JP2003249764A - A method for producing a B-stage resin composition sheet containing a substrate for an additive. - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To provide a method for producing an adhesive sheet for a build-up printed wiring board, which is excellent in heat resistance and reliability, has high plating copper adhesive strength and elastic modulus by an additive method. SOLUTION: A resin composition layer for an additive, preferably a metal foil or a release film is disposed on one side of a base-reinforced B-stage resin composition sheet, and laminated and integrated to form an additive-containing B-staged resin composition sheet. A stage resin composition sheet is manufactured.

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 substrate for a multilayer printed wiring board by an additive method. The obtained B-stage resin composition sheet is especially copper-bonded. Force, elastic modulus (rigidity)
It is suitable for producing high-density multi-layer printed wiring boards with high heat resistance and reliability, and the obtained multi-layer printed wiring boards are equipped with semiconductor chips as high-density small printed wiring boards. , Mainly used for small and lightweight new 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 therein, and the additive method multilayer printed wiring board using an adhesive sheet in which an adhesive containing a large amount of rubber added to a conventional epoxy resin is attached to a release film is If there is no base material and the inner layer board is thin, if additive adhesive sheets without base material reinforcement are used on both sides, the build-up multilayer printed wiring board has a mechanical strength such as bending strength and tensile strength. The mechanical strength and elastic modulus (rigidity) are inferior, and warpage and twisting are likely to occur, which is a cause of defects in the assembly process and the like. Furthermore, the thickness variation during lamination molding is large, and it is difficult to control the plate thickness.

[0003]

DISCLOSURE OF THE INVENTION The present invention has solved the above problems, and has an elastic modulus (rigidity) of a multilayer printed wiring board,
Small warp and twist, good plate thickness accuracy, copper adhesion,
It is intended to provide a method for producing a B-stage resin composition sheet with a metal foil containing a base material for producing a high-density multilayer printed wiring board excellent in heat resistance, reliability, etc. by an additive method.

[0004]

The present invention is a B-stage resin composition sheet containing a base material for producing 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. The B-stage resin composition sheet containing a base material to be adhered to this substrate is manufactured by attaching a resin composition layer for additive to one side of a base material-reinforced B-stage resin composition sheet (prepreg). It is preferable to laminate a sheet in which a resin composition layer for additive is attached to a metal foil or a release film having surface irregularities on one side of a base material reinforced B-stage resin composition sheet (prepreg) by laminating adhesion. Using the product manufactured by the above, place it on the inner layer board, heat press bond it and bond it, and form a circuit by the additive method to make a printed wiring board. .

Further, at least the additive insulating layer of the B-stage resin composition sheet containing the substrate contains a resin component and a soluble component which are hardly soluble in the roughening solution when roughened with the roughening solution after the curing treatment. As a resin component which is blended, the (a) polyfunctional cyanate ester monomer and 100 parts by weight of the cyanate ester prepolymer are used as the sparingly soluble resin component, and (b) an epoxy resin 15-liquid at room temperature. 500 parts by weight of (c) thermosetting catalyst was added to (a + b) 100 parts by weight of 0.005
It is preferable to use a curable resin composition containing a resin composition containing 10 to 10 parts by weight as an essential component in order to improve heat resistance and reliability. By using two or more components out of the three components of the butadiene-containing resin, the organic powder and the inorganic powder as the components soluble in the chemical solution, it was possible to obtain the one having excellent adhesion to the plated copper.

Since the B-stage resin composition sheet with a metal foil containing a substrate or with a release film contains a substrate, a print obtained by build-up using a particularly thin inner layer plate. Wiring boards have a higher elastic modulus (rigidity), less warp and twist, and excellent molding thickness when laminated, compared to conventional printed wiring boards using B-stage resin composition sheets that do not contain a base material. As a result, a thin type suitable for a high density printed wiring board by the additive method was obtained.

The method for producing a B-stage resin composition sheet containing a substrate of the present invention is as follows: (1) A substrate-reinforced B-stage resin composition sheet (prepreg) is prepared, and a varnish for additive or a solventless resin composition is formed on one side of the sheet. (3) A method in which a product is thinly coated with a roll coater or the like and dried to form a B stage, and a metal foil or a release film is laminated on the B stage resin composition layer side for additive under heating and pressure, (3)
A base material-reinforced B-stage resin composition sheet (prepreg) and a metal foil or a release film-attached B-stage resin composition sheet for additive are separately prepared, and one side of the base material-reinforced B-stage resin composition sheet is heated, It is a method of laminating under pressure and adhering and integrating a metal foil or a release film-attached B-stage resin composition sheet for an additive to obtain a B-stage resin composition sheet with a metal foil containing a base material or a release film. . When the solvent-free resin composition is used, the resin composition is adhered only by pressing without heating, but in order to further improve the adhesiveness, the composition is preferably adhered under pressure by heating.

The resin composition layer for additive of the B-stage resin composition sheet with a metal foil containing a substrate or a release film of the present invention is a resin composition capable of forming a circuit by an additive method, and is a thermosetting type, a photocurable type. Examples include generally known ones such as a combination of curing and thermosetting. The resin composition of the B-stage resin composition sheet for additive is not particularly limited, and a generally known resin composition is used. 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 terms “soluble” and “poorly soluble” used in the present invention have relatively high dissolution rates when immersed in a roughening solution containing the same acid or oxidizing agent for the same time after the curing treatment. The ones are described as "soluble" and the slow ones 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 uniformly dispersed and mixed in a poorly soluble resin. These are not particularly limited, but specifically, polybutadiene rubber, acrylonitrile-butadiene rubber, epoxidized products thereof, maleated products, imidized products, carboxyl group-containing products, imidized products, (meth) acrylic compounds, etc., styrene-butadiene rubber And the like. 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 crosslink and the properties are improved.

The soluble organic powder of the present invention is not particularly limited, but powders of thermosetting resin, thermoplastic resin, etc. may 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, 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 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 monomer, and 100 parts by weight of the cyanate ester prepolymer, (b) 15 to 500 parts by weight of a liquid epoxy resin at room temperature is blended, and (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. With this composition, the resin layer does not become brittle when attached to a metal foil or a release film and is preferable in use.

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, and 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 and liquid prepolymers can also be used.

As the epoxy resin which is liquid at room temperature, 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 with respect to 100 parts by weight of the polyfunctional cyanate ester compound and the cyanate ester prepolymer,
It is preferably 20 to 300 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 epoxies that can be crushed at room temperature, further cresol novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, etc., are used alone or in combination of two or more as poorly soluble resins. used.

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-containing compounds, known inorganic or organic fillers other than the above,
Various additives such as dyes, pigments, thickeners, lubricants, defoamers, dispersants, leveling agents, photosensitizers, flame retardants, brighteners, polymerization inhibitors, and thixotropic agents can be added as desired. They are used in appropriate combination. 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 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 100% thermosetting resin (a + b)
It is 0.005 to 10 parts by weight, preferably 0.01 to 5% 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 one component, but preferably two or more components among the three components are used. 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. In addition, a solvent is added to obtain a viscosity suitable for the processing method.

The metal foil having an uneven surface used in the present invention is not particularly limited, and specific examples thereof include aluminum foil and copper foil. The unevenness of the surface to which the resin is attached is not particularly limited, but the average roughness Rz is preferably 1 to 10 μm, more preferably 2 to 7 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.

Of course, a metal foil having a smooth surface can also be used. Also, a known release film can be used. Examples thereof include polyethylene terephthalate (PET) film, poly-4-methylpentene-1 film, fluororesin film and the like. These surfaces may have irregularities. Further, a release agent treatment, an antistatic treatment or the like may be performed.

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 a protective film, drying and B-stage after placing the metal foil on the resin composition side, heating, pressure roll And the like to obtain a B-stage resin composition sheet with a metal foil integrated by pressure bonding. The same applies to the case of coating on a release film. 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 generally 3 to 100 μm from the tip of the convex of the metal foil, preferably 4 to
It is 50 μm, more preferably 5 to 20 μm. This thickness is appropriately selected according to the resin layer thickness from the glass fiber of the prepreg to the surface layer used together, and when roughened with an acid or an oxidant in order to form irregularities that can secure the adhesive strength of the plated copper, the tip of the recess is Avoid reaching the woven glass fibers.

The prepreg which is the base material reinforced B-stage resin composition sheet of the present invention is produced by a known method. As the resin, the above-mentioned known resins and additives are used. Although components soluble in the roughening solution used in the additive resin composition may be used, many components lower reliability as compared with the resin composition not added, and the amount used should be an appropriate amount. Is preferred. 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. In the case of a non-woven fabric, a binder is attached to connect the fibers to each other, or pulp and fibers are mixed, and the non-woven fabric of JP-A-11-255908 used as a binder by heating and melting the pulp at a temperature of about 300 ° C. Can be used. The amount of the binder is not particularly limited, but in order to maintain the strength of the nonwoven fabric, it is preferably 3 to 8% by weight.
Attach it. 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.

A heat-resistant film base material can also be used.
The heat-resistant film is not particularly limited, and known ones can be used. Specific examples include polyimide film, wholly aromatic polyamide film, liquid crystal polyester film and the like. The surface can be used without any treatment, but a well-known treatment for improving resin adhesion, for example, plasma treatment, corona treatment, chemical treatment, sandblast treatment, etc. is preferably used.

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 layer may have the same thickness on both sides of the substrate, or the resin layer on the surface to which the B-stage resin layer with a metal foil adheres is thinned, and the thin resin layer surface has a B-stage resin layer with a metal foil or a release film. Can also be attached. The resin composition to be used may be the same as the additive resin of the B-stage resin composition sheet with the metal foil-clad or release film, but is preferably a resin which is hardly soluble in a roughening solution such as an acid or an oxidizing agent. Mainly used. By doing so, when the roughening treatment with the roughening solution, the soluble resin of the surface layer is dissolved, the resin adhered to the base material of the prepreg is hardly dissolved, the base material fiber is not exposed, and Since the adhesion of the electroless copper plating does not reach the base material, the one having excellent reliability such as migration resistance can be obtained. Further, preferably, by using a polyfunctional cyanate ester resin composition for this resin as well, a multilayer printed wiring board having high heat resistance and migration resistance between inner layer copper foils and between insulating layers can be produced. . There are no particular restrictions on the conditions for laminating, but generally the temperature is 60 to 150 ° C and the linear pressure is 1 to 20 kgf / cm. In addition, a method in which a resin layer for additive is continuously applied to one surface of the prepreg, dried and made into a B stage, and then a metal foil or a release film is arranged on the resin layer side for additive and laminated to integrate the same. Manufactured.

In the case of multi-layering of the present invention, the metal containing the above-mentioned base material is applied to the conductor of the inner layer plate on which the conductor circuit is formed, after known surface treatment, or on the front and back of the inner layer circuit plate using the double-sided roughening foil. A B-stage resin composition sheet with a foil or a release film is placed, and laminated by heat and pressure, preferably under vacuum, by a known method. After stacking, the metal foil is removed by etching or the like.

The lamination molding conditions for forming the multi-layer of the present invention are as follows:
Although not particularly limited, conditions under which roughening with an acid or an oxidizing agent can be appropriately performed are appropriately selected depending on the resin composition used.
Generally, the temperature is 60-250 ℃, the pressure is 2-50kgf / cm2, 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 vacuum press can be used as the device.

After removing the metal or the release film on the surface layer of the metal foil-clad sheet obtained by the present invention, the resin is roughened with an acid or an oxidizing agent by a known method. Examples of the acid to be used include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid and the like, and oxidizing agents such as sodium permanganate and potassium permanganate.
Examples thereof include chromic acid and chromic sulfuric acid, but are not limited thereto. 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, an average roughness Rz of 0.1 to 10 μm, preferably 0.2 to 5 μm. The average roughness Rz is 3 to 15 μm, and preferably Rz is 5 to 12 μm.

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

After that, electroless plating, thick electroless plating, vapor deposition, sputtering, etc. are performed by a known semi-additive method, full-additive method or the like, and generally, electroplating is performed to thicken the conductor. When curing is performed to the extent that it can be roughened by the additive method, it generally depends on the resin composition, but in general, the resin is not sufficiently cured, and if a printed wiring board is used as it is without post-curing, heat resistance However, it is not possible to manufacture a device having the original characteristics in reliability and the like. Therefore, generally, after the copper plating is attached, it is post-cured in an oven or the like.

The post-curing conditions are not particularly limited, but the conditions are such that the attached copper plating does not peel off. Generally the temperature is 60-25
The temperature is 0 ° C., the time is 0.5 to 5 hours, and the resin composition has a curing degree that causes no problems in the printed wiring board processing step and the subsequent assembly step. Further, it is preferable to raise the temperature stepwise so as not to cause copper plating peeling.

After that, circuits are formed by known methods to obtain printed wiring boards. Through hole if necessary,
A blind via hole is opened, and after roughening and desmearing, the same process is repeated in sequence to build up a multilayer structure.

This B-stage resin composition sheet containing a substrate can also be used for lamination of general copper-clad laminates and multilayer boards, and the B-stage resin composition sheet with a release film is
It is also possible to laminate using copper foil and manufacture a printed wiring board by the subtractive method.

[0035]

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.) 70 parts, bisphenol F type epoxy resin (trade name: EXA830LVP, Dainippon Ink and Chemicals Co., Ltd.) 80 parts,
50 parts of novolac type epoxy resin (Brand name: DEN438, manufactured by Dow Chemical Co., Ltd.), bisphenol A type epoxy resin (Brand name: Epicoat 100) as a solid epoxy resin at room temperature
1, Japan Epoxy Resin Co., Ltd.) 200 parts, cresol novolac type epoxy resin (trade name: ESCN220F, Sumitomo Chemical Co., Ltd.) 100 parts were mixed, and 0.3 parts of acetylacetone iron 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 parts, epoxy resin powder (trade name: Trepearl EP-B, average particle size 0.5)
(50 μm, manufactured by Toray Industries, Inc.) and well mixed with stirring to form a uniform varnish B.

This varnish B was continuously applied to a 18 μm thick copper foil mat surface (unevenness 3.6 to 6.1 μm, average roughness Rz: 4.5 μm), dried, and copper having a height of 5.1 μm from the tip of the convex portion. A sheet C with a B-stage resin composition layer with a foil (gelling time at 170 ° C: 43 seconds) was prepared, and when it came out, a protective PET film with a thickness of 25 μm was placed on the resin surface and the temperature was 100 ° C and the wire It was laminated with a roll having a pressure of 4 kgf / cm and wound up.

Further, the polyfunctional cyanate ester monomer of Example 1 above, the solid content of the prepolymer varnish A is 500 parts,
Bisphenol F type epoxy resin (trade name: EXA830LV
P, manufactured by Dainippon Ink and Chemicals, Inc.) 150 parts, novolac type epoxy resin (trade name: DEN438, manufactured by Dow Chemical Co., Ltd.) 1
50 parts, cresol novolac type epoxy resin (trade name: E
SCN220F, manufactured by Sumitomo Chemical Co., Ltd.) (150 parts) was mixed, and 0.2 part of zinc octylate as a thermosetting catalyst was dissolved in methyl ethyl ketone and added. Epoxy-group-modified acrylic rubber with multiple structure (trade name: Staphyloid IM-203, average particle size
50 parts of 0.3 μm, manufactured by Ganz Kasei Co., Ltd.) were added and mixed well with stirring to obtain a uniform varnish D. This was continuously impregnated into a glass woven cloth having a thickness of 50 μm and dried to prepare a prepreg E having a gelling time of 60 seconds and a total thickness (glass woven cloth + resin layer) of 65 μm,
When it came out, a release PET film having a thickness of 25 μm was arranged on both sides, laminated with a roll having a temperature of 100 ° C. and a linear pressure of 5 kgf / cm, and wound up.

While the protective PET fill of the B-stage resin composition sheet C with the copper foil was peeled off and the PET film on one side of the prepreg E was peeled off, the resin surfaces were joined together at a temperature of 100 ° C. and a linear pressure of 5 kgf. The laminate was continuously laminated with a heating roll of / cm, and integrated to form a B-stage resin composition sheet F with a copper foil containing a base material, which was wound up.

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., Ltd.), and a B-stage resin composition sheet F with a copper foil containing the above-mentioned base material is formed on a PET film on both sides of a substrate on which a copper foil has been subjected to black copper oxide treatment. After peeling off and arranging so that the resin layer faces the inner layer substrate side and charging it in the press machine, the temperature is raised from room temperature to 170 ° C in 25 minutes, the pressure is 15 kgf / cm2 from the beginning, and the vacuum degree is 0.5To.
After holding at 170 ° C. for 30 minutes at rr, it was cooled and taken out to obtain a multi-layer board G having four layers. After removing the copper foil on this surface by etching,
A blind via hole having a hole diameter of 100 μm was opened by irradiating one shot with an output of a carbon dioxide gas laser of 12 mJ. Swell, desmear (dissolve) and neutralize with potassium permanganate-based desmear solution (Japan MacDermid Co., Ltd.) to remove the concaves from the resin surface.
It was set to 3.5 to 5.2 μm (average roughness Rz: 4.2 μm). At this time, the tip of the concave portion did not reach the glass fiber of the prepreg E laminated together. At the same time, the resin layer remaining at the bottom of the blind via hole was dissolved and removed. Next, 0.7 μm electroless copper plating and 25 μm electrolytic copper plating on the roughened surface,
Place in a heating furnace and gradually raise the temperature from 100 ° C to 150 ° C in 30 minutes, and then gradually raise the temperature to 200 ° C at 200 ° C.
Cured by heating for 60 minutes. 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 evaluation results 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.) 450 parts, imidazole-based curing agent (trade name: 2E4MZ, Shikoku Kasei Co., Ltd.) ) 30 parts, carboxyl group-modified acrylic multi-layered powder (Product name: Staphyroid IM-3
01, average particle size 0.2 μm) 60 parts, finely pulverized silica (average particle size 2.4 μm) 40 parts, and acrylonitrile-butadiene rubber (trade name: Nipol 1031, Nippon Zeon Co., Ltd.) 30 parts dissolved in methyl ethyl ketone, Add the dispersed solution and disperse well with 3 rolls to obtain Varnish H.

A 25-μm-thick release PET film, which had been treated with a release agent and an antistatic treatment, was continuously applied on one side and dried to form a 15 μm resin layer with a release film on the B-stage resin. Composition sheet I (gelation time at 170 ° C, 51 seconds) was prepared, and when it came out, the resin surface had a thickness of 15 μm.
Arrange a protective polypropylene film, temperature 100 ℃,
It was continuously laminated with a roll having a linear pressure of 5 kgf / cm 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 4.0 μm) are added to a triple roll Well dispersed evenly to obtain Varnish J.
This varnish J was continuously impregnated into a glass woven cloth having a thickness of 40 μm while rubbing one side with a squeeze roll, and dried, and the resin thickness from the glass woven cloth on one side was 9 μm, and the resin thickness from the other glass woven cloth was 16 μm, total thickness (glass woven cloth + resin layer) 65 μm, gelling time 85 seconds prepreg K was made, and when it came out, 25 μm thick release PET film was placed on both sides, temperature 100 ° C, wire It was continuously laminated with a roll having a pressure of 5 kgf / cm and wound up.

While peeling off the protective polypropylene film of the above B-stage resin composition sheet I with release film, and further peeling off the polypropylene film on one side of the resin layer thickness 9 μm side of the above prepreg K, the resin surfaces were joined together, A B-stage resin composition sheet L with a release film containing a substrate was laminated by continuously laminating with a heating roll having a temperature of 100 ° C. and a linear pressure of 5 kgf / cm, and this was wound.

On the other hand, a 0.2 mm thick, 12 μm double-sided copper foil epoxy resin copper clad laminate (trade name: CCL-EL170, Mitsubishi Gas Chemical
Co., Ltd.), a conductor circuit was formed thereon, and after black copper oxide treatment was applied thereto, the release film on one side of the B-stage resin composition sheet L with the release film was peeled off and placed on both sides of the conductor circuit. Then, gradually raise the temperature from room temperature to 170 ° C in 25 minutes, set the pressure from the beginning to 15 kgf / cm2, and set the vacuum degree.
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 4-layer multilayer board M. After removing the release film on this surface, a blind via hole having a hole diameter of 100 μm was formed by irradiating one shot with a carbon dioxide gas laser output of 12 mJ.

Roughening treatment was carried out with a chromic acid solution to make irregularities from the surface layer to be 5.4 to 10.9 μm (average roughness Rz: 8.2 μm). At this time, the tip of the concave portion did not reach the glass woven fabric fibers 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 0.7μm, electrolytic copper plating 25μm on this roughened surface
After adhering, put in a heating furnace and gradually raise the temperature from 100 ° C to 150 ° C in 30 minutes, and then gradually raise the temperature to 170 ° C.
It was cured by heating at 60 ° 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 evaluation results are shown in Table 1.

Comparative Examples 1 and 2 In Examples 1 and 2, a B-stage resin composition sheet with a metal foil and a release film was prepared by adhering a B-stage resin layer having a thickness of 65 μm to the copper foil and the release film. In the same manner as in Examples 1 and 2, the prepreg was not used, and only the B-stage resin composition sheet with the release film and the metal foil was used to carry out the lamination curing treatment and the roughening treatment in the same manner. As in Examples 1 and 2, the total unevenness from the surface layer
The thickness was 5 to 11 μm (average roughness Rz: 8 to 9 μm), and a multilayer printed wiring board of 6 layers was similarly prepared. 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 obtain a thickness of 65 μm and a gelling time (170 ° C.).
A 55 second prepreg N was prepared. 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 this surface copper foil by etching, blind via holes are formed, and roughening treatment is performed in the same manner to make the total unevenness from the surface layer 5 to 11 μm, the same circuit formation after electroless copper plating, conductor black oxidation Copper treatment, prepreg N placement, 18μ
A copper foil of 6 m was laminated, similarly laminated, and then the copper foil on the surface layer was removed, blind via holes were formed, desmear treatment, copper plating and circuit formation were performed to produce a 6-layer multilayer printed wiring board. 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 multi-layered organic powder, finely pulverized silica, and acrylonitrile-butadiene rubber were not used. A B-stage resin composition sheet O with a release film on which a resin layer having a gelling time (170 ° C.) of 80 seconds was formed was coated and dried so as to have a thickness of 65 μm. One B-stage resin composition sheet O with this release film is placed on each side of the inner layer board, and similarly laminated and cured to form a four-layer multi-layer board. After removing the release film on the surface layer, Similarly, a blind via hole is formed with a CO2 laser, a roughening treatment is performed under the same conditions as in Example 2, a conductor circuit is formed after copper plating, a conductor black copper oxide treatment, and a B-stage resin composition sheet O arrangement with a release film. Then, lamination molding was 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 1.38 1.23 1.38 1.16 0.46 Solder heat resistance No abnormality No abnormality No abnormality Partial swelling Partial swelling Glass Transition temperature DMA (° C) 198 153 198 153 198 168 168 Modulus of elasticity 25 ° C (kgf / mm2) 1910 1750 1002 962 2001 860 Warp / twist (mm) 1.7 2.0 4.9 5.7 1.5 5.4 Thickness variation (μm) 10.7 11.2 19.3 20.4 10.4 22.7 Blind via hole / heat cycle test, resistance change rate (%) 1.5 2.0 2.0 3.0 1.8> 10 Crack generation 200 cycles 0/1000 0/1000 0/1000 0/1000 0/1000 210/1000 400 cycles 0/1000 45 / 1000 0/1000 75/1000 65/1000 970/1000 migration resistance (Omega) normal ^{5x10 13 4x10 13 5x10 13 5x10 13} 4x10 13 5x10 13 200hrs. 6x10 11 5x10 9 3x10 10 4x10 8 2x10 9 1x10 9 500hrs. 8x10 ¹⁰ <10 ⁸ 7x10 ¹⁰ <10 ⁸ <10 ⁸ <10 ⁸

<Measurement method> 1) Copper adhesive 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, 5hrs.), 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 a laminated prepreg with 13 sheets and has a thickness of 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 laminated layers on one side of the 6x250x250 mm printed wiring board of 5) was measured with a thickness meter and expressed as (maximum thickness variation per layer). 7) Blind via hole ・ Change in resistance value by heat cycle test and crack: Blind via hole (hole diameter 100 μm, land 180 μm) formed on the second to third layers of each 6-layer printed wiring board. Alternately, connect 1000 holes, and in the gas phase, -65 ℃ / 30 minutes ← → ＋ 150 ℃ / 30 minutes as one cycle 200
The cycle was repeated and the maximum change in resistance was measured.
Further, the cross section of the hole at 200 and 400 cycles was observed, and the occurrence of resin cracks was observed. 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.

[0051]

EFFECTS OF THE INVENTION In a production method of adhering a B-stage resin composition layer for additive to at least one surface of a base material reinforced B-stage resin composition sheet (prepreg), preferably on the B-stage resin composition layer for additive. By using a B-stage resin composition sheet containing a base material for an additive to which a metal foil or a release film is attached and adhering under heat and pressure, the multilayer printed wiring board obtained has a high elastic modulus (rigidity). It was possible to manufacture products with excellent warp, twist, and thickness accuracy. Further, at least the resin composition for additives of the B-stage resin composition containing the base material is (a) a polyfunctional cyanate ester monomer and 100 parts by weight of the cyanate ester prepolymer as a resin component which becomes hardly soluble after curing treatment. On the other hand, (b) 15 to 500 parts by weight of a liquid epoxy resin at room temperature is mixed, and (c) a thermosetting catalyst is added (a +
b) A multilayer printed wiring board having excellent reliability such as heat resistance and migration resistance 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. I was able to get Then, by making two or more components out of the three components of butadiene-containing resin, organic powder, and inorganic powder as essential components soluble in the roughening solution even after the curing treatment, the anchoring effect due to the roughening is increased, A product having a large adhesion of plating was obtained.

[Brief description of drawings]

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

[Explanation of symbols]

a base material reinforced B stage resin composition sheet (prepreg) b additive B stage resin composition layer c copper foil d release film e glass woven fabric f heating roll

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F100 AB01C AB17C AB33C AG00                       AK01B AK53 AK53B AL05B                       AT00D BA02 BA03 BA04                       BA07 BA10A BA10C DG12                       DH01A EH012 EJ19 EJ42                       EJ82 GB43 JB11B JJ03                       JK06 JK07 JL11 JL14D                       YY00B                 4J002 CD02X CD05X CD06X CD08X                       CM02W FD140 GQ00                 5E343 AA02 AA13 AA17 AA36 AA38                       BB15 BB24 BB71 CC03 DD32                       DD75 EE53 ER31 GG04                 5E346 AA06 AA12 BB01 CC02 CC09                       CC32 DD02 DD33 EE31 FF03                       FF04 GG02 GG17 GG22 GG27                       GG28 HH11 HH18

Claims (6)

[Claims] 1. A B-stage resin composition containing a base material for additive, which is produced by producing a base material-reinforced B-stage resin composition sheet (prepreg) and then adhering a resin composition layer for additive to one surface of the sheet. Sheet manufacturing method. 2. A sheet in which a resin composition layer for additive is formed on one surface of a metal foil having surface unevenness on one surface of the substrate-reinforced B-stage resin composition sheet,
2. The B-stage resin composition sheet with a metal foil containing a base material for additive according to claim 1, wherein the resin surface is arranged so that the base material reinforced B-stage resin composition sheet side and laminated and bonded. Manufacturing method. 3. A base material reinforced B-stage resin composition sheet having a release film on which a resin composition layer for additive is formed on one side of the base material reinforced B stage resin composition sheet, the resin surface being the base material reinforced B stage resin composition sheet side. The method for producing a B-stage resin composition sheet with a release film containing a base material for an additive according to claim 1, wherein the sheet is arranged so as to face and adhere. 4. A base-layer-reinforced B-stage resin composition is formed by thinly forming a resin layer on one side, and the B-stage resin composition sheet for additive is formed on the thin resin layer side for production. A method for producing a B-stage resin composition sheet containing an additive substrate according to claim 1, 2 or 3. 5. A resin component which is hardly soluble in a roughening solution when roughened with a roughening solution after curing treatment, at least the additive resin composition and the base material-reinforced B-stage resin composition. And a soluble component are mixed, and as the resin component which becomes insoluble, (a) a polyfunctional cyanate ester monomer, 100 parts by weight of the cyanate ester prepolymer, (b) a liquid at room temperature 15-500 parts by weight of the epoxy resin of (c) thermosetting catalyst, (a + b) 100
The method for producing a B-stage resin composition sheet containing a base material for additive according to claim 1, 2, 3 or 4, wherein a resin composition blended in an amount of 0.005 to 10 parts by weight with respect to parts by weight is an essential component. 6. A solubilizing component in the roughening solution after the curing treatment, wherein two or more components out of three components of butadiene-containing resin, organic powder and inorganic powder are used as essential components. A method for producing a B-stage resin composition sheet containing an additive substrate according to 3, 4, or 5.