JP2003249751A - Additive method multilayer printed wiring board manufacturing method - Google Patents

Abstract

(57) [Summary] (with correction) [Problem] Build with excellent adhesion, high elastic modulus, small warpage and twisting, good thickness accuracy, excellent heat resistance, reliability, etc. by the additive method. Obtain a method of manufacturing an up-printed wiring board. SOLUTION: When forming an interlayer insulating layer, a prepreg f is arranged on both sides of an inner layer plate, and a metal foil a having surface irregularities b is adhered to one side of a metal foil a on the outside thereof. The B-stage resin composition sheet with the B-stage resin composition layer is arranged so that the B-stage resin composition layer faces the prepreg side, and laminated and cured under heating and pressure to produce a double-sided metal foil clad board. Then, the metal foil on both sides is removed. Then, after roughening the surface layer with a roughening solution, a conductor circuit j is formed by an additive method,
This is sequentially repeated to build up a multilayer printed wiring board.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a multilayer printed wiring board by an additive method, and particularly to a high density multilayer printed wiring board excellent in heat resistance, copper foil adhesive strength, reliability and the like. A multilayer printed wiring board is a high-density, small-sized printed wiring board on which semiconductor chips are mounted,
It is mainly used for new lightweight semiconductor plastic packages.

[0002]

2. Description of the Related Art In recent years, higher and higher density multilayer printed wiring boards have been used in electronic devices that are becoming smaller, thinner and lighter. This multilayer printed wiring board has a fine circuit formed, and the additive method multilayer printed wiring board using an adhesive agent in which a large amount of rubber is added to the conventional epoxy resin has high reliability, electrical characteristics,
Inferior in heat resistance, etc., there was a limit to use as a high density printed wiring board. Also, when the inner layer board is thin, if adhesive adhesive films without base material reinforcement are used on both sides, the build-up multilayer printed wiring board is inferior in mechanical strength such as bending strength and tensile strength and rigidity. Also, warpage is likely to occur, which is a cause of defects in the assembly process and the like.

[0003]

DISCLOSURE OF THE INVENTION The present invention has solved the above problems and has a high density of a multilayer printed wiring board having a high rigidity, excellent copper foil adhesion, heat resistance and the like, and excellent reliability. It is intended to provide a method for producing a multilayer printed wiring board by an additive method.

[0004]

The present invention is a method of sequentially laminating a conductor circuit and an interlayer resin insulation layer on a substrate and manufacturing a multilayer printed wiring board by an additive method, wherein the interlayer insulation layer is formed. At this time, a B-stage resin composition sheet with a metal foil, in which prepregs are arranged on both sides of the inner layer plate, and the resin composition for an additive is attached to one surface of the metal foil having surface irregularities on the outside thereof, the resin composition for additive is attached to the B-stage resin. Arranged so that the composition layer faces the prepreg side, after heating and laminating and curing treatment under pressure to produce a double-sided metal foil-clad plate, remove the metal foil on both sides, roughen the surface layer with a roughening solution. Then, copper plating is attached by an additive method, and the resin composition is post-cured. In the case of curing treatment, the resin reacts and becomes less soluble in the roughening solution, and due to the difference in solubility between the soluble component and the roughening solution, unevenness occurs when the surface layer is roughened.
Since the resin has not been completely cured by this curing treatment, if it is used as it is for a printed wiring board, the adhesive strength to copper plating is low, and if it is heated after absorbing moisture, it swells and cannot be used. Therefore, in the semi-additive method, after the entire surface is copper-plated, in the full-additive method, it is heat-cured before or after the conductor circuit is formed to obtain a printed wiring board. By sequentially repeating this and building up to manufacture a multilayer printed wiring board, a copper adhesive strength, a high elastic modulus (rigidity), a small warp / torsion, and a good board thickness accuracy were obtained. .

Further, the additive resin composition 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 the curing treatment. As a poorly soluble resin component, (a) a polyfunctional cyanate ester monomer, and 100 parts by weight of the cyanate ester prepolymer, (b) an epoxy resin which is liquid at room temperature
15 to 500 parts by weight of (c) thermosetting catalyst, (a + b) using a curable resin composition containing 0.005 to 10 parts by weight of 100 parts by weight of the resin composition as an essential component This makes it possible to manufacture a multilayer printed wiring board having excellent reliability such as heat resistance and migration resistance. By making two or more components out of the three components of the butadiene-containing resin, the organic powder, and the inorganic powder as essential components soluble in the roughening solution even after the curing treatment, the anchoring effect due to the roughening increases, and copper It is possible to obtain a plate having a large adhesive force.

DETAILED DESCRIPTION OF THE INVENTION The resin composition layer of the B-stage resin composition sheet with a metal foil for additive used in the production method of the present invention is not particularly limited, and a generally known one is used. . This resin layer contains a component soluble in the roughening solution when cured, and a resin component hardly soluble in the roughening solution, and the soluble component was uniformly dispersed in the resin component poorly soluble. It is a thing. 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".

Examples of the soluble resin of the present invention include generally known ones. 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,
Known compounds such as maleates, imides, carboxyl group-containing substances, imides, (meth) acrylates, and styrene-butadiene rubbers 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 powder of the present invention is not particularly limited, but powders of thermosetting resin, thermoplastic resin and the like can be mentioned, and when immersed in a roughening solution, it is more difficult than the hardened resin which has been hardened. There is no particular limitation as long as it has a high solubility. There are spherical shapes, crushed amorphous shapes, needle shapes, and the like, which can be used in combination. Spherical, crushed is preferably used, the particle size is not particularly limited, preferably an average particle size 0.1 ~ 10 (mu) m, more preferably an average particle size 0.2 ~ 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 7 μm or less, preferably 6 μm or less so that the particles do not come out of the resin surface after coating. In this case, the average particle size 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, SBR, ABS and the like, 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 hardly soluble resin of the present invention, known resins such as thermosetting resins and photosensitive resins may be used alone or in combination of two or more, and are not particularly limited, but specifically, epoxy resin, Examples thereof include polyimide resins, polyfunctional cyanate ester resins, maleimide resins, double bond-added polyphenylene ether resins, polyolefin resins, epoxy acrylates, unsaturated group-containing polycarboxylic acid resins, and polyfunctional (meth) acrylates. 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. In particular,
Suitably (a) a polyfunctional cyanate ester compound, with respect to 100 parts by weight of the cyanate ester prepolymer, (b) 15 to 500 parts by weight of a liquid epoxy resin is blended at room temperature, (c) a thermosetting catalyst A thermosetting resin composition containing as an essential component a resin composition prepared by mixing 0.005 to 10 parts by weight with respect to 100 parts by weight of the component (a + b) is used.

The polyfunctional cyanate ester compound (a) preferably used in the present invention is a compound having two or more cyanato groups in the molecule. To give a concrete example, 1,3-
Or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanato Naphthalene, 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. Known bromine adducts of the above compounds are also used. Also, the above-mentioned known compounds which are liquid at room temperature can be used.

As the epoxy resin which is liquid at room temperature, which is the component (b) of the present invention, generally known epoxy resins can be used. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, diglycidylated product of polyether polyol, epoxidized acid anhydride, alicyclic epoxy resin, etc. Used alone or in combination of two or more. The amount used is 15 to 500 parts by weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of the polyfunctional cyanate ester compound and the cyanate ester prepolymer.

In addition to these liquid epoxy compounds, known solid epoxy resins as described above, and cresol novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, etc., may be used alone or as a poorly soluble resin.
Used in combination of two or more species.

The thermosetting resin composition of the present invention may contain various additives other than those mentioned above, if desired, within a range in which the original properties of the composition are not impaired. Examples of these additives include various resins, known inorganic and organic fillers, dyes, pigments, thickeners, lubricants, defoamers, dispersants, leveling agents, photosensitizers, flame retardants, and brighteners. Various additives such as a polymerization inhibitor, a thixotropic agent, and the like are used in an appropriate combination as desired. If necessary, a known curing agent and a catalyst may be appropriately added to the compound having a reactive group.

The thermosetting resin composition of the present invention itself is cured by heating, but the curing speed is slow and the workability and economy are poor. Therefore, the known thermosetting catalyst for the thermosetting resin used. Can be used. The amount used is 100% thermosetting resin (a + b)
It is 0.005 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on parts by weight.

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 ... These components may be of one type, but preferably two or more of the three components are used. or,
By using different particle sizes than the same,
The shape of the unevenness becomes more complicated, the anchor effect increases, and the one having excellent copper plating adhesive strength is obtained.

The method of uniformly kneading each component 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. In addition, a solvent is added to obtain a viscosity suitable for the processing method.

The prepreg is produced by a known method. As the resin, the above-mentioned known thermosetting resin composition is used. As the base material, an organic or inorganic fiber cloth base material is used.
Although the type is not particularly limited, liquid crystal polyester fibers, polybenzazole fibers, wholly aromatic polyamide fibers, and other non-woven fabrics and woven fabrics are preferably used as the organic fiber fabrics. When using a non-woven fabric, attach a binder to connect the fibers or mix pulp and fibers,
The non-woven fabric of JP-A-11-255908, which is used as a binder by heating and melting pulp at a temperature of about 0 ° C., can be used. Although the amount of the binder is not particularly limited, it is preferably 3 to 8% by weight in order to maintain the strength of the nonwoven fabric. As the inorganic fiber cloth, a known glass fiber woven cloth or non-woven cloth having a general circular cross section and a flat cross section, and further a ceramic fiber woven cloth or non-woven cloth are used.

Known heat-resistant films such as polyamide film, liquid crystal polyester film and wholly aromatic polyamide film can also be preferably used as the substrate. The surface of the film is preferably subjected to a known surface treatment such as plasma treatment, corona treatment, chemical treatment in order to increase the adhesive strength.

The method for producing the prepreg is not particularly limited, and known methods can be used. For example, a method of impregnating a base material and drying it, or a method of arranging resin layers on both surfaces of the base material and integrating them by thermocompression bonding to prepare a prepreg can be mentioned. The resin composition used may be the same as the resin of the metal foil-clad B-stage resin composition sheet, but preferably a resin that is hardly soluble in an acid or an oxidizing agent is used. By doing so, when treated with an acid or an oxidizing agent, the soluble resin in the surface layer is dissolved, and the resin adhering to the base material of the prepreg is hardly dissolved. Since the adhesion of the plating by electrolytic copper plating does not reach the base material, it is possible to obtain a product having excellent reliability such as migration resistance.

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 7 μm,
More preferably, the average roughness is 2 to 5 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. If the roughness is too large, the depth due to the subsequent roughening becomes too deep, copper plating becomes difficult, and variations easily occur. 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. Of course, a copper foil with a smooth surface can also be used.

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. When used, the release film is peeled off. The thickness of the resin composition is not particularly limited, but is preferably 3 to 100 μm from the tip of the convex portion of the metal foil, preferably 4 to 50 μm,
More preferably, it is 5 to 20 μm. This thickness is appropriately selected depending on the thickness of the resin layer from the glass fiber of the prepreg used to the surface layer, and when roughened with a roughening solution to form irregularities that can secure the adhesive strength of the plated copper, the concave portion has a glass cloth. Try not to reach.

In the case of the multi-layering of the present invention, after the conductor of the inner layer board on which the conductor circuit is formed is subjected to a known surface treatment, or on the front and back of the inner layer circuit board using the double-sided roughening foil, the prepreg and the metal foil are attached. A B-stage resin composition sheet is placed, and laminated and molded by a known method under heating, pressure, and preferably under vacuum. After lamination, the metal foil is removed by etching or the like.

There are no particular restrictions on the lamination molding conditions for carrying out the lamination hardening treatment of the present invention, but the conditions under which roughening with a roughening solution can be appropriately performed are appropriately selected depending on the resin composition used.
Generally, the temperature is 60 to 250 ° C, the pressure is ^{2 to} 50 kgf / cm ² , and the time is 0.
5 to 3 hours. Further, it is preferable to carry out lamination molding under vacuum. A known device such as a vacuum laminator press or a general multi-stage press can be used as the device.

As a constitution, a conductor circuit is formed on a multilayer board obtained by laminating using ordinary prepreg, and after chemically treating the conductor, the prepreg and the B-stage resin composition sheet with a metal foil are arranged. It is also possible to fabricate only one surface layer, which is laminated and molded into a multilayer board, with this configuration. It is also possible to appropriately combine these laminating methods.

After removing the metal on the surface layer of the metal foil-clad sheet obtained by the present invention, the resin is roughened by a known method. 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, average roughness Rz 0.1 ~ 10 μm, preferably 0.2 apart from the unevenness of the metal foil.
~ 5 μm. The roughness of the unevenness of the metal foil and the roughness due to roughening is generally an average roughness Rz of 3 to 15 μm, preferably Rz is
The resin composition, the particle size of the soluble component, etc. are appropriately selected and used so as to be 5 to 12 μm.

After that, electroless plating, thickening electroless plating, vapor deposition, sputtering, etc. are performed by a known semi-additive method, full-additive method or the like, and more generally, electroplating is performed to thicken the conductor. . Further, circuits are formed by known methods to obtain printed wiring boards. If necessary, through holes and blind via holes are opened, and after desmearing, the same steps are sequentially repeated to build up multiple layers.

Of course, it is also possible to laminate using a B-stage resin composition sheet with copper foil and manufacture a printed wiring board by the subtractive method.

[0031]

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 of 2,2-bis (4-cyanatophenyl) propane monomer
Part 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. A bisphenol A type epoxy resin (trade name: Epicoat 828, Japan Epoxy Resin <
Co., Ltd.) 50 parts, bisphenol F type epoxy resin (trade name: EXA830LVP, Dainippon Ink and Chemicals Co., Ltd.) 100 parts,
50 parts of novolac type epoxy resin (trade name: DEN438, manufactured by Dow Chemical Co., Ltd.), as a solid epoxy resin at room temperature,
Bisphenol A type epoxy resin (trade name: Epicoat
1001, 300 parts of Japan Epoxy Resin Co., Ltd., cresol novolac type epoxy resin (trade name: ESCN220F,
100 parts of Sumitomo Chemical Co., Ltd.) was blended, and 0.3 parts of iron acetylacetone as a thermosetting catalyst was dissolved in methyl ethyl ketone and added. Liquid epoxidized polybutadiene resin (trade name: E-1000-8.0, manufactured by Nippon Petrochemical Co., Ltd.) 100
Part, epoxy group-modified acrylic rubber powder (trade name: Staphyloid IM203, average particle size 0.3 μm, MAX. Particle size 0.5 μm,
50 parts of Ganz Kasei Co., Ltd.) was added and mixed well by stirring to form a uniform varnish B.

This varnish B was continuously applied to a 18 μm thick copper foil matte surface (unevenness 3.6 to 6.1 μm, average roughness Rz: 4.5 μm), dried, and the height of Max. A sheet C having a B-stage resin composition layer (gelling time at 170 ° C., 43 seconds) of Example 3 was prepared.

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, Mitsubishi Gas Chemical Co., Ltd.), a circuit was formed and black copper oxide treatment was applied to the copper foil on both sides of a BT resin prepreg (trade name: GHPL-830, Mitsubishi Gas Chemical (Stock> product)
1 sheet each, and the B-stage resin composition sheet with the copper foil is placed on both outsides thereof so that the resin layer faces the prepreg side, and after being placed in a press machine, it takes 25 minutes from room temperature to 170 ° C. Raise the temperature and pressure from the beginning to 15 kgf / cm ² ,
The vacuum was maintained at 170 ° C. for 30 minutes at a vacuum of 0.5 Torr, then cooled and taken out to obtain a four-layered multilayer plate D. 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. Potassium permanganate-based desmear solution (Japan McDermid
Strain>), desmear (dissolve), and neutralize to 3.3-5.0 μm concaves from the resin surface (average roughness Rz: 4.1 μm), and 6.8 to 11.0 μm total average irregularities from the surface layer (average roughness) Rz: 8.7 μm). At this time, the concave portion did not reach the glass cloth of the prepreg laminated together. At the same time, the resin layer remaining at the bottom of the blind via hole was dissolved and removed. Next, electroless copper plating 0.5μm, electrolytic copper plating 25μm on this roughened surface
The mixture was attached, placed in a heating furnace, and the temperature was gradually raised from 100 ° C. to 150 ° C. in 30 minutes, and further gradually raised to 200 ° C. for 60 minutes for heat curing. Using this, a copper conductor circuit was formed by the semi-additive method, the conductor circuit surface was further treated with black copper oxide, and the same process was repeated to fabricate a 6-layer multilayer printed wiring board. The results of measuring this property are shown in Table 1.

Example 2 Bisphenol A type epoxy resin (trade name: Epicort 1
001, Yuka Shell Epoxy Co., Ltd.) 500 parts, phenol novolac type epoxy resin (trade name: DEN438, Dow Chemical Co., Ltd.) 500 parts, imidazole curing agent (trade name: 2)
E4MZ, Shikoku Kasei Co., Ltd.) 30 parts, carboxyl group-modified acrylic multi-layer structure powder (trade name: Staphyloid IM-301, average particle size 0.2 μm, Max. Particle size 0.9 μm) 50 parts, finely pulverized silica ( Average particle size 2.4 μm, Nax. Particle size 5.0 μm) 40 parts, and acrylonitrile-butadiene rubber (trade name: Nipol 103
1. A solution prepared by dissolving 30 parts of Nippon Zeon Co., Ltd. in methyl ethyl ketone was added and well dispersed by a three-roll mill. This has a thickness of 20 μm and surface irregularities of 1.3 to 5.5 μm (average roughness Rz: 4.0 μm
m) aluminum foil (trade name: 20CF1, Japan Condenser Industry <
Co., Ltd.) on one side continuously, dry and then from the tip of the protrusion
A B-stage resin composition sheet E with an aluminum foil having a resin layer of 6.0 μm (gelling time at 170 ° C., 51 seconds) was prepared.

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, and the conductor is treated with black copper oxide, and then 60 μm thick epoxy prepreg (product name: GEPL-
170, manufactured by Mitsubishi Gas Chemical Co., Inc.) is placed on each side, and the above-mentioned sheet E with the B-stage resin composition with aluminum foil is placed on the outside thereof, and after being placed in a press machine, the temperature is raised to 170 ° C in 25 minutes Raise the pressure from the beginning to 15 kgf / cm ^2, and set the degree of vacuum.
After holding at a temperature of 170 ° C. for 30 minutes at 0.5 Torr ^2, it was cooled and taken out to obtain a four-layer multilayer plate F. The aluminum foil on this surface was dissolved and removed with a 10% hydrochloric acid solution, and the carbon dioxide gas laser output was 12 m.
Blind via holes with a diameter of 100 μm were made by irradiating one shot with J.

After roughening with a chromic acid-based roughening solution, the recesses from the resin surface were adjusted to 3.6 to 5.1 μm (average roughness Rz: 4.0 μm). 4.7 to 10.1 μm (total roughness Rz: 8.1 μm) in total from the surface irregularities
And At this time, the concave portion did not reach the glass cloth of the prepreg laminated together. At the same time, the resin layer remaining at the bottom of the blind via hole was dissolved and removed.

Next, an electroless copper plating layer is formed on the roughened surface.
0.7 μm and 25 μm of electrolytic copper plating were adhered, put in a heating furnace and heated and cured at 150 ° C. for 30 minutes and 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 results of measuring this property are shown in Table 1.

Comparative Examples 1 and 2 In Examples 1 and 2, the thickness of the resin layer of the B stage attached to the uneven portions of the copper foil and the aluminum foil was 65 μm from the tip of the convex portion.
A B-stage resin composition sheet with a metal foil was prepared by adhering, and a prepreg was not used in Examples 1 and 2 and a B-stage resin composition sheet with a metal foil alone was used and laminated and cured similarly. In the same manner as in Examples 1 and 2, the roughening treatment was performed in the same manner, and the total unevenness from the surface layer was 5 to 11
μm (average roughness Rz: 8 to 9 μm), and similarly a multilayer printed wiring board having 6 layers. The evaluation results are shown in Table 1.

Comparative Example 3 In Example 1, a glass cloth having a thickness of 50 μm was impregnated with varnish B and dried to have a thickness of 65 μm and a gelling time (170 ° C.).
55 seconds of prepreg G was manufactured. 1 each for this prepreg
It was arranged on both sides of the inner layer plate, and a copper foil of 18 μm was placed on the outer side of the inner layer plate, and similarly laminated and cured to form a four-layer multilayer plate. After removing the copper foil on the surface layer by etching, blind via holes are formed, and roughening treatment is performed in the same manner to make the total irregularities from the surface layer 5 to 11 μm. Copper treatment, prepreg G arrangement, 18μ
6 layers of multilayer printed wiring board is prepared by arranging m copper foil, similarly removing the copper foil on the surface layer, forming blind via holes, desmearing, electroless copper plating, electrolytic copper plating and circuit formation. did. When the copper-plated cross section was observed, a roughening recess reached the glass cloth and there were many places where the 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 multilayered structure powder, finely pulverized silica, and acrylonitrile-butadiene rubber were not used. Was coated and dried to a thickness of 65 μm, and a B-stage resin composition sheet H with an aluminum foil having a resin layer having a gelation time (170 ° C.) of 80 seconds was prepared. One B-stage resin composition sheet H with an aluminum foil is arranged on each side of the inner layer plate,
Similarly, a multilayer curing treatment was performed to form a four-layer multi-layer plate, the aluminum foil on the surface layer was dissolved and removed with 10% hydrochloric acid, and then blind via holes were similarly formed with a CO2 laser.
Roughening treatment under the same conditions as above, followed by electroless copper plating and electrolytic copper plating, followed by conductor circuit formation, conductor black copper oxide treatment, B-stage resin composition sheet H placement with aluminum foil, and lamination molding, and then similar processing Then, a 6-layer printed wiring board was obtained. 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 1.37 1.23 1.37 1.16 0.46 Soldering heat resistance No abnormality No abnormality No abnormality Partial swelling Partial swelling Glass Transition temperature DMA (° C) 196 153 197 153 196 168 Elastic modulus 25 ° C (kgf / mm ² ) 1910 1783 1002 976 2001 860 Warp / twist (mm) 1.6 1.9 4.7 5.3 1.5 5.4 Thickness variation (μm) 10.5 11.0 19.0 20.3 10.4 22.7 Blind via hole / heat cycle test Resistance change rate (%) 1.5 2.1 2.0 2.9 1.8> 10 Crack generation 200 cycles 0/1000 0/1000 0/1000 0/1000 0/1000 210/1000 400 cycles 0/1000 55 / 1000 0/1000 72/1000 67/1000 970/1000 migration resistance (Omega) normal ^{5x10 12 3x10 12 5x10 12 6x10 12} 4x10 12 5x10 12 200hrs. 6x10 11 7x10 9 3x10 10 6x10 8 2x10 9 1x10 9 500hrs. 8x10 ¹⁰ <10 ⁸ 7x10 ¹⁰ <10 ⁸ <10 ⁸ <10 ⁸

<Measurement Method> 1) Copper Adhesion Strength: 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 laminating 14 prepregs and the thickness is almost 0.
The one with 8 mm was used. 4) Elastic Modulus: The elastic modulus at 25 ° C of the DMA chart measured in 2) is shown. 5) Warp and twist: Using a 6-layer printed wiring board manufactured with a size of 250x250 mm, it was placed on a surface plate and the maximum values of warp and twist were measured. 6) Thickness variation: The thickness variation of the layer laminated on one side of the 6x250x250 mm printed wiring board of 5) was measured with a thickness measuring instrument and expressed as (maximum value-minimum value). 7) Blind via hole, resistance value change and crack by heat cycle test: 2 from the surface layer of each 6-layer printed wiring board
Blind via hole formed in the second layer (hole diameter 100 μm, land
Connect 180 μm to the second layer and the third layer alternately for 1000 holes at -65 ℃ /
200 cycles were repeated with 30 minutes ← → 150 ° C / 30 minutes as one cycle, and the maximum change in resistance was measured. Also, 200, 400
Occurrence of resin cracks was observed by observing the hole cross section in the cycle. The number of occurrences is shown in the numerator, and the number of tests is shown in the denominator. 8) Migration resistance: A circuit of line / space = 50/50 μm is formed on the surface layer of each of the four-layer boards of Examples and Comparative Examples,
After laminating in the same manner as in each of the examples and comparative examples to form a 6-layer plate, the surface metal foil was dissolved and removed, and the test piece was subjected to 85 ° C / 85 ° C.
50% DC was applied at% RH and the insulation resistance between the terminals was measured.

[0043]

EFFECT OF THE INVENTION A method of manufacturing a multilayer printed wiring board by an additive method by sequentially laminating a conductor circuit and an interlayer resin insulation layer on a substrate, and forming the interlayer insulation layer on both sides of the inner layer board. A B-stage resin composition sheet with a metal foil, in which a prepreg is placed and a resin composition for additive is attached to one side of a metal foil having surface irregularities on the outside, is placed such that the B-stage resin composition layer faces the prepreg side. Then, after laminating and curing under heat and pressure to produce a double-sided metal foil-clad plate, the metal foils on both sides are removed, the surface layer is roughened with a roughening solution, and then copper plating is attached by an additive method. By repeating the steps of post-curing and circuit formation and building up to manufacture a multilayer printed wiring board, it is possible to obtain a product with high elastic modulus (rigidity), small warpage and twist, and good board thickness accuracy. .

Further, the resin composition for additive is a mixture of a resin component and a soluble component which are hardly soluble in the roughening liquid after roughening with the roughening liquid after the curing treatment. As a poorly soluble resin component, (a) a polyfunctional cyanate ester monomer, 100 parts by weight of the cyanate ester prepolymer, (b) an epoxy resin 15-liquid at room temperature
By blending 500 parts by weight, (c) 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 It was possible to obtain a multilayer printed wiring board excellent in reliability such as heat resistance and migration resistance. By making two or more components out of the three components of the butadiene-containing resin, the organic powder, and the inorganic powder as essential components soluble in the roughening solution even after the curing treatment, the anchoring effect due to the roughening increases, and copper A product having a large adhesion of plating was obtained.

[Brief description of drawings]

FIG. 1 is a manufacturing process of a printed wiring board of Example 1. (1) B-stage resin composition sheet with a copper foil having a cover film on the resin side (2) Configuration during lamination molding (3) Roughening after etching and removing the copper foil on the surface layer (4) Roughened resin surface

FIG. 2 is a process of manufacturing a printed wiring board of Comparative Example 3. (1) Configuration during laminated molding (2) Roughening after removing the copper foil on the surface layer by etching (3) Resin surface roughened to glass fiber

[Explanation of symbols]

a Copper foil b Copper foil irregularities c B stage resin composition layer d Resin powder e Release film f prepreg g Fiberglass yarn h Glass fiber cross section Resin between glass cloth and B-stage resin layer j Inner layer board conductor circuit k Inner layer board insulation layer l Roughened surface resin layer m Surface irregularities after removing copper foil by etching n Location that reached the glass cloth due to roughening

[Procedure amendment]

[Submission date] February 26, 2002 (2002.2.2)
6)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition layer of the B-stage resin composition sheet with metal foil for additive used in the production method of the present invention is not particularly limited, and a generally known resin composition layer is used. This resin layer contains a component soluble in the roughening solution when cured, and a resin component hardly soluble in the roughening solution, and the soluble component was uniformly dispersed in the resin component poorly soluble. It is a thing. 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".

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 C08L 63/00 Z 79/00 79/00 H05K 3/38 H05K 3/38 AF term ( (Reference) 4J002 BB00W BB00X BC03W BG04W BH02X BN15W BN16W CC03W CD00W CD00X CD20X CH07W CH07X CM02X CM04W CM04X CP03W DE077 DE147 DE237 DJ007 DJ017 AA BB AA32A25ADD32A25ADD32A25ADD16A32A27ABB16A32A21ABB16A32A21ABB32A24A5 CC02 CC08 CC09 CC32 CC58 DD02 DD33 EE31 EE35 EE38 FF03 FF04 GG02 GG17 GG22 GG27 GG28 HH07 HH11 HH18

Claims (5)

[Claims] 1. A method for manufacturing a multilayer printed wiring board by an additive method, in which a conductor circuit and an interlayer resin insulation layer are sequentially laminated on a substrate, and both sides of an inner layer board are formed when the interlayer insulation layer is formed. A B-stage resin composition sheet with a metal foil, in which a prepreg is placed and a resin composition for additive is attached to one side of a metal foil having surface irregularities on the outside, is placed such that the B-stage resin composition layer faces the prepreg side. Then, after laminating and curing under heat and pressure to produce a double-sided metal foil-clad plate, the metal foils on both sides are removed, and the surface layer is roughened with a roughening solution, and then a conductor circuit is formed by the additive method. A manufacturing method of an additive method multilayer printed wiring board, characterized in that the multilayer printed wiring board is manufactured by sequentially repeating the above steps to build up. 2. The resin composition for additive is a mixture of a resin component and a soluble component which are hardly soluble in a roughening solution when roughened with a roughening solution after curing treatment. As a resin component to be, (a) polyfunctional cyanate ester monomer, with respect to 100 parts by weight of the cyanate ester prepolymer, (b) compounding 15 to 500 parts by weight of a liquid epoxy resin at room temperature, (c) Thermosetting catalyst for 100 parts by weight of (a + b)
The method for producing an additive-type multilayer printed wiring board according to claim 1, wherein a resin composition mixed in an amount of 0.005 to 10 parts by weight is an essential component. 3. The method according to claim 1, wherein two or more components out of three components of a butadiene-containing resin, an organic powder and an inorganic powder are used as essential components as components soluble in the roughening solution after the curing treatment. Additive method for manufacturing multilayer printed wiring boards. 4. The additive-type multilayer printed wiring according to claim 1, 2 or 3, wherein the thickness of the B-stage resin composition layer of the B-stage resin composition sheet with metal foil is 5 to 20 μm from the tip of the convex portion of the metal foil. Method of manufacturing a plate. 5. The additive-type multilayer printed wiring according to claim 1, wherein the surface layer is roughened with a roughening solution, copper plating is adhered, and then post-cured by heating. Method of manufacturing a plate.