement are inferior in reliability such as migration resistance in the Z direction, especially when the insulating layer is thin, and also inferior in electrical characteristics and heat resistance. , There was a limit to use as a high-density printed wiring board. Furthermore, when the inner layer board is thin, if adhesive adhesive sheets for the additive without base material reinforcement are used on both sides, the build-up multilayer printed wiring board has mechanical strength such as bending strength, tensile strength, and elastic modulus ( The rigidity was inferior, warpage and twisting were likely to occur, and the thickness variation after molding was large, causing defects in the assembly and other processes. This adhesive sheet for additive is manufactured by directly applying it on a metal foil or a release film and converting it to the B stage, and no adhesive sheet for additive manufactured with the constitution of the present invention was found.

[0004]

DISCLOSURE OF THE INVENTION The present invention has solved the above problems and has a multilayer printed wiring board having good mechanical properties, excellent copper adhesion, heat resistance and the like, and excellent reliability. Provided is a method for producing a metal foil with a heat-resistant film attached to a B-stage resin composition layer or a B-stage resin composition sheet with a release film, which can produce a high-density multilayer printed wiring board by a subtractive method or an additive method. .

[0005]

According to the present invention, when a multilayer printed wiring board is manufactured, a conductor circuit and an interlayer resin insulation layer are sequentially laminated on a substrate, and the multilayer printed wiring board is processed by a subtractive method or an additive method. A metal foil based on a heat-resistant film, which is used as an adhesive sheet for producing Alternatively, it is a method for producing a B-stage resin composition sheet with a release film, wherein the metal foil containing a heat-resistant film substrate to be adhered to the inner layer substrate or the B-stage resin composition sheet with a release film is a metal foil having surface irregularities, or On the surface of the release film having a smooth or uneven surface, preferably 5 to 20 μm from the tip of the convex portion of the metal foil or the release film having surface unevenness. A sheet having a B-stage resin composition layer having a thickness formed thereon and further having the B-stage resin composition layer formed on a release film having a smooth surface is placed with the resin surface facing the heat-resistant film base material, and then added. The above-mentioned problems are solved by using a metal foil containing a heat-resistant film base material or a B-stage resin composition sheet with a release film, which is manufactured by laminating with a pressure / heating roll and adhering and integrating them.

Further, at least the additive insulating layer on the metal foil side and the release film side of the metal foil containing the heat-resistant film base material or the B-stage resin composition sheet with the release film is roughened with a roughening solution after curing treatment. In this case, the roughening solution is a mixture of a sparingly soluble resin component and a sparingly soluble component, and the sparingly soluble resin component includes (a) a polyfunctional cyanate ester monomer and the cyanate ester prepolymer. (B) Epoxy resin liquid at room temperature with respect to 100 parts by weight of polymer
15 to 500 parts by weight, (c) thermosetting catalyst, (a + b) using a curable resin composition containing 0.005 to 10 parts by weight per 100 parts by weight of a resin composition as an essential component Is suitable for improving heat resistance, reliability, etc., and three components of a butadiene-containing resin, an organic powder, and an inorganic powder are soluble components in the roughening solution even after the curing treatment of the curable resin composition. By using two or more of these components as essential components, it was possible to obtain an adhesive having excellent plated copper adhesion.

The B-stage resin composition sheet with a metal foil containing a base material or a release film, which contains a heat-resistant film base material, was obtained by build-up using a thin inner layer plate. The printed wiring board has higher mechanical strength, less warpage and twist than the conventional printed wiring board using a B-stage resin composition sheet containing no base material, and has an excellent molding thickness when laminated. As a result, a thin type suitable for a subtractive method or an additive method high-density printed wiring board was obtained. Further, since the Z-direction is blocked by the heat-resistant film, a printed wiring board having particularly high insulation reliability in the Z-direction and very excellent migration resistance was obtained.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition layer adhered to the metal foil or the release film of the heat-resistant film-containing metal foil or the release film B-stage resin composition sheet used for the outer layer side of the present invention is a A resin composition capable of forming a circuit by the active method or the additive method, and generally known ones such as thermosetting type and photocuring / thermosetting type are used. The resin composition layer of the metal foil containing the heat-resistant film substrate or the B-stage resin composition sheet with the release film is not particularly limited, and a generally known resin composition layer is used.
In the case of an additive resin composition, this resin layer contains
A component that is soluble in the roughening solution when cured and a resin component that becomes difficult to dissolve in the roughening solution are contained, and the soluble component is uniformly dispersed in the resin component that becomes difficult to dissolve.
Here, the meanings of "soluble" and "poorly soluble" used in the present invention are "soluble" and "slow" for those having a relatively high dissolution rate when immersed in the same roughening solution for the same time after the curing treatment. Things are described as "poorly soluble".

As the soluble resin of the present invention, generally known resins can be mentioned. This resin is soluble in a solvent or liquid, and is mixed in a sparingly soluble resin. These are not particularly limited, but specifically, polybutadiene rubber, acrylonitrile-butadiene rubber, epoxidized products of these,
Maleated products, imidized products, carboxyl group-containing products,
Known compounds such as (meth) acrylates and styrene-butadiene rubber can be used. In particular, those having a butadiene skeleton in the molecule are preferably used from the viewpoint of solubility in a roughening solution, electrical characteristics, and the like. Further, those containing a functional group rather than non-functional ones are preferable, because they react with the functional groups of other unreacted resins in the post-curing treatment to be crosslinked and the characteristics are improved. The soluble resin is not limited to this.

Examples of the soluble organic powder of the present invention include powders of thermosetting resins, thermoplastic resins, etc., which have a faster solubility when immersed in a roughening solution than the hard-soluble resin which has been hardened. So long as it is not limited. There are spherical shapes, crushed amorphous shapes, needle shapes, and the like, which can be used in combination. Spherical, crushed ones are preferably used,
The particle size is not particularly limited, but preferably an average particle size of 0.1 to 10
The average particle size is 0.2 to 5 μm. It is preferable to use a combination of large and small particles. In this case, one having a maximum diameter smaller than the thickness of the resin layer applied on the metal foil is used. For example, when the coating resin layer has a thickness of 7 μm from the convex of the metal foil, the maximum particle diameter is
It is set to 7 μm or less, preferably 6 μm or less so that particles do not come out of the resin surface after coating. In this case, the average particle size is
It is less than 6 μm.

Specific examples include epoxy resin, polyimide resin, polyphenylene ether resin, polyolefin resin, silicone resin, phenol resin, acrylic rubber,
Examples thereof include powders of polystyrene, MBS rubber, ABS, etc., and rubber powders of these multiple structures (core shell). These may be used alone or in combination of two or more.

The soluble inorganic powder of the present invention is not particularly limited, but examples thereof include aluminum compounds such as alumina and aluminum hydroxide; calcium compounds such as calcium carbonate; magnesium compounds such as magnesia; silica, zeolite and the like. Examples thereof include silica compounds, and one kind or a combination of two or more kinds is used.

As the sparingly soluble resin of the present invention, known resins such as a thermosetting resin and a photosensitive resin soluble in an alkaline aqueous solution may be used alone or in combination of two or more, and are not particularly limited. Include epoxy resin, polyimide resin,
Polyfunctional cyanate ester resin, maleimide resin, double bond addition polyphenylene ether resin, epoxidized or cyanated polyphenylene ether resin, polyolefin resin, epoxy acrylate, unsaturated group-containing polycarboxylic acid resin, polyfunctional (meth) acrylate, etc. Is mentioned. Further, these known bromides and phosphorus-containing compounds are also used. Among these, polyfunctional cyanate ester resins are preferable from the viewpoints of migration resistance, heat resistance, heat resistance after moisture absorption, and the like. Particularly preferably, (a) a polyfunctional cyanate ester monomer, the cyanate ester prepolymer
For 100 parts by weight, (b) 15 parts of liquid epoxy resin at room temperature
Approximately 500 parts by weight of (c) thermosetting catalyst is added to this (a + b) component 100
A thermosetting resin composition is used, which contains 0.005 to 10 parts by weight of resin composition as an essential component with respect to parts by weight.

The polyfunctional cyanate compound preferably used in the present invention is a compound having two or more cyanato groups in the molecule. Specifically, 1,3-or
1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene , 1,3,6-tricyanatonaphthalene, 4,4-dicyanatobiphenyl, bis (4-dicyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis
(3,5-dibromo-4-cyanatophenyl) propane, bis (4
-Cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, tris (4-cyanatophenyl) phosphite, tris
Examples thereof include (4-cyanatophenyl) phosphate, and cyanates obtained by reacting novolac with cyanogen halide.

In addition to these, Japanese Examined Patent Publications 41-1928 and 43-1846
8, polyfunctional cyanate ester compounds described in JP-A-51-63149 and JP-A-44-4791, JP-A-45-11712, JP-A-46-41112 and JP-A-47-26853 can also be used. Further, a prepolymer having a molecular weight of 400 to 6,000 and having a triazine ring formed by trimerizing the cyanato group of these polyfunctional cyanate ester compounds is used. This prepolymer is obtained by polymerizing the above-mentioned polyfunctional cyanate ester monomer using, for example, acids such as mineral acid and Lewis acid; bases such as sodium alcoholate and tertiary amines; salts such as sodium carbonate as a catalyst. It is obtained by The prepolymer also contains some unreacted monomer and is in the form of a mixture of the monomer and the prepolymer. Such a raw material is suitably used for the purpose of the present invention. Generally, it is used by dissolving it in a soluble organic solvent. These bromine addition compounds,
Liquid resins and the like can also be used.

As the epoxy resin which is liquid at room temperature, generally known epoxy resins can be used. Specifically, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin, a diglycidylated product of a polyether polyol, an epoxidized product of an acid anhydride, etc., or a combination of two or more thereof. Used. The amount of the polyfunctional cyanate ester monomer and the cyanate ester prepolymer 100 is used.
15 to 500 parts by weight, preferably 20 to 300 parts by weight
Parts by weight. Liquid at room temperature refers to substances that cannot be crushed at room temperature (25 ° C). In addition to these liquid epoxy compounds, known solid epoxy resins that can be crushed at room temperature can be used. Specifically, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin or the like is used as a hardly soluble resin, or two or more kinds thereof are used in combination.

The thermosetting resin composition of the present invention may contain various additives other than those mentioned above, if desired, as long as the characteristics inherent to the composition are not impaired. As these additives, various resins, known bromine of these resins,
Phosphorus compounds, known inorganic and organic fillers other than the above, dyes, pigments, thickeners, lubricants, defoamers, dispersants, leveling agents, photosensitizers, flame retardants, brighteners, polymerization inhibitors, Various additives such as a thixotropic agent are appropriately combined and used as desired. If necessary, when a compound having a reactive group is used, a known curing agent and catalyst are appropriately added.

The thermosetting resin composition of the present invention is itself cured by heating, but has a slow curing rate and is inferior in workability and economical efficiency. Therefore, a known thermosetting catalyst is used for the thermosetting resin used. Can be used. The amount used is 0.005 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the thermosetting resin.

The amount of the soluble resin, the organic powder, and the inorganic powder uniformly dispersed in the resin composition of the present invention is not particularly limited, but is preferably 3 to 50% by weight, and further preferably For 5
Use ~ 35% by weight ... Although one of these components may be used, two or more of the three components are preferably used to improve the copper plating adhesive strength. Further, by using particles having different particle diameters than the same particle diameter, the shape of the unevenness becomes more complicated, the anchor effect is increased, and the adhesive strength of copper plating is excellent.

The method of uniformly kneading the respective components of the present invention is
Generally known methods can be used. For example, after the respective components are blended, they are kneaded with a triple roll at room temperature or under heating, or generally known ones such as a ball mill and a liquor machine are used. Further, it is used without a solvent, or a solvent is added to obtain a viscosity suitable for the processing method.

There are no particular restrictions on the metal foil used in the present invention having irregularities on the surface, and specifically, aluminum foil, copper foil,
Examples include nickel foil. The unevenness of the surface to which the resin is attached is not particularly limited, but preferably the average roughness Rz is 1 to 12 μm,
More preferably, it is 4 to 10 μm. This is because if the irregularities are large before roughening, the roughening time is short, and the penetration of water is small, so that blistering of the plated copper layer due to heating can be reduced.

The thickness of the metal foil is not particularly limited, but it is preferably thin so that it can be removed by etching or the like thereafter, and preferably 9 to 20 μm is used. 3-5 with carrier sheet
Copper foil of μm can also be used. Of course, a metal foil having no unevenness can also be used, but for the reason described above, one having an uneven surface is preferable.

When the B-stage resin composition layer is attached to the metal foil, a known method can be used. For example, by directly applying a roll on a metal foil, drying to B-stage, or applying to a release film, drying and B-stage after placing the metal foil on the resin composition side, heating, pressurization A B-stage resin composition sheet with a metal foil integrated by pressure bonding with a roll or the like is formed. In this case, a small amount of solvent may remain in the resin composition. The thickness of the resin composition is not particularly limited, but is generally 3 to 100 μm, preferably 4 to 50 μm, and more preferably 5 to 20 μm from the tip of the convex of the metal foil. This thickness is appropriately selected depending on the intended thickness of the insulating layer together with the thickness of the heat-resistant film, and is a thickness for providing unevenness that can secure the adhesive force of the plated copper.

Known release films can be used. For example, known films such as polyethylene terephthalate (PET) film, poly-4-methylpentene-1 film and polypropylene film can be used. The thickness is not particularly limited, but a thickness of 15 to 50 μm is preferably used. This film surface may be smooth or may have irregularities. The unevenness is preferably the same as that of the metal foil. Further, since static electricity is generated at the time of peeling, known products such as an antistatic treated product and a release agent treated product are used. The same method as described above is used for forming the B-stage resin composition on the release film.

The heat-resistant film base material of the B-stage resin composition sheet containing the heat-resistant film base material used in the present invention is not particularly limited in kind and thickness, and known materials can be used.
Specifically, a polyimide (Kapton) film, a polyparabanic acid film, a liquid crystal polyester film, a wholly aromatic polyamide (aramid) film, or the like is used. The thickness is appropriately selected depending on the purpose. In order to reduce the thickness between insulating layers after laminating to about 20 to 40 μm, a heat resistant film having a thickness of 4 to 20 μm, and more preferably 4.5 to 12 μm is used. When the B-stage resin composition layer is formed on the surface of the heat-resistant film, it may be untreated, but it is preferably subjected to known surface treatments such as plasma treatment, corona treatment, chemical treatment and sandblast treatment to improve the resin adhesive strength. I do. The heat-resistant film base material is produced by laminating and adhering the resin surface of the metal foil or the release film-attached B-stage resin composition sheet to both surfaces of the heat-resistant film base material under pressure, preferably heating.

In the resin layer adhered to the heat-resistant film base material, a known resin composition can be used for the inner layer plate side. Further, a resin composition for additive may be used, but the soluble component added for additive is often inferior in chemical resistance and the like, and it is generally preferable to use a resin mainly composed of the poorly soluble resin. . By using the heat-resistant film, a multilayer printed wiring board having excellent reliability such as migration resistance in the Z direction can be produced.

In the case of the multi-layering of the present invention, after the conductor is subjected to a known surface treatment using an inner layer plate on which a conductor circuit is formed using a copper clad laminate or a heat resistant film base reinforced copper clad sheet Alternatively, the heat resistant film substrate-containing metal foil or the release film-attached B-stage resin composition sheet is placed on the front and back of an inner layer circuit board using a double-sided roughened foil, and heating, pressurization, or heating is performed by a known method. In this case, lamination molding or lamination is performed under vacuum, and the resin composition for additive is cured until it can be roughened with a roughening solution. After laminating or laminating, the metal foil is removed by etching or the like. The release film is removed by peeling. In the subtractive method, it is completely cured or almost cured at the time of laminate molding.

Curing Lamination Molding for Multi-Layering of the Present Invention
The conditions are not particularly limited, but for additive use, acid or
Is the conditions under which roughening with a roughening solution such as an oxidizing agent can be properly performed.
It is appropriately selected depending on the resin composition used. Generally temperature
60 ~ 250 ℃, Pressure 2 ~ 50kgf / cm ² , The time is 0.5 ~ 3 hours
It Further, it is preferable to carry out lamination molding under vacuum. Device is true
Known laminator presses, general multi-stage vacuum presses, etc.
Things can be used. For subtractive ones as well
It is appropriately selected from the above depending on the resin composition.

For additive use, after removing the metal foil or the release film on the surface of the metal foil-clad plate or the plate with the release film obtained in the present invention, the resin is roughened by a known method such as an acid or an oxidizing agent. Done in. Examples of the acid used include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid and the like, and examples of the oxidizing agent include sodium permanganate, potassium permanganate, chromic acid and chromic sulfuric acid, but are not limited thereto. is not. If necessary, a known swelling solution is used before this treatment, and after the treatment, it is neutralized with a neutralizing solution. The average roughness of the roughened surface formed by this roughening treatment is, apart from the unevenness of the metal foil or the release film, the average roughness Rz 0.1 to 14 μm, preferably 2 to 1
0 μm. The roughness that combines the irregularities of the metal foil or the release film and the irregularities due to roughening is preferably an average roughness Rz of 3
-15 μm, and more preferably Rz 5-12 μm.

Since the curable resin composition of the present invention contains two or more components having high solubility in the roughening solution, small irregularities are roughened even if the average roughness is not so large. It is in the dent, and the adhesion is high when it is plated with copper. With one component, the unevenness is not complicated and it is difficult to obtain high copper adhesion.

After that, the conductor is thickened by electroless plating, thickening electroless plating, and if necessary, electroplating by a known semi-additive method, full-additive method or the like. Although it depends on the resin composition, in general, the degree of curing of the resin that can be roughened, if the printed wiring board is used as it is
It cannot be used as a high-density printed wiring board due to poor copper adhesion, heat resistance, reliability, etc. Therefore, in the semi-additive method, post-curing is generally performed before forming a circuit. Although it depends on the resin composition, it is generally cured at a temperature of 60 to 250 ° C. for 30 minutes to 5 hours. The curing condition is selected according to the resin composition so that the attached copper plating does not peel off. Next, a circuit is formed by a known method to obtain a printed wiring board. This same process is sequentially repeated to build up a multilayer structure.

This B-stage resin composition sheet containing a heat-resistant film substrate is used for general copper-clad laminated boards and laminated B for multilayer boards.
It can also be used as a stage resin composition sheet, and when a release film is used, the release film is peeled off, then copper foil is placed on top of it, placed between inner layer boards, etc., and laminated, and printed wiring by the subtractive method. Produce a board.

[0033]

The present invention will be specifically described below with reference to Examples and Comparative Examples. Unless otherwise specified, “part” means part by weight. Example 1 400 parts of 2,2-bis (4-cyanatophenyl) propane monomer was melted at 150 ° C. and reacted for 4 hours with stirring to obtain a prepolymer having an average molecular weight of 1,900. This was dissolved in methyl ethyl ketone to obtain varnish A. Bisphenol A type epoxy resin (trade name: Epicoat 828, Japan Epoxy Resin <
Co., Ltd.) 100 parts, bisphenol F type epoxy resin (trade name: EXA830LVP, Dainippon Ink and Chemicals Co., Ltd.) 50 parts,
50 parts of novolac type epoxy resin (trade name: DEN438, manufactured by Dow Chemical Co., Ltd.), bisphenol A type epoxy resin (trade name: Epicor 100) as a solid epoxy resin at room temperature
1. 300 parts of Japan Epoxy Resin Co., Ltd.) and 100 parts of cresol novolac type epoxy resin (trade name: ESCN220F, Sumitomo Chemical Co., Ltd.) are mixed, and 0.3 parts of acetylacetone iron is dissolved in methyl ethyl ketone as a thermosetting catalyst. And added. 100 parts of liquid epoxidized polybutadiene resin (trade name: E-1000-8.0, manufactured by Nippon Petrochemical Co., Ltd.),
Epoxy group-modified acrylic multi-layered organic powder (Product name: Staphyloid IM-203, average particle size 0.2 μm, Max. Particle size 0.5
μm) 30 parts, and mixed well with stirring to form a uniform varnish B.

This varnish B was continuously applied to a 18 μm thick copper foil matte surface (unevenness 3.5 to 6.2 μm, average roughness Rz: 4.6 μm), dried, and 5.7 from the tip of the Max. B-stage resin composition layer with a height of μm (gelling time at 170 ° C: 48 seconds)
The thickness on the resin side when it comes out of the drying zone
Arrange a protective polypropylene film of 15μm, 100 ℃, 4k
A B-stage resin composition sheet C with a copper foil was produced by laminating with a linear pressure of gf / cm.

Further, the varnish B was applied on a release film having a thickness of 25 μm and dried to form a B-stage resin layer having a gelling time of 50 seconds and a thickness of 23 μm, and the resin surface when leaving the drying zone. Apply a 15 μm thick polypropylene protective film to 1
Lamination was carried out at 00 ° C. and a linear pressure of 4 kgf / cm to prepare a B-stage resin composition sheet D with a release film. While peeling off this protective film, further peeling off the protective film of the B-stage resin composition sheet C with the copper foil, the thickness 12
B-stage resin composition sheet E with copper foil containing heat-resistant film base material, which is obtained by arranging μm polyimide films on both sides treated with plasma and continuously laminating them at 100 ° C. and a linear pressure of 5 kgf / cm for integration. Was produced. The thickness of this insulating layer was about 41 μm from the tip of the convex portion of the copper foil.

On the other hand, as the inner layer plate, the insulating layer thickness is 0.2 mm, 12
BT resin copper clad laminate with μm double-sided copper foil (Product name: CCL-HL83
0, manufactured by Mitsubishi Gas Chemical Co., Inc.), and a B-stage resin composition sheet E with a copper foil containing the heat-resistant film substrate is formed on both sides of a plate in which a circuit is formed on the copper foil and black copper oxide treatment is applied to the resin. After placing the layers so that they face the inner layer plate side and charging them in a press machine, raise the temperature from room temperature to 170 ° C in 25 minutes, the pressure from the beginning to 15 kgf / cm ² , and the degree of vacuum to 170 ° C at 0.5 Torr. After holding for 30 minutes, it was cooled and taken out to obtain a multi-layer plate F having four layers. After removing the copper foil on this surface by etching, one shot was irradiated with a carbon dioxide gas laser output of 12 mJ to form a blind via hole having a hole diameter of 100 μm. Swelling, desmearing (dissolving), and neutralization with potassium permanganate-based desmear solution (Nippon MacDermid Co., Ltd.), and the total unevenness from the surface layer is 6.9 to 11.0 μm.
(Average roughness Rz: 8.6 μm). At the same time, the resin layer remaining at the bottom of the blind via hole was dissolved and removed. Next, electroless copper plating 0.7 μm and electrolytic copper plating 25
μm deposit, put in a heating furnace and gradually increase the temperature from 100 ℃ to 30
The temperature is raised to 150 ℃ in minutes, and the temperature is gradually increased to 60 ℃ at 200 ℃.
It was cured by heating for a minute. When the thickness between the insulating layers was measured by the cross section, it was about 25 μm. Using this, a copper conductor circuit was formed by a semi-additive method, the conductor circuit surface was further treated with black copper oxide, and the same steps were repeated, and a 6-layer multilayer printed wiring board was produced by buildup. The results of measuring this property are shown in Table 1.

Example 2 Bisphenol A type epoxy resin (trade name: Epicort 1
001, Japan Epoxy Resin Co., Ltd.) 500 parts, Phenol novolac type epoxy resin (trade name: DEN438, Dow Chemical Co., Ltd.) 500 parts, imidazole curing agent (trade name: 2E4MZ, Shikoku Kasei Co., Ltd.) ) 30 parts, carboxyl group-modified acrylic multi-layered organic powder (trade name: Staphyroid
IM-301, average particle size 0.2 μm, Max. Particle size 0.5 μm) 50 parts, finely pulverized silica (average particle size 2.4 μm, Max. Particle size 5.0 μm) 100
Parts and acrylonitrile-butadiene rubber (trade name:
A solution prepared by dissolving 30 parts of Nipol 1031 (manufactured by Nippon Zeon Co., Ltd.) in methyl ethyl ketone was added and well dispersed by a three-roll mill to give a varnish F. A B-stage resin composition sheet with a release film in which this is applied to a release PET film having a smooth surface of 25 μm and dried to form a resin layer having a thickness of 15.4 μm
G (gel time at 170 ℃ 51 seconds) was made, and when it came out of the drying zone, a protective polypropylene film with a thickness of 25 μm was placed on the resin surface, and it was placed on a roll with a temperature of 100 ℃ and a linear pressure of 5 kgf / cm. And continuously laminated and wound up.

Bisphenol A type epoxy resin (trade name: Epicort 1001, Japan Epoxy Resin Co., Ltd.)
500 parts, phenol novolac type epoxy resin (product name: DEN438, Dow Chemical Co., Ltd.) 450 parts, imidazole-based curing agent (product name: 2E4MZ, Shikoku Kasei Co., Ltd.) 30
Part, 50 parts of a carboxyl group-modified acrylic multi-layered organic powder (trade name: Staphyloid IM-301, average particle size 0.2 μm), and 300 parts of talc (average particle size 1.8 μm) were added, and 3
The varnish H was well-dispersed well with this roll. This varnish H was applied to a release PET film having a thickness of 25 μm and dried to prepare a B-stage resin composition sheet I having a B-stage resin composition thickness of 20 μm and a gelation time of 65 seconds. The object sheet and the protective polypropylene film of G above are peeled off and placed on both sides of a 4.5 μm-thick plasma-treated wholly aromatic polyamide film.
A B-stage resin composition sheet J with a release film containing a heat-resistant film base material was produced by continuously laminating with a heating roll having a linear pressure of 5 kgf / cm at 0 ° C. The thickness of this insulating layer was about 40 μm.

On the other hand, an epoxy-based copper clad laminate of 0.2 mm thick and 12 μm double-sided copper foil (trade name: CCL-EL170, Mitsubishi Gas Chemical Co., Ltd.
Circuit) with a copper residual rate of 30%, and after the conductor is treated with black copper oxide, the release P on one side of the B-stage resin composition sheet J with release film containing the above heat-resistant film substrate on both sides
Peel off the ET film, place it, and load it into the press machine.
The temperature is raised to 170 ℃ in 25 minutes, and the pressure is 15kgf / cm ² from the beginning.
Then, after holding for 30 minutes at a temperature of 170 ° C. at a vacuum degree of 0.5 Torr, curing treatment was carried out, and then the laminate was cooled and taken out to obtain a four-layer multilayer board K. After removing the release film on this surface, one shot was irradiated with a carbon dioxide gas laser output of 12 mJ to form a blind via hole having a hole diameter of 100 μm.

Roughening treatment was performed with an aqueous chromic acid solution so that irregularities from the surface were adjusted to 4.8 to 10.3 μm (average roughness Rz: 8.2 μm).
At this time, the tip of the concave portion did not reach the heat resistant film.
At the same time, the resin layer remaining at the bottom of the blind via hole was dissolved and removed. Next, electroless copper plating on this roughened surface.
7 μm and 25 μm of electrolytic copper plating were deposited, and the mixture was placed in a heating furnace and gradually heated from room temperature to 150 ° C. in 30 minutes, and further heated and cured at 170 ° C. for 60 minutes. Using this, a conductor circuit was formed by a semi-additive method, the conductor circuit was further treated with black copper oxide, and processed in the same manner to produce a 6-layer multilayer printed wiring board. The thickness between insulating layers after molding is almost
It was 20 μm. The results of measuring this property are shown in Table 1.

Comparative Examples 1 and 2 In Examples 1 and 2, the heat-resistant film base material was not used, but the thickness of the resin layer of the B stage adhered to the copper foil and the release film was set to In the case of a release film, a metal foil or a B-stage resin composition sheet with a release film is prepared by adhering 40 μm on each surface, and only the B-stage resin composition sheet with a metal foil or a release film is used. Then similarly laminated curing treatment molding, similarly subjected to roughening treatment, in the same manner as in Examples 1 and 2, 5 to 11 μm (average roughness Rz: 8 to 9 μm) in terms of total irregularities from the surface layer, and similarly. A 6-layer multilayer printed wiring board was used. The evaluation results are shown in Table 1.

Comparative Example 3 In Example 1, a glass woven cloth having a thickness of 20 μm was impregnated with varnish B and dried to obtain a total thickness (glass woven cloth + resin composition layer).
A prepreg L having a size of 40 μm and a gelation time (170 ° C.) of 54 seconds was manufactured. This prepreg was placed on both sides of each inner layer board, and 18 μm copper foil was placed on the outer side of the inner layer board, and similarly laminated and cured to form a four-layered multilayer board. After removing this surface copper foil by etching, form blind via holes and perform roughening treatment in the same manner to make the total unevenness from the surface layer 5 to 11 μm, similarly form a circuit after copper plating, conductor black copper oxide treatment , Prepreg L arrangement, copper foil arrangement of 18 μm, copper foil removal on the surface layer, blind via hole formation, desmear treatment, copper plating, circuit formation were carried out in the same manner to produce a 6-layer multilayer printed wiring board. . When observing the copper plating cross section,
Roughening depressions reached the glass cloth, and there were many places where copper plating was attached. The evaluation results are shown in Table 1.

Comparative Example 4 A varnish was prepared in the same manner as in Example 2 except that the carboxyl group-modified acrylic multi-layered organic powder, finely pulverized silica and acrylonitrile-butadiene rubber were not used. A B-stage resin composition sheet M with a release film, on which a resin layer having a gelation time (170 ° C.) of 79 seconds was formed, was produced by coating so as to have a thickness of 40 μm and drying. This B-stage resin composition sheet with release film
One M is placed on each side of the inner layer board, and similarly, lamination hardening treatment is molded to produce a four-layer multi-layer board. After removing the release film on the surface layer, a blind via hole is similarly formed with a carbon dioxide laser. Formed and subjected to a roughening treatment under the same conditions as in Example 2,
After copper plating, conductor circuit formation, conductor black copper oxide treatment, placement of B-stage resin composition sheet M with release film and lamination molding were performed, and then the same processing was performed to obtain a 6-layer printed wiring board. The evaluation results are shown in Table 1.

(Table 1) Item Example Comparative Example 1 2 1 2 3 4 Copper adhesion (kgf / cm) 1.24 1.35 1.24 1.37 1.16 0.44 Solder heat resistance No abnormality No abnormality No abnormality Partial swelling Partial swelling Glass Transition temperature DMA (℃) 201 153 201 153 202 168 Elastic modulus 25 ℃ (kgf / mm ² ) 1506 1301 1007 912 1829 700 Warp / twist (mm) 1.3 1.7 4.0 5.9 1.8 6.2 Thickness variation (μm) 4.5 6.5 9.8 13.4 7.9 13.9 Blind via hole / heat cycle test Resistance change rate (%) 1.6 2.2 2.0 3.3 1.8> 10 Crack generation 200 cycles 0/1000 0/1000 0/1000 0/1000 0/1000 241/1000 400 cycles 0/1000 51 / 1000 0/1000 366/1000 0/1000 978/1000 migration resistance (Omega) normal ^{6x10 13 4x10 13 5x10 13 6x10 13} 4x10 13 6x10 13 200hrs. 7x10 11 8x10 10 2x10 11 6x10 8 5x10 9 8x10 9 500hrs. 3x10 ¹¹ 6x10 ¹⁰ 3x10 ¹⁰ <10 ⁸ <10 ⁸ <10 ⁸

<Measurement Method> 1) Copper Adhesion: Measured according to JIS C6481. 2) Solder heat resistance: A 6-layer printed wiring board was subjected to a pressure cooker test treatment (PCT: 121 ° C, 203kPa, 4hrs.), Immersed in solder at 260 ° C for 30 seconds, and then observed for abnormalities. 3) Glass transition temperature: each varnish is applied on a copper foil and dried to obtain a thickness of 0.8 mm, and then the copper foil is placed on this resin composition surface and cured under each lamination curing condition, and then the surface layer The copper foil was etched and measured by the DMA method. Comparative Example 3
Is made by stacking multiple prepregs to make the thickness almost
What was 0.8 mm was used. 4) Elastic Modulus: With a 6-layer board structure, a copper foil is not used and laminated to form a laminated board, and using this, the elastic modulus is measured by the DMA method, and the elastic modulus of the DMA chart at 25 ° C is measured. Indicated. 5) Warp and twist: Using a 6-layer printed wiring board manufactured with a size of 250 x 250 mm, the warp and twist were measured on the surface plate, and the maximum value was shown. 6) Thickness variation: The thickness variation of the layer laminated on one side of the 6-layer printed wiring board of 250x250 mm in 5) was measured with a thickness measuring instrument, and the maximum variation per layer was expressed. 7) Blind via hole, resistance value change and crack due to heat cycle test: 2 to 3 of 6-layer printed wiring board
Blind via hole formed in the second layer (hole diameter 100 μm, land
180 μm, 1000 layers are alternately connected to the second and third layers, and in the gas phase
-65 ℃ / 30 minutes ← → ＋ 150 ℃ / 30 minutes was repeated as 200 cycles, and the maximum change in resistance was measured. or,
Occurrence of resin cracks was observed by observing the cross section of the hole at 200 and 400 cycles. The number of occurrences is shown in the numerator, and the number of tests is shown in the denominator. 8) Migration resistance: 100 mm square copper foil was left at the same position on the second and third layers of the six-layer board of each of the examples and comparative examples.
Insulation resistance value between the connecting and Z-direction insulating layers is 85 ℃ ・ 85% R
It was measured by applying 100 VDC at H.

[0046]

INDUSTRIAL APPLICABILITY In a B-stage resin composition sheet containing a heat-resistant film substrate in which B-stage resin composition layers are attached to both sides of a heat-resistant film substrate, each B-stage resin composition sheet is used as a metal foil or a release film. These B-stage resin composition sheets are adhered and produced separately, and the B-stage resin composition sheets are placed on both sides of the heat-resistant film and laminated and adhered under pressure and heat,
A method for integrally manufacturing a metal foil with a heat-resistant film base material for subtractive or additive or a B-stage resin composition sheet with a release film, wherein the obtained metal foil with a heat-resistant film base material or a release film B
By using a stage resin composition sheet, it is possible to manufacture a multilayer printed wiring board having a high elastic modulus (rigidity), excellent warpage, twisting, thickness accuracy, and reliability such as migration resistance in the Z direction. I was able to.

Further, as a resin component which becomes hardly soluble after curing treatment in a resin composition for additive of a metal foil containing a heat-resistant film base material or a B-stage resin composition with a release film, and further as a resin component for subtractive, (a) Polyfunctional cyanate ester monomer, with respect to 100 parts by weight of the cyanate ester prepolymer, (b) blending 15 to 500 parts by weight of a liquid epoxy resin at room temperature, (c) a thermosetting catalyst, a +
b) By using a curable resin composition containing 0.005 to 10 parts by weight per 100 parts by weight of a resin composition as an essential component, heat resistance is high, and reliability such as migration resistance and crack resistance is improved. An excellent multilayer printed wiring board could be obtained.

Further, by making two or more components out of the three components of butadiene-containing resin, organic powder and inorganic powder as essential components as components soluble in the roughening solution even after the curing treatment,
The anchor effect due to the roughening was increased, and a copper plating having a high adhesive strength was obtained.

[Brief description of drawings]

1 is a manufacturing process of a B-stage resin composition sheet with a copper foil containing a heat-resistant film base material for additive of Example 1. FIG.

[Explanation of symbols]

a heat resistant film b B-stage resin composition layer for additive adhering to copper foil c copper foil d B-stage resin composition layer for laminating on inner layer board e release film f heating roll

Continued front page    F-term (reference) 4F100 AA01B AA01D AA33E AB01A                       AB01E AB17 AB33 AB33A                       AK01A AK01B AK01C AK01D                       AK01E AK29B AK29D AK49                       BA25B BA25C BA25D CB00B                       CB00D DD07B DD07D DE01B                       DE01D EH71 EJ08B EJ08D                       GB41 GB43 JJ03 JJ03C                       JL11 JL14A JL14E YY00B                       YY00C YY00D                 4F211 AC03 AD03 AD05 AD08 AG01                       AG03 AH36 SA07 SC07 SH22                       SN01 SN03 SN05 SP01 SP21                 5E346 AA06 AA12 AA15 AA38 BB01                       CC02 CC09 CC10 CC12 CC31                       DD02 DD33 EE33 EE38 FF03                       FF04 GG02 GG17 GG22 GG27                       GG28 HH08 HH11 HH18

Claims (7)

[Claims] 1. A B-stage resin composition sheet containing a heat-resistant film substrate, wherein B-stage resin composition layers are adhered to both sides of a heat-resistant film substrate, wherein each B-stage resin composition sheet is a metal foil or a release film. These B-stage resin composition sheets are adhered and produced separately, and the B-stage resin composition sheets are placed on both sides of the heat-resistant film and laminated and adhered under pressure and heat,
A method for producing a B-stage resin composition sheet with a metal foil containing a heat-resistant film base material or a release film, which is produced integrally. 2. Of the B-stage resin composition layer adhered to the heat-resistant film, B adhered to at least a metal foil.
The stage resin composition layer is for additive use.
A method for producing a B-stage resin composition sheet with a metal foil containing a heat-resistant film base as described above. 3. The heat-resistant film-base metal-containing B according to claim 1, wherein the thickness of the B-stage resin composition layer attached to the surface of the metal foil is 5 to 20 μm from the tip of the convex portion.
A method for producing a stage resin composition sheet. 4. The additive according to claim 1, wherein in the sheet having the B-stage resin composition layer with release films attached to both surfaces of the heat-resistant film, at least one B-stage resin layer is a resin composition for additive. For producing a B-stage resin composition sheet with a release film containing a heat-resistant film base material for use in an automobile. 5. The resin composition for additives is a mixture of a resin component and a soluble component which are hardly soluble in the roughening solution when roughened with a roughening solution after curing treatment. As a resin component consisting of (a) a polyfunctional cyanate ester monomer, and 100 parts by weight of the cyanate ester prepolymer, (b) blending 15 to 500 parts by weight of a liquid epoxy resin at room temperature, (c) heat The curing catalyst was 0.0 per 100 parts by weight of (a + b).
B stage with a metal foil or a release film containing a heat-resistant film base material for additive according to claim 1, 2, 3 or 4, wherein a curable resin composition containing a resin composition in an amount of 05 to 10 parts by weight as an essential component is used. A method for producing a resin composition sheet. 6. A butadiene-containing resin, an organic powder, and an inorganic powder, which are soluble in the roughening solution even after the curing treatment, and use two or more of them as essential components. A method for producing a metal foil containing a heat-resistant film base material for additive or a B-stage resin composition sheet with a release film according to 3, 4, or 5. 7. The B-stage resin composition with a metal foil or a release film containing a heat-resistant film substrate according to claim 1, wherein the heat-resistant film substrate has a thickness of 4 to 20 μm. Sheet manufacturing method.