JP2003246843A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a curable resin composition which excels in adhesion to plating copper, heat resistance, reliability and the like and can be used for the additive method. <P>SOLUTION: The composition comprises a component soluble and a component hardly soluble in a roughing solution after a heat curing treatment. The hardly-soluble component comprises a resin composition as the essential component which comprises 100 pts.wt. of (a) a polyfunctional cyanic acid ester monomer and a prepolymer of the cyanic acid ester, 5-400 pts.wt. of (b) an epoxy resin solid at room temperature and (c) a heat curing catalyst in an amount of 0.005-10 pts.wt. based on 100 pts.wt. of the sum (a)+(b). To this hardly soluble components, there are homogeneously dispersed and incorporated, as the soluble component, two or more components of the following three components, i.e., (d) a resin containing butadiene, (e) an organic powder soluble in the roughing solution and (f) an inorganic powder soluble in the roughing solution, so as to make 3-50 wt.% to obtain the curable resin composition. Therefore, the curable resin composition for additive use is obtained which is high in adhesion to copper, heat resistance and the like and excellent in reliability such as migration resistance, crack resistance and the like. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The curable resin composition of the present invention is used in adhesives, prepregs, castings, paints and the like. In particular, the present invention relates to a curable resin composition capable of producing a known printed wiring board by a method using an additive method, and the obtained printed wiring board has a high density and small size with excellent heat resistance, copper adhesion, reliability, etc. As a printed wiring board, a semiconductor chip is mounted, and it is mainly used for small and lightweight novel semiconductor plastic packages.

[0002]

2. Description of the Related Art In recent years, high density multilayer printed wiring boards have come to be used in electronic devices that are becoming smaller, thinner and lighter. This multi-layer printed wiring board has a fine circuit formed, and the additive method multi-layer printed wiring board that uses a conventional epoxy resin with a large amount of rubber added has reliability, electrical characteristics, and heat resistance. Etc. was inferior, and there was a limit in using it as a high-density printed wiring board.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and is intended for producing a high-density printed wiring board excellent in heat resistance, reliability, etc., particularly a multilayer printed wiring board, by the additive method. The present invention provides a suitable curable resin composition.

[0004]

According to the present invention, a curable resin composition is a mixture of a soluble component and a sparingly soluble component in a roughening solution such as an acid or an oxidizing agent after a heat curing treatment. , (A) a polyfunctional cyanate ester monomer as a poorly soluble component, and the cyanate ester prepoly
(a) multifunctional cyanate ester monomer, 100 parts by weight of the cyanate ester prepolymer, (b) blending 5 to 400 parts by weight of a solid epoxy resin at room temperature, (c) a thermosetting catalyst, a + b) 0.005 to 10 parts by weight relative to 100 parts by weight of a resin composition as an essential component, as a soluble component (d)
A curable resin composition characterized in that two or more components out of three components of a butadiene-containing resin, (e) organic powder, and (f) inorganic powder are uniformly dispersed and mixed to be 3 to 50% by weight. Use things.

When the printed wiring board is manufactured by the additive method, the obtained cured product has higher heat resistance, various reliability, adhesive strength, etc. than the additive method printed wiring board manufactured by using the conventional epoxy resin. It is excellent and can be obtained as a high-density printed wiring board.

When the curable resin composition of the present invention is used as an additive, it is necessary to dissolve a part of the resin composition in a roughening solution to form irregularities on the surface for roughening. In this case, it is essential that the resin composition is partially soluble when it is immersed in a roughening solution such as an acid or an oxidizing agent for a certain period of time, and is sparingly soluble in other portions. If the resin composed of the above-mentioned components (a) to (c) of the B stage is immersed in the roughening solution as it is without being heat-cured, it will almost dissolve or swell, so this resin component should be heated even if it is not completely cured. The resin should be crosslinked to increase the degree of curing to a certain extent, and should be cured so that it is hardly dissolved when immersed in a roughening solution for a certain period of time. On the other hand, in order to make unevenness, a component which is soluble in the roughening solution is required. As this ingredient
Using two or more components out of three components of (d) a resin or a liquid resin that dissolves in the solvent of the butadiene skeleton, (e) a roughenable organic powder, and (f) a roughenable inorganic powder. (a) ~ (c)
Is uniformly dispersed in a resin composition containing as an essential component. It is preferable that the curable resin composition uniformly dispersed is applied onto the inner layer plate and dried and cured by heating.

When flexibility is imparted to the curable resin composition, a B-stage resin composition sheet with a metal foil or a release film is placed on the inner layer plate and heated and pressed. , Preferably, the laminate is heated and cured under vacuum, and then the metal foil or the release film on this surface is removed,
The surface layer is roughened with a roughening solution, copper plating is adhered by an additive method, and then the resin composition is post-cured. Of course, it is also possible to post-cure before copper plating. It is also possible to apply electroless copper plating to a slightly thicker layer, post-cure it, remove the surface oxide film by soft etching or the like, and then perform electrolytic copper plating.

When cured, the resins (a) and (b) react and crosslink to become insoluble in the roughening solution, resulting in (d), (e) and (f).
There is a difference in solubility in the roughening solution from the soluble component consisting of, and 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, copper plating is deposited on the entire surface, followed by thermosetting to form a circuit and form a printed wiring board. By sequentially repeating this and building up to manufacture a multilayer printed wiring board,
Copper adhesive strength and elastic modulus (rigidity) are high, warpage and twisting are small, and good plate thickness accuracy can be obtained. The printed wiring board can be manufactured even by the full additive method.

When the curable resin composition of the present invention is used as an additive, the resin composition contains a component which is soluble in the roughening solution and a resin component which is hardly soluble in the roughening solution when it is cured. In this case, the soluble component is uniformly dispersed in the poorly soluble resin component. Here, the meanings of "soluble" and "poorly soluble" used in the present invention are "soluble" and "slow" for those having a relatively high dissolution rate when immersed in the same roughening solution for the same time after the curing treatment. Things are described as "poorly soluble".

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

The (e) organic substance powder which is soluble in the roughening solution after the curing treatment of the present invention is not particularly limited, but powders such as thermosetting resins and thermoplastic resins can be mentioned. When soaked, there is no particular limitation as long as the solubility is faster than that of the hardened resin which has been cured. There are spherical shapes, crushed amorphous shapes, needle shapes, and the like, which can be used in combination. Spherical, crushed one is preferably used, the particle size is not particularly limited, preferably an average particle size of 0.1 ~ 10μ
m, more preferably 0.2 to 5 μm in average particle size.

It is preferable to use a combination of large and small particles. When the B-stage sheet is used, a sheet having a maximum diameter smaller than the thickness of the resin layer applied on the metal foil or the release film 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.

Among the inorganic powders (f) of the present invention, the soluble inorganic powder used for additive is not particularly limited, but examples thereof include aluminum compounds such as alumina and aluminum hydroxide; calcium compounds such as calcium carbonate. Kind;
Magnesia and other magnesium compounds; silica, zeolite and other silica compounds, and the like may be used, and one type or two or more types may be used in combination.

In the curable resin composition of the present invention, as a resin which becomes sparingly soluble in the roughening solution after the curing treatment for additive, (a) a polyfunctional cyanate ester compound, the cyanate ester prepolymer, It contains (b) an epoxy resin that is solid at room temperature and (c) a curing catalyst as essential components, and is generally used by dissolving it in a soluble solvent. Although the amount of each component used is appropriately selected, (a) the polyfunctional cyanate ester monomer, the cyanate ester prepolymer 10
To 0 parts by weight, (b) 5 to 400 parts by weight of a solid epoxy resin at room temperature is blended, and (a + b) 100 parts by weight, (c) a thermosetting catalyst 0.005 to 10 parts by weight are essential components. The resin composition formulated as is used.

The polyfunctional cyanate ester compound (a) 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, Examples thereof include tris (4-cyanatophenyl) phosphate, and cyanates obtained by reacting novolac with cyanogen halide.

In addition to these, Japanese Examined Patent Publication Nos. 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, a known liquid at room temperature may be used.

As the epoxy resin which is the component (b) of the present invention and is solid 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, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, etc., alone or in combination. The above is used in combination. The amount used is 5 to 400 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. Solid at room temperature refers to what can be ground at room temperature. In addition to these solid epoxy compounds, known liquid epoxy resins may be used alone or in combination of two or more.

The thermosetting resin composition of the present invention, which is cured by heating itself, has a slow curing rate and is inferior in workability and economical efficiency.
A curing catalyst is used. The amount used is 0.005 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the curable resin (a + b).

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 polyimide resins, maleimide resins, double bond-added polyphenylene ether resins, polyolefin resins, epoxy acrylates, polyfunctional (meth) acrylates, and various other known bromides, phosphorus-containing compounds, and other resins. Known inorganic or organic fillers other than the above, dyes, pigments, thickeners, lubricants, defoamers, dispersants, leveling agents, photosensitizers, flame retardants, brighteners, polymerization inhibitors, thixo Various additives such as a sex imparting agent 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 amount of soluble resin, resin powder and inorganic powder uniformly dispersed in the resin composition of the present invention is 3 to 50.
% By weight, preferably 5 to 35% by weight. These components are 3 in order to properly form unevenness with high adhesive strength with a roughening solution.
Use two or more of the ingredients. 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 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.

When used as a molded product, it is preferably used without a solvent. As the paint, either solvent-free or varnish can be used. In the adhesive sheet, a flexibility-imparting agent is added to the resin composition, and the adhesive sheet is directly coated on a metal foil or a release film with a roll or the like, and dried to be B-staged.

The prepreg is produced by a known method. For example, the base material is impregnated with varnish and dried to form a B-stage, or resin layers are arranged on both surfaces of the base material and integrated by thermocompression bonding or the like to prepare a prepreg. 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. 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.

A heat-resistant film such as a polyimide film, a liquid crystal polyester film or a wholly aromatic polyamide (aramid) film can also be used as the substrate. In this case, B-stage resin layers are formed on the front and back of the heat-resistant film, and the resin composition for additive is attached as at least the resin layer on the outer layer side. The surface of the heat-resistant film is preferably subjected to a known treatment such as plasma treatment, corona treatment, or chemical treatment in order to increase the adhesive strength with the resin.

As the release film to which the B-stage resin composition is attached in the present invention, a known film is generally used. Examples thereof include polyethylene terephthalate film, poly-4-methylpentene-1 film, fluororesin film and the like. Further, a film having a release agent attached to the surface of these films, an antistatic film, a film having an average of 1 to 7 μm unevenness on the surface chemically or mechanically is preferably used. . The thickness is not particularly limited, but generally 15 to 100 μm is used.

The metal foil used in the present invention is not particularly limited, and specific examples thereof include aluminum foil, copper foil and the like having irregularities formed on the surface. 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, it is 2 to 5 μm. This is because when the resin surface is roughened by the additive method, if the unevenness is large before roughening, the roughening time is short and the penetration of water is small, so that the blistering of the plated copper layer can be reduced by heating. 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.

A B-stage resin composition sheet is obtained by coating the surface of a metal foil or a release film with a roll coater or the like and drying it, but a small amount of solvent may remain in the resin composition. It is preferable to use a protective film on the opposite resin surface from the viewpoint of preventing contamination. It is preferable that the protective film is laminated by applying a linear pressure with a heating roll or the like to be integrated.
When this is laminated or laminated on a substrate, this protective film is peeled off before use. The thickness of the resin composition is not particularly limited, but generally 3 to 100 μm, preferably 5 to 20
μm, which is appropriately selected depending on the thickness of the copper foil of the inner layer plate.

When the B-stage sheet of the present invention is used for multilayering, the conductor of the inner layer board on which the conductor circuit is formed is subjected to known surface treatment, or the inner layer circuit board using the double-sided roughened foil is used. Place the B-stage resin composition sheet with a metal foil or a release film on the front and back, and heat by a known method,
Laminated or laminated under pressure, preferably vacuum. After lamination, the metal foil is removed by etching or the like. The release film is peeled off. Of course, a prepreg is placed on the inner layer board, and the B-stage resin composition sheet is placed on the prepreg and bonded in the same manner. A known method can be used as the bonding method.

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 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 B-stage resin composition sheet with a metal foil or a release film is formed by forming a conductor circuit on a multilayer board obtained by laminating using ordinary prepreg and chemically treating the conductor. And / or it is also possible to fabricate only one surface layer such that a prepreg is arranged and laminated and molded to form a multilayer board. It is also possible to appropriately combine these laminating methods. It is also possible to use the prepreg obtained by the present invention alone. When using this prepreg for additive use, the amount of prepreg resin in which the recess does not reach the glass cloth due to roughening (to increase the resin thickness of the glass cloth surface layer to a certain extent, preferably 10 μm or more) is migration resistance. It is preferable in terms of reliability such as sex.

After removing the metal foil or the release film on the surface layer of the metal foil or the release film-clad sheet obtained by the present invention, or by roughening the resin layer coated on the inner layer plate with an acid or an oxidizing agent. The known method is used. 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.

Prior to this treatment, a known swelling solution is used if necessary, 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.
Also, when a smooth release film is used on the surface or when applied, the release film is peeled and then roughened as it is, or the surface is roughened by a known method such as buffing or sandblasting and then roughened. Treatment is preferred.

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

After that, 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. 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.

This resin composition can also be used as a general copper clad laminate or prepreg, and it is also possible to produce a printed wiring board by a subtractive method by laminating with a copper foil.

[0037]

The present invention will be specifically described below with reference to Examples and Comparative Examples. Unless otherwise specified, “part” means part by weight. Example 1 150% of 2,2-bis (4-cyanatophenyl) propane monomer
It was melted at ℃ and reacted for 4 hours with stirring to obtain a prepolymer having an average molecular weight of 2,000. This was dissolved in methyl ethyl ketone to obtain varnish A. Solid content of this varnish A 10
Solid bisphenol A epoxy resin (trade name: Epicoat 1001, Yuka Shell Epoxy Co., Ltd.) 700
Part, fail novolac type epoxy resin (trade name: ESCN
-220F, manufactured by Sumitomo Chemical Co., Ltd.) (100 parts) was mixed, and 0.5 part of iron acetylacetone as a curing 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.)
200 parts, 100 parts of epoxy group-modified acrylic multi-layered powder (trade name: Staphyloid IM-203, average particle size 0.3 μm, MAX. Particle size 0.5 μm) were added and well mixed by stirring to form a uniform varnish B. .

On the other hand, as the inner layer plate, the insulating layer thickness is 0.8 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 the above varnish B is simultaneously applied to both sides of a plate in which black copper oxide treatment is applied to a copper foil, dried and then a B stage with a thickness of 50 μm from the substrate. (170
Gelation time at 55 ° C. 55 seconds) A resin layer was formed. On top of this,
18 μm thick copper foil (matte unevenness 3.6-6.1 μm, average roughness
(Rz: 4.5 μm) was placed and charged in a press machine, then the temperature was raised from room temperature to 170 ° C in 25 minutes, and the pressure was 15 kgf / c from the beginning.
and m ^2, the vacuum degree after 30 minutes at 170 ° C. at 0.5 Torr, taken out and cooled to obtain a cured treated multilayer board of four layers. After the copper foil on this surface was removed by etching, a blind via hole having a hole diameter of 100 μm was opened by irradiating one shot with a carbon dioxide laser output of 12 mJ. Swell, desmear (dissolve) and neutralize with potassium permanganate-based desmear solution (manufactured by Japan MacDermid Co., Ltd.), and the concaves from the resin surface are 3.5 to 5.0 μm (average roughness) regardless of the copper foil irregularities. Rz: 4.2 μm), and the total unevenness from the surface layer was set to 6.6 to 10.9 μm (average roughness Rz: 8.5 μm). At the same time, the resin layer remaining at the bottom of the blind via hole was dissolved and removed. Next, electroless copper plating 0.7μ on this roughened surface
m, electrolytic copper plating 25μm attached, put in a heating furnace and 100
The temperature was gradually raised from 150 ° C to 150 ° C in 30 minutes, further gradually raised to 200 ° C, heated at 200 ° C for 60 minutes, and then cured. 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 1000 of 2,2-bis (4-cyanatophenyl) propane monomer
Part, bis (4-maleimidophenyl) methane monomer 100 parts was melted at 150 ° C., reacted for 5 hours with stirring to form a prepolymer, and then dissolved in methyl ethyl ketone and N, N-dimethylformamide to obtain varnish E. . The solid epoxy resin bisphenol A used in Example 1 was added to this.
1870 parts of epoxy resin (Epicoat 1001) and 1000 parts of cresol novolac epoxy resin (trade name: ESCN220F, manufactured by Sumitomo Chemical Co., Ltd.), a liquid epoxy resin bisphenol F epoxy resin (trade name: EXA830
LVP, manufactured by Dainippon Ink and Chemicals, Inc.) 130 parts, and 1.2 parts of zinc octylate as a curing catalyst were dissolved in methyl ethyl ketone and added. Liquid epoxidized polybutadiene resin (trade name: E-1800-6.5, manufactured by Nippon Petrochemical Co., Ltd.) 400
Part, epoxy group-modified acrylic multi-layer structure powder (trade name: Staphyloid IM-203, average particle size 0.3 μm, Max. Particle size 0.5
μm) 300 parts, finely pulverized silica (average particle size 2.4 μm, Max. particle size 5.0 μm) 200 parts, and acrylonitrile-butadiene rubber (trade name: Nipol 1031, manufactured by Nippon Zeon Co., Ltd.) 30 parts dissolved in methyl ethyl ketone The resulting solution was added, and the mixture was well kneaded and dispersed with a three-roll mill, and then methyl ethyl ketone was added to prepare a varnish F. This was attached to the matte surface of the 18 μm thick copper foil used in Example 1 so that the thickness would be 65 μm, and a B-stage resin composition sheet with copper foil (gelling time at 170 ° C. 69 seconds) G was obtained. It was made.

On the other hand, a BT resin copper-clad laminated board (trade name: CCL-HL830, Mitsubishi Gas Chemical Co., Ltd. with a thickness of 0.2 mm and double-sided 12 μm copper foil
>) After forming a circuit and treating the conductor with black copper oxide, place one sheet of each of the above-mentioned B-stage resin composition sheets with copper foil G on both sides of the conductor, charge it in a press machine, and then from room temperature to 170 ° C.
The temperature was raised in 25 minutes, the pressure was 15 kgf / cm ² from the beginning, the vacuum degree was 0.5 Torr and the temperature was maintained at 170 ° C. for 40 minutes, then cooled and taken out to obtain a 4-layer cured multilayer board. After removing the copper foil on this surface by etching, output of the carbon dioxide laser
Blind via holes with a hole diameter of 100 μm were made by irradiating one shot at 12 mJ. Swelling with potassium permanganate-based desmear solution (manufactured by Japan MacDermid Co., Ltd.), desmear (dissolution),
Neutralize to remove the concaves from the resin surface regardless of the copper foil irregularities.
The average roughness was 3.7 to 5.2 μm (average roughness Rz: 4.3 μm), and the total unevenness from the surface layer was 6.7 to 10.6 μm (average roughness Rz: 8.6 μm). At the same time, dissolve the resin layer remaining at the bottom of the blind via hole, then deposit 0.5 μm electroless copper plating and 25 μm electrolytic copper plating on this roughened surface, put it in a heating furnace and gradually increase the temperature from 100 ° C. Was raised to 150 ° C. in 30 minutes, the temperature was gradually raised to 200 ° C., and heat-cured at 200 ° C. 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.

Comparative Example 1 In Example 1, a varnish was prepared without using a resin soluble in an acid or an oxidant, an organic powder, or an inorganic powder, and then laminated in the same manner to form a four-layer board. A B-stage resin layer having a gelation time (170 ° C.) of 60 seconds was formed by coating the circuit-formed substrate on both sides so as to have a thickness of 50 μm and drying. The 18 μm-thick copper foil used in Example 1 was placed on top of this, and lamination molding, etching, and drilling were performed in the same manner, and the desmear treatment conditions were the same, copper plating and circuit formation were repeated, and 6-layer printing was performed. A wiring board was produced. The evaluation results are shown in Table 1.

Comparative 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) 50 parts, finely pulverized silica (average particle size 2.4)
μm) 40 parts and 30 parts of acrylonitrile-butadiene rubber (trade name: Nipol 1031, manufactured by Nippon Zeon Co., Ltd.) in methyl ethyl ketone were added and well dispersed with a three-roll to form a varnish H.

On the other hand, an epoxy-based copper-clad laminate of 0.8 mm thick and 12 μm double-sided copper foil (trade name: CCL-EL170, Mitsubishi Gas Chemical Co., Ltd.
>), The conductor circuit is treated with black copper oxide, and the varnish H is applied to both sides of the resin so that the resin coating thickness is 50 μm, and the gelation time (170 ° C) is 81 seconds. B
A stage resin layer was formed. On top of this, 18 μm of Example 1
After placing the copper foil and placing it in the press machine, raise the temperature to 170 ° C in 25 minutes, the pressure from the beginning to 15 kgf / cm ² , and the vacuum degree.
After keeping at a temperature of 170 ° C. for 30 minutes at 0.5 Torr, it was cooled and taken out, the copper foil on this surface was removed by etching, and 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.

Treated with an aqueous solution of chromic acid, the recesses from the resin surface were 3.8 to 4.9 μm (average roughness: 4.2
μm), 6.5 to 10.3 μm in total of irregularities from the surface layer (average roughness Rz:
8.3 μm). At the same time, the resin layer remaining on the bottom of the blind via hole was also dissolved and removed. Next, 0.7μm electroless copper plating on the roughened surface, 25μm electrolytic copper plating is attached,
In a heating furnace, the temperature was gradually raised from 100 ° C to 150 ° C in 30 minutes, further gradually raised to 170 ° C, heated at 170 ° C for 60 minutes, and then cured. 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.

Example 3 150 parts of the bisphenol A type epoxy resin (Epicoat 1001) of the solid epoxy resin used in Example 1 and 1000 parts of the solid content of the varnish E of Example 2 and cresol novolac type epoxy resin (commercial product) Name: ESCN220F, Sumitomo Chemical Co., Ltd.
>) 50 parts of zinc octylate as a curing catalyst
Parts were dissolved in methyl ethyl ketone and added. 70 parts of epoxy group-modified acrylic multi-layered powder (trade name: Staphyroid IM-203, average particle size 0.3 μm), acrylonitrile-butadiene rubber (trade name: Nipol 1031, ZEON Japan <
Co., Ltd.) solution of 20 parts dissolved in methyl ethyl ketone, 200 parts of finely pulverized silica (average particle size 2.4 μm) and 300 parts of talc (average particle size 1.8 μm) were added, and well dispersed by 3 rolls. , Varnish I. This varnish I is 100 μm thick
The prepreg J having a resin amount of 47% by weight was prepared by applying the coating to the glass woven fabric of No. 1 and drying.

On the other hand, a BT resin copper-clad laminated board (trade name: CCL-HL830, Mitsubishi Gas Chemical Co., Ltd. with a thickness of 0.2 mm and double-sided 12 μm copper foil
>) Circuit is formed, and the conductor is treated with black copper oxide, and then one prepreg J is placed on each side of the conductor.
Place a 12 μm thick electrolytic copper foil with the shiny surface treated with nickel and place it under a vacuum of 200 ° C, 20 kgf / cm ² , 10 Torr or less.
It was laminated and molded into a four-layer board K. Blind via holes having a hole diameter of 100 μm were made by directly irradiating two shots with a carbon dioxide laser output of 10 mJ on both surfaces of the four-layer plate K. A circuit is formed on the copper foil on this surface by a conventional method, and after black copper oxide treatment is applied, one piece of each of the above prepregs J is arranged on both outsides thereof, and an electrolytic copper foil having a general thickness of 12 μm is arranged on the outside thereof. It was placed and laminated in the same manner to form a 6-layer board. A hole having a hole diameter of 1.0 mm was made with a mechanical drill, and after desmearing with the potassium permanganate solution of Example 1, a printed wiring board was obtained.
The evaluation results are shown in Table 2.

Comparative Example 3 In Example 3, a resin soluble in the roughening liquid, an organic powder,
A varnish was prepared without using the inorganic powder, and a 6-layer printed wiring board was produced in the same manner. The evaluation results are shown in Table 2.

(Table 1) Item Example Comparative Example 1 2 1 2 Copper adhesion (kgf / cm) 1.20 1.24 0.41 1.35 Solder heat resistance No abnormality No abnormality Partially swollen Partially swollen Glass transition temperature DMA (° C) 204 188 214 153 Blind via hole / heat cycle test Resistance change rate (%) 1.4 1.3 1.8 2.8 Crack generation 300 cycles 0/1000 0/1000 2/1000 24/1000 500 cycles 0/1000 0/1000 11/1000 253/1000 migration resistance (Omega) normal ^{5x10 13 4x10 13 4x10 13 6x10 13} 200hrs. 5x10 11 4x10 11 7x10 11 4x10 9 600hrs. 3x10 10 1x10 10 5x10 10 <10 8

(Table 2) Item Example Comparative example 3 3 Solder heat resistance No abnormality No abnormality Glass transition temperature DMA (° C) 232 241 Blind via hole / heat cycle test Crack generation 500 cycles 0/1000 17/1000

<Measurement method> 1) Copper adhesive strength: Measured according to JIS C6481. 2) Solder heat resistance: The copper foil on the surface is removed by etching.
Cut into 50x50mm test pieces and pressure cooker test P
After processing with CT (121 ℃ / 203kPa) for 4 hours, take out and 260 ℃
After being immersed in the solder for 30 seconds, the presence or absence of abnormality was observed. 3) Glass transition temperature: each varnish is applied on a copper foil, dried and laminated to a thickness of 0.8 mm, and then a copper foil is placed on this resin composition surface and cured under each lamination condition, and then a copper layer on the surface layer is formed. The foil was etched and measured by the DMA method. Eight prepregs were piled up, laminated molding was performed in the same manner, the copper foil was removed by etching, and the same measurement was performed by the DMA method. 4) Blind via hole, resistance change and crack by heat cycle test: 2 from the surface 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 ℃ /
30 minutes ← → + 150 ° C / 30 minutes was set as one cycle, and 200 cycles were repeated to measure the maximum value of the resistance change rate. Also, 30
After repeating 0 and 500 cycles, the product was taken out and the cross section was observed to check for the presence of resin cracks. The number of cracks is shown in the molecule. The denominator is the number of tests. 5) Migration resistance: A circuit having a 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 metal foil or the release film on the surface layer was removed, and the test piece was applied at 85 ° C / 85% RH, 50VDC between the terminals. The insulation resistance value of was measured.

[0051]

EFFECT OF THE INVENTION A curable resin composition in which a soluble component and a sparingly soluble component are blended in a roughening solution after a heat curing treatment, and as the sparingly soluble component therein, (a) a polyfunctional cyanate ester is used. Monomer, the cyanate ester prepolymer 10
To 0 parts by weight, (b) 5 to 400 parts by weight of a solid epoxy resin at room temperature is blended, (c) a thermosetting catalyst, (a + b) 0.005 to 10 parts by weight per 100 parts by weight resin The composition as an essential component, as a soluble component in this (d) butadiene-containing resin,
(e) Organic powder soluble in the roughening solution, (f) Inorganic powder soluble in the roughening solution Two or more components out of the three components are uniformly dispersed and mixed in a proportion of 3 to 50% by weight, and cured. By using a conductive resin composition, it can be used for additive printed wiring boards, has excellent copper adhesion, and has higher heat resistance and reliability than additive printed wiring boards made using conventional epoxy resin. It has excellent properties and is suitable as a high-density printed wiring board.

[Brief description of drawings]

FIG. 1 is a manufacturing process of a printed wiring board of Example 1. (1) Configuration during four-layer board lamination molding (2) Roughening after copper foil on the surface layer is removed by etching after lamination (3) Roughened resin surface

2 is a manufacturing process of a printed wiring board of Comparative Example 1. FIG. (1) Configuration during four-layer board lamination molding (2) Roughening after copper foil on the surface layer is removed by etching after lamination (3) Roughened resin surface

[Explanation of symbols]

a Copper foil b Copper foil irregularities c B stage resin composition layer d Organic powder e Inner layer conductor circuit f Inner layer insulation layer Surface roughness after removing copper foil by etching h Roughened surface resin layer

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J036 AC01 AC08 AD08 DC32 DC45                       GA00 GA17 JA08 JA11                 4J043 PA02 QB64 RA47 SA13 SB01                       XB13 ZB60                 5E346 AA12 CC02 CC09 CC32 CC54                       DD02 DD03 DD25 DD33 EE33                       EE38 FF07 FF15 GG15 GG17                       GG27 HH40

Claims (2)

[Claims] 1. A mixture of a roughening solution with a soluble component and a sparingly soluble component after heat curing treatment, wherein the (a) polyfunctional cyanate ester monomer and the cyanate ester prepolymer are used as the sparingly soluble component. With respect to 100 parts by weight of the polymer, (b) 5 to 400 parts by weight of a solid epoxy resin at room temperature was blended, and (c) a thermosetting catalyst was blended with 0.005 to 10 parts by weight per 100 parts by weight of (a + b). Of the three components, the resin composition is an essential component, and the soluble component is (d) butadiene-containing resin, (e) organic powder soluble in the roughening solution, and (f) inorganic powder soluble in the roughening solution. A curable resin composition, characterized in that two or more components are uniformly dispersed and blended so as to be 3 to 50% by weight. 2. The curable resin composition according to claim 1, wherein the curable resin composition is used in an additive method printed wiring board.