JP2002356563A - B-stage resin composition sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high-density build-up print-wiring sheet excellent in an electric property, heat resistance, without cracking in a cold and hot impact test of IVH and the surface. SOLUTION: Organic spherical powder having a multi-layered structure wherein a resin layer having a elasticity exists at least and its outermost layer is covered with a rigid resin layer, is essentially blended in a thermosetting resin composition. As its result, the cracking resistance by cold and hot impact test is greatly improved. By adding an inorganic filler, a small hole for the high- density print-wiring sheet, is produced by a gas laser. Preferably, a polyfunctional cyanic acid ester compound is blended in the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a thermosetting resin composition wherein at least a resin layer having rubber elasticity is present therein.
A B-stage resin composition sheet containing, as an essential component, a multi-structure organic spherical powder in which the outermost layer is coated with a glassy resin layer, which is used as a build-up laminate material or the like, and is provided on at least one surface of the inner layer plate. In the case of a resin composition sheet in which the copper foil is not attached to one side, the copper foil is arranged on the outside and laminated and molded, or a release film is arranged on the outside of the resin composition and laminated and molded. After that, the resin surface is roughened and plated with copper. In the case of a B-stage resin composition sheet with a copper foil, the resin surface is arranged facing the inner layer plate side and build-up lamination is performed. The printed wiring board made using the multilayer board thus obtained is drilled with a carbon dioxide laser or the like, and as a high-density small printed wiring board, a semiconductor chip is mounted. Mainly used for applications. Further, it is also used for a motherboard printed wiring board for mobile phones and the like.

[0002]

2. Description of the Related Art In recent years, high-density multilayer printed wiring boards manufactured by a build-up method have been used in electronic devices that are becoming smaller, thinner, and lighter. This high-density printed wiring board generally has an inner via hole (IVH) in an inner layer plate, and a hole filling resin is used to fill this portion. In this case, a step of filling the hole and polishing the resin that has protruded from the surface layer is required. However, during the polishing, there is a problem that the inner layer board becomes thin and stretched, and it is difficult to produce a high-density thin printed wiring board. Met. Further, in this case, depending on the laminated material to be built up thereon, cracks and the like occur due to stress at the boundary of the resin portion, and there was a problem in reliability.

[0003] In the case of a B-stage resin composition sheet or a B-stage resin composition sheet with copper foil, it is arranged on the surface of the inner layer plate, and the IVH of the inner layer plate is embedded with a resin during lamination molding. Although possible, this resin had a problem of cracking in a reliability test.
On the other hand, when a non-through hole and / or a through hole is formed by high heat such as a carbon dioxide laser or the like, it is a common practice to add an inorganic filler because a processed shape is poor only with resin. However, as the inorganic filler is added, the elongation becomes smaller, and a thin printed wiring board having flexibility has a defect that a resin crack occurs in a thermal shock test or the like. In addition, when a high-density printed wiring board is used, the distance between the hole walls may be 150 μm or less, and the distance between the insulating layers may be 50 μm or less, which has a problem in reliability such as migration resistance. Met.

[0004]

SUMMARY OF THE INVENTION The present invention provides a build-up material for a high-density printed wiring board, which has the above problems, in which the occurrence of resin cracks is extremely small, and in which a small-diameter hole can be formed. Further, a printed wiring board having excellent migration resistance, heat resistance, heat resistance after moisture absorption, and the like is obtained.

[0005]

Means for Solving the Problems In the thermosetting resin composition, at least a resin layer having rubber elasticity is present,
By compounding the multi-layer organic spherical powder with the outermost layer coated with a glassy resin layer as an essential component, even if build-up lamination molding is performed on the inner layer plate, embedding in IVH in the inner layer plate is also good. In the case of a thin inner layer plate, the flexibility is also improved. Even when a semiconductor chip is mounted and a thermal shock test is performed, resin cracks in the IVH portion and resin cracks in the surface layer do not occur. In addition, when producing a high-density printed wiring board, if a through hole and / or a non-through hole of 180 μm or less is opened with a carbon dioxide gas laser or the like, the resin portion will be largely processed. By adding the agent, the piercing property was also improved, and the multilayer printed wiring board obtained by the build-up was excellent in mechanical strength such as tensile strength and bending strength. Furthermore, when a high-density printed wiring board is used, a compound having excellent migration resistance, heat resistance, heat resistance after moisture absorption, etc. is obtained by blending a polyfunctional cyanate compound as an essential component in the resin. Was done.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a resin layer having rubber elasticity is present at least in a thermosetting resin composition of a laminate material for build-up, and the outermost layer is covered with a glassy resin layer. Compound organic powder with multiple structures. As the spherical powder having the multiple structure, generally known ones can be used, but a rubber-like resin having an elastic modulus is used for the inner resin layer, and the outermost layer is coated with a glass-like resin. Those having a layer structure of two or more layers are used. Alternatively, a multi-layered structure in which the central portion is a glassy spherical resin, the outer layer is a rubbery resin, and the outer layer is a glassy resin may be used.

[0007] The rubber-like resin is not particularly limited, but acrylic rubber, a copolymer thereof, polybutadiene crosslinked rubber and the like are preferably used. Also, the outermost layer glassy resin is not particularly limited, acrylonitrile-styrene resin, methyl methacrylate resin, styrene resin, styrene-methyl methacrylate resin, epoxy group-containing resin, carboxyl group-containing resin, hydroxyl group-containing resin, etc. Powder is used. When a polyfunctional cyanate compound is blended, a compound coated with an epoxy group-containing resin is preferably used. A part of the functional group remains and reacts with the thermosetting resin composition to be integrated, thereby improving properties such as elongation. In addition, since the glassy resin layer is excellent in chemical resistance, the resin dissolves and swells during compounding so that blocking does not easily occur, the dispersion is good, a homogeneous material is obtained, and there is no variation in characteristics. Is obtained. The particle size is not particularly limited, but is generally 0.05 to 50 μm, preferably 0.1 to 20 μm.
m is used.

[0008] The spherical resin in the middle layer is obtained by a generally known polymerization method. For example, a spherical resin having a predetermined size is produced by emulsion polymerization, solution polymerization, suspension polymerization, or the like. Outside this,
The desired glassy resin is coated. It is preferable to leave a part of the functional groups, and to use the one that reacts with the compounded resin to be integrated to maintain elongation and strength. The amount of addition is not particularly limited, but is preferably an amount that does not significantly impair the properties of the original resin composition, and is preferably 1
~ 30% by weight.

[0009] The thermosetting resin is not particularly limited.
For example, a generally known thermosetting resin such as a polyfunctional cyanate resin, a polyfunctional maleimide resin, a polyimide resin, an epoxy resin, and a double-bonded polyphenylene oxide resin is used. These are used alone or in combination of two or more. Among them, a polyfunctional cyanate ester resin is preferably used in terms of migration resistance, heat resistance, heat resistance after moisture absorption, and the like. The amount used is preferably (a) a polyfunctional cyanate compound, 100 parts by weight of the cyanate ester prepolymer, and (b) 50 to 10,000 parts by weight of a liquid epoxy resin at room temperature, With respect to 100 parts by weight of the (a + b) component, the heat curing catalyst was added in an amount of 0.
A thermosetting resin composition containing, as an essential component, a resin composition mixed with 005 to 10 parts by weight is used. Also, epoxy resin etc.
A polymer film is also preferably used.

The polyfunctional cyanate compound used in the present invention is a compound having two or more cyanato groups in a molecule. Specific examples include 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 (4-cyanatophenyl) phosphate, and cyanates obtained by reacting novolak with cyanogen halide. Those in which a bromine atom is bonded in the molecule can also be used.

In addition to these, Japanese Patent Publication Nos. 41-1928 and 43-1846
8, polyfunctional cyanate compounds described in JP-A-44-4791, JP-A-45-11712, JP-A-46-41112, JP-A-47-26853 and JP-A-51-63149 can also be used. Further, a prepolymer having a molecular weight of 400 to 6,000 and having a triazine ring formed by trimerization of a cyanato group of these polyfunctional cyanate compounds is used. This prepolymer is obtained by polymerizing the above-mentioned polyfunctional cyanate ester monomer with a catalyst such as an acid such as a mineral acid or a Lewis acid; a base such as a tertiary amine such as sodium alcoholate; or a salt such as sodium carbonate. It can be obtained by: The prepolymer also contains some unreacted monomers, and such a raw material is suitably used for the purpose of the present invention. Generally, it is used after being dissolved in a soluble organic solvent.

An epoxy resin is preferably used in combination with the polyfunctional cyanate component. Either a solid or a liquid at room temperature can be used, but a component that is liquid at room temperature is partially suitably blended. As the epoxy resin which is liquid at room temperature, generally known ones having bromine attached in the molecule and those having no bromine attached can be used. Specifically, bisphenol A type epoxy resin, bisphenol F
Epoxy resins, phenol novolak type epoxy resins, diglycidylated polyether polyols, epoxidized acid anhydrides, alicyclic epoxy resins and the like are used alone or in combination of two or more. The amount used is 50 to 10,000 parts by weight, preferably 100 to 5,000 parts by weight, based on 100 parts by weight of the polyfunctional cyanate ester compound and the cyanate ester prepolymer. Further, a known high molecular weight epoxy resin or the like which forms a film is also preferably used.

Various additives can be added to the thermosetting resin composition of the present invention, if desired, as long as the inherent properties of the composition are not impaired. These additives include polymerizable double bond-containing monomers such as unsaturated polyesters and prepolymers thereof; polybutadiene, epoxidized butadiene, maleated butadiene, butadiene-
Low molecular weight liquid to high molecular weight elastic rubbers such as acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, fluororubber, and natural rubber; polyethylene, polypropylene, polybutene, poly-4-methyl Penten, polystyrene, AS
Resin, ABS resin, MBS resin, styrene-isoprene rubber,
Polyethylene-propylene copolymer, 4-fluoroethylene-
6-fluorinated ethylene copolymers; high molecular weight prepolymers or oligomers such as polycarbonate, polyphenylene ether, polysulfone, polyester, and polyphenylene sulfide; and polyurethane are exemplified, and are appropriately used. In addition, other known inorganic and organic fillers,
Various additives such as dyes, pigments, thickeners, lubricants, defoamers, dispersants, leveling agents, photosensitizers, flame retardants, brighteners, polymerization inhibitors, and thixotropic agents may be used as desired. They are used in an appropriate combination. If necessary, the compound having a reactive group is appropriately blended with a curing agent and a catalyst.

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

An inorganic filler is added to the resin component of the present invention for the purpose of reducing the coefficient of thermal expansion, improving the laser workability, and the like. Specifically, generally known materials such as wollastonite, barium titanate-based ceramic, various glass components, synthetic mica, synthetic silica, talc, calcined talc, aluminum hydroxide, kaolin and the like are used. In addition, these needle-like needle-like inorganic fillers can be used or used in combination. Of course, generally known needle (fiber) -shaped organic fibers can also be used together. The shape of the acicular inorganic filler generally has a cross section of 1 to 15 μm, and any of a circular shape, an irregular shape, and a flat shape can be used. The length is not particularly limited, but is longer than the cross-sectional length, and a length of 5 to 50 μm is preferably used. The amount used is not particularly limited, but is generally blended to be 3 to 75% by weight, preferably 5 to 70% by weight.

The method for uniformly kneading the components of the present invention is as follows:
Generally known methods can be used. For example, after the respective components are blended, they are kneaded with a three-roll mill at room temperature or under heating, or generally known materials such as a ball mill and a raikai machine are used. It is also possible to add a solvent and stir with a homomixer or the like so as to have a viscosity suitable for the processing method.

The B-stage resin composition sheet of the present invention and the B-stage resin composition sheet with copper foil can be used alone by heating and curing as they are.
This B-stage resin composition sheet is disposed on at least one side of an inner layer plate whose surface is chemically treated with a copper foil, and a copper foil is placed on the outside of the B-stage resin composition sheet, a release film is disposed, or
The stage resin composition sheet is placed and laminated under heat and pressure, preferably under vacuum to form a copper-clad multilayer board. If necessary, hole formation, desmear treatment, copper plating, circuit formation, copper foil surface chemical treatment, laminate molding After repeating build-up lamination, a printed wiring board is obtained. The copper foil is not particularly limited, but an electrolytic copper foil having a thickness of 3 to 12 μm is preferably used. Of course, rolled copper foil can also be used.

The lamination molding conditions of the copper clad board used in the present invention are generally a temperature of 150 to 250 ° C., a pressure of 5 to 50 kgf / cm ² , and a time of 1 to 5 hours. Further, it is preferable to perform lamination molding under a vacuum having a degree of reduced pressure of 30 mmHg or less.

The multilayer copper-clad board obtained by using the sheet with the B-stage resin composition and the sheet with the B-stage resin composition with copper foil can be drilled with a mechanical drill. Drilling with a laser is preferred. In order to form a hole having a hole diameter of 80 to 180 μm, a carbon dioxide laser is preferable from the viewpoint of processing speed and the like. The drilling method is not particularly limited, but the drilling auxiliary layer is placed on the multilayer copper-clad laminate and directly irradiated with a high-energy carbon dioxide laser, or the copper foil surface is exposed to the energy absorption rate of the carbon dioxide laser. Using a large cobalt metal, nickel metal treatment or a treatment of these alloys, a chemical solution treatment, or a known surface treatment such as black copper oxide, and directly irradiating a carbon dioxide gas laser from above, the through holes and / or
Alternatively, it is possible to easily form a non-through hole (blind via hole). When drilling through holes and / or blind via holes,
If the thickness of the copper foil is large, copper foil burrs remain around the hole. This can be removed by polishing or the like, but it is highly possible that burrs remain. Preferably, a copper foil burr generated in a part of the copper foil surface layer in the thickness direction of the copper foil and around the hole is removed by a chemical solution. At 1
After etching and removing to a thickness of about 7 μm, preferably 2 to 5 μm, and performing copper plating, a circuit is formed on the front and back surfaces to obtain a printed wiring board.

Of course, when a general copper foil is used, a part of the surface copper foil is removed by etching in advance to reduce the thickness to 1 to 5 μm.
It is also possible to form a blind via hole by irradiating a carbon dioxide laser from above. For drilling, generally known drilling methods such as an excimer laser, a YAG laser, a carbon dioxide laser, and a mechanical drill can be used, but from the viewpoint of workability, drilling speed, etc.
It is preferable to use a carbon dioxide gas laser for the through-holes and / or blind via holes of about 180 μm. Of course, it is also possible to use a combination of the drilling methods.

The through hole and / or the blind via hole having a hole diameter of 20 μm or more and 180 μm or less are generally formed by laser. Pore diameter 20μm or more, less than 80μm pores, excimer laser, YAG laser is preferred, those with a pore diameter of 80μm or more and 180μm or less, metal oxide treatment or chemical treatment on the copper foil surface, or melting point 900 ℃ or more And a coating material containing 3 to 97% by volume of one or more of metal compound powder, carbon powder, or metal powder having a binding energy of 300 kJ / mol or more,
Alternatively, a sheet-like material, preferably, having a total thickness
It is arranged on a copper foil surface with a thickness of 30 to 200 μm, and the output of a carbon dioxide laser is preferably formed by directly irradiating a carbon dioxide laser having an energy selected from 20 to 60 mJ to form through holes and / or blind via holes. .

In drilling, a copper foil is used as a drilling auxiliary layer by subjecting the shiny surface of the copper foil to a nickel metal treatment, a cobalt metal treatment, or an alloy thereof, and the like. Can directly form a through hole and / or a blind via hole by directly irradiating a carbon dioxide gas laser of 5 to 60 mJ. Further, a chemical solution treatment (for example, CZ treatment, MEC Co., Ltd.) can be applied to the surface of the copper foil to form holes similarly. After processing, the surface of the copper foil can be deburred by mechanical polishing, but to completely remove the burr,
Preferably, both surfaces of the copper foil are etched two-dimensionally in the thickness direction, and a part of the original metal foil is etched away, and at the same time, copper burrs protruding in the holes are also etched away. Because the copper foil is thinner, high-density printing is possible without the occurrence of defects such as short-circuits and pattern breaks in the circuit formation of fine wires of the front and back copper foils obtained by plating up by subsequent metal plating. Wiring boards can be created.

When thinning the front and back copper foils by etching, the resin layer adhering to the surface of the inner copper foil exposed inside the holes is preferably removed by etching after at least a gas phase treatment. The inside of the hole can be filled with 50% by volume or more by copper plating. Further, in the case of a through-hole after being formed into a multilayer board, a hole having extremely excellent connection can be obtained by processing and plating the surface copper foil and the inner layer copper foil inside the hole. In addition, the processing speed was remarkably faster as compared with the case of drilling, and the productivity was good and the economical efficiency was excellent. When a hole having a hole diameter of more than 180 μm is formed, a mechanical drill is preferably used.

The auxiliary material used in the present invention has a melting point of 90.
As the metal compound having a binding energy of 300 kJ / mol or more at 0 ° C. or more, generally known metal compounds can be used. Specifically, as the oxide, titania such as titanium oxide, magnesia such as magnesium oxide, iron oxide such as iron oxide, nickel oxide such as nickel oxide, manganese dioxide, zinc oxide such as zinc oxide , Silicon oxide, aluminum oxide, rare earth oxides, cobalt oxides such as cobalt oxide, tin oxides such as tin oxide, and tungsten oxides such as tungsten oxide. Examples of the non-oxide include generally known materials such as silicon carbide, tungsten carbide, boron nitride, silicon nitride, titanium nitride, aluminum nitride, barium sulfate, and rare earth oxysulfide. In addition, carbon can also be used. Further, various glasses which are a mixture of the metal oxide powders may be mentioned. In addition, carbon powders may be mentioned, and further, simple substances such as silver, aluminum, bismuth, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, antimony, silicon, tin, titanium, vanadium, tungsten, zinc and the like. An alloy metal powder is used. These may be used alone or in combination of two or more. The average particle size is
Although not particularly limited, 1 μm or less is preferable.

Since the molecules are dissociated or melted and scattered by the irradiation of the carbon dioxide laser, the metal adheres to the hole walls and the like, and does not adversely affect the semiconductor chip and the hole wall adhesion. preferable. Since Na, K, Cl ions and the like particularly adversely affect the reliability of the semiconductor, those containing these components are not suitable. The compounding amount is 3 to 97% by volume, preferably 5 to 95% by volume, and is preferably mixed with the water-soluble resin and uniformly dispersed.

The water-soluble resin as an auxiliary material is not particularly limited, but when kneaded, applied to the copper foil surface and dried,
Alternatively, in the case of a sheet shape, a material that does not lose peeling is selected. For example, generally known materials such as polyvinyl alcohol, polyester, polyether polyol and starch are used.

The method of preparing the metal compound powder, carbon powder, or the composition comprising the metal powder and the resin is not particularly limited, but is kneaded at a high temperature without a solvent using a kneader or the like, and extruded into a sheet on a thermoplastic film. A method of dissolving a water-soluble resin in water, adding the powder to the mixture, stirring and mixing the mixture uniformly, and applying the mixture to a thermoplastic film as a paint, followed by drying to form a film. And other generally known methods. The thickness is not particularly limited, but is generally used in a total thickness of 30 to 200 μm.

Alternatively, it is also possible to perform a chemical solution treatment on the surface of the copper foil and then drill holes in the same manner. Although this processing is not particularly limited, for example, CZ processing (MEC Corporation) or the like can be preferably used. Alternatively, after the copper foil is etched with a chemical solution to a thickness of 5 μm or less, the hole can be processed by directly irradiating a carbon dioxide gas laser.

On the back side, when a through hole is formed, a back-up sheet in which a water-soluble resin or the like is adhered to a metal plate is laminated and adhered on the back side to avoid damage to the table of the carbon dioxide laser. Is preferred.

The auxiliary material is applied as a coating film on the surface of the copper foil, or is applied on a thermoplastic film to form a sheet. When heating the sheet to the copper foil surface, laminating under pressure, the auxiliary material, the backup sheet together with the applied resin layer toward the copper foil surface, with a roll, the temperature is generally 40 ~ 150 ℃, preferably 60 ~ 120 ℃ , The linear pressure is generally 1-20 kgf / cm, preferably
Lamination is performed under a pressure of 2 to 10 kgf / cm, and the resin layer is melted and brought into close contact with the copper foil surface. The selection of the temperature depends on the melting point of the water-soluble resin used, and also depends on the linear pressure and the laminating speed.
Laminate at high temperature.

A carbon dioxide laser, preferably having an output of 5 to 60 m
When a hole is formed by irradiating a J pulse with oscillation, burrs occur around the hole. This is not a particular problem in a double-sided copper-clad laminate with a thin copper foil, and the resin remaining on the copper foil surface is removed by gas phase or liquid phase treatment, and copper plating inside the hole is performed as it is. , Preferably copper plating more than 50% by volume of the inside of the hole, the surface layer is also plated at the same time, the copper foil thickness is 18μm
It is possible to: However, preferably, a copper foil having a thickness of 9 to 12 μm is used, and after piercing by directly irradiating a carbon dioxide gas laser, an etching solution is sprayed or sucked through the hole to pass through, and the overhanging copper foil burr is removed. At the same time as dissolving and removing, the thickness of the surface copper foil is 1 to 7 μm, preferably 2 to 5
Etch to a thickness of μm and perform copper plating. In this case, etching with a chemical solution is more preferable than mechanical polishing in terms of removing burrs from holes, dimensional change due to polishing, and the like.

Also, a method of forming a hole by directly irradiating a carbon dioxide gas laser after etching to a thickness of preferably 1 to 5 μm with a chemical solution, or laminating a copper foil of 3 to 5 μm in advance and directly forming a carbon dioxide Method of drilling by irradiating gas laser, 12
Etching several μm on a μm copper foil to make it uneven, and irradiating it directly with a carbon dioxide gas laser to drill holes. Blind via (non-penetrating) holes can be made by irradiating a carbon dioxide laser.

The method of etching and removing copper burrs generated in the holes according to the present invention is not particularly limited. For example, JP-A Nos. 02-22887, 02-22896, 02-25089, and 02-2
5090, 02-59337, 02-60189, 02-166789, 03-25
995, 03-60183, 03-94491, 04-199592, 04-263
Method for dissolving and removing metal surfaces with chemicals disclosed in 488
(SUEP: referred to as S urface U niform E tching P rocess method) can be used. The etching rate is generally 0.02
Perform at ~ 1.0 µm / sec.

The carbon dioxide laser is in the infrared wavelength range.
Wavelengths of 9.3 to 10.6 μm are commonly used. The output is preferably processed at 5 to 60 mJ to form a hole in the copper foil. Excimer laser has a wavelength of 248 to 308 nm, YAG laser has a wavelength of 351
355355 nm is commonly used, but is not limited. The processing speed of the carbon dioxide laser is remarkably fast and economical.

When drilling through holes and / or blind via holes, a method of irradiating an energy selected from 5 to 60 mJ from the beginning to the end, a method of changing the energy in the middle, and the like can be used. When removing the surface copper foil,
By selecting a higher energy, the number of irradiation shots is small and the efficiency is good. When processing an intermediate resin layer,
High output is not necessarily required, and can be appropriately selected depending on the base material and the resin. For example, the output can be selected from 5 to 35 mJ. Of course, high-power processing can be performed until the end. The processing conditions can be changed with or without the inner layer copper foil inside the hole.

In most cases, a resin layer of about 1 μm remains in the inner layer copper foil inside the hole processed by the carbon dioxide laser. Further, when a hole is drilled with a mechanical drill, smear may remain. By removing this resin layer, the connection reliability between the further copper plating and the copper in the inner and outer layers is improved. In order to remove the resin layer, generally known treatments such as desmear treatment can be performed.However, when the liquid does not reach the inside of the small-diameter hole, the removal residue of the resin layer remaining on the copper foil surface of the inner layer occurs. Connection failure with copper plating may occur. Therefore, more preferably, the inside of the hole is first treated in the gas phase to completely remove the residual layer of the resin, and then the inside of the hole is wet-treated, preferably by using ultrasonic waves.

As the gas phase treatment, generally known treatments can be used, and examples thereof include a plasma treatment and a low ultraviolet treatment. As the plasma, low-temperature plasma in which molecules are partially excited by a high-frequency power source and ionized is used. For this, high-speed processing using ion bombardment and gentle processing using radical species are generally used, and reactive gases and inert gases are used as processing gases. As the reactive gas, oxygen is mainly used, and the surface is chemically treated. As the inert gas, an argon gas is mainly used. Using this argon gas or the like, physical surface treatment is performed. Physical treatment uses ion bombardment to clean the surface. The low ultraviolet ray is an ultraviolet ray having a short wavelength region, and irradiates a short wavelength region having a peak at 184.9 nm and 253.7 nm, and decomposes and removes the resin layer. Then, since the resin surface is often hydrophobized, especially in the case of a small-diameter hole, it is preferable to perform a wet treatment using ultrasonic waves and then perform a copper plating. The wetting treatment is not particularly limited, but includes, for example, an aqueous solution of potassium permanganate, an aqueous solution for soft etching, and the like.

Although the inside of the hole can be electrically connected without filling with 50% by volume or more by copper plating, it is preferably filled with 50% by volume or more, more preferably 90% by volume or more. However, if the inside of the hole is filled with a longer plating time, the workability is poor, and a method using a pulse plating additive (manufactured by Nippon Rironal Co., Ltd.) suitable for filling the hole is preferably used.

[0039]

The present invention will be specifically described below with reference to examples and comparative examples. Unless otherwise specified, “parts” indicates parts by weight. Example 2 2,2-bis (4-cyanatophenyl) propane monomer (component
1,000 parts of A-1) were melted at 150 ° C., and reacted with stirring for 4 hours to obtain a prepolymer having an average molecular weight of 1,900 (component A-2). As a liquid epoxy resin at room temperature, bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd., component B-1), bisphenol F type epoxy resin (trade name: EXA830LVP, Dainippon Ink & Chemicals, Inc.) Industrial B. component B-2), novolak type epoxy resin (trade name: DEN431, manufactured by Dow Chemical Co., Ltd., component B-)
3), Br-modified bisphenol A type epoxy resin (trade name: DER5
15. Compounded by Dow Chemical Co., Ltd., component B-4), and iron acetylacetone (component C-1), 2-ethyl-
4-methylimidazole (component C-2), and as an additive, an epoxysilane coupling agent (trade name: A-187, manufactured by Nippon Yunika Co., Ltd., component D-1), dicyandiamide (component E-
1) was blended to form a varnish. Organic spherical powder having a double structure (trade name: staphyloid, spherical resin in which is acrylic rubber, particle diameter 2 μm, powder whose surface layer is coated with epoxy acrylate, epoxy group-containing, average particle diameter 2.2
μm, component F-1. And Staphyrod AC-3355, having no functional group, an average particle diameter of 0.6 μm, and a component F-2. Ganz Kasei Co., Ltd.), talc (component G-1) as an insulating inorganic filler
E) glass fiber (circular cross-sectional shape, cross-sectional diameter 7 μm, length 20 μm, component G-2) as needle-like inorganic filler,
Wollastonite (Circular cross section, cross section diameter 12μm, length 30
μm, component G-3) as shown in Table 1 and uniformly kneaded with a homomixer for 10 minutes. If the viscosity is high, add a small amount of methyl ethyl ketone and apply an appropriate viscous viscosity. And a varnish in which sedimentation of the inorganic filler was extremely slow. This varnish is 80μm thick continuously on one side of a matte surface of 12μm thick electrolytic copper foil (trade name: JTC-LP, manufactured by Japan Energy Co., Ltd.) and one side of a 50μm thick polyethylene terephthalate (PET) film. Apply and dry so that the resin flow at 170 ° C., 20 kgf / cm ² and 5 minutes is 10-20
A resin composition sheet X with a copper foil and a B-stage resin composition sheet Y which were B-staged so as to have a thickness of mm were produced. These sheets X and Y were cut into 530 x 530 mm.

Examples 1 and 2 Double-sided copper-clad laminates (trade name: CCL-HL83) were used as inner-layer copper-clad boards.
0 0.2mm 12μm copper foil, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
After a through hole having a hole diameter of 250 μm was drilled with a mechanical drill and copper plating was performed at 15 μm, circuits were formed on both surfaces thereof, and a black copper oxide treatment was performed thereon, thereby producing an inner layer plate P. The B-stage resin composition sheet Y cut to 530 x 530 mm is placed on both sides of the sheet, laminated with a hot roll of 90 ° C at a linear pressure of 5 kgf / cm and attached to an inner layer plate, and then the PET film is peeled off. On the outside, a copper foil (product name: 3FB-WS foil, a 12μm thick electrolytic copper foil with a shiny surface treated with a cobalt alloy)
Furukawa Circuit Foil Co., Ltd.), 200 ° C, 20k
The laminate was molded under a vacuum of gf / cm ² and 30 mmHg for 2 hours to obtain a four-layer plate. From this copper foil surface, carbon dioxide laser energy 10
By irradiating two shots at mJ, blind via holes having a hole diameter of 100 μm were formed on both surfaces. SUEP dissolves the thickness of the surface copper foil to 4 μm, dissolves and removes the copper foil burr generated around the hole, and performs desmear treatment.
A circuit is formed on the copper foil on this surface, black copper oxide treatment is applied, the B-stage resin sheet Y is placed on both sides again, and the above-mentioned cobalt alloy-treated copper foil is placed outside the same, and the laminate is formed in the same manner. Thus, a six-layer plate was obtained. From this copper foil, 10mJ
Irradiates 2 shots of CO2 laser with a hole diameter of 100μm
A blind via hole is formed, and the thickness of the copper foil is dissolved and removed in the same manner with SUEP to 4 μm, and the copper foil burr generated around the hole is dissolved and removed, and a desmear treatment is performed.
15 μm was applied, and then a pattern was formed on the surface layer to produce a six-layer build-up printed wiring board. Table 2 shows the evaluation results of the printed wiring board.

Examples 3 and 4 B-stage resin composition sheet with copper foil on both sides of inner layer plate P
X was arranged, and Example 3 was laminated and molded in the same manner as Example 1 to produce a four-layer plate. In Example 4, 190 ° C., 20 kgf / cm ² , 3
Laminate molding was performed for 2 hours under a vacuum of 0 mmHg or less to obtain a four-layer plate.
On the other hand, black copper oxide powder (average particle size: 0.
8 μm) of 800 parts was added to a varnish prepared by dissolving polyvinyl alcohol powder in water, and uniformly stirred and mixed. This is thickness 50
μm on one side of a PET film to a thickness of 30 μm, dried at 110 ℃ 30 minutes, the metal compound powder content 45
A volume% of auxiliary material T was made. A varnish obtained by dissolving polyvinyl alcohol in water was applied to one surface of an aluminum foil having a thickness of 50 μm to a thickness of 20 μm, and dried to prepare a backup sheet Q. The auxiliary material T is placed on the upper side of the four-layer plate, and the backup sheet Q is placed on the lower side so that the resin surface faces the copper foil side, and laminated at 100 ° C. and 5 kgf / cm. With a carbon dioxide laser,
Directly irradiate 7 shots at 25 mJ output, drill through holes, peel off auxiliary material and backup sheet, perform SUEP treatment, etch the surface copper foil to 4 μm, and dissolve and remove burrs around the holes did. After desmearing,
Copper plating is deposited by 15 μm, patterns and solder ball lands are formed on the front and back by the existing method, and at least the semiconductor chip mounting portion, the bonding pad portion, and the solder ball land portion are covered with a plating resist, and nickel, Gold plating was performed to produce a printed wiring board. Table 2 shows the evaluation results.

Comparative Examples 1 and 2, 2,000 parts of epoxy resin (trade name: Epicoat 5045, manufactured by Japan Epoxy Resins Co., Ltd.), 70 parts of dicyandiamide, 2
-Ethyl imidazole (2 parts) was dissolved in a mixed solvent of methyl ethyl ketone and dimethylformamide, mixed with stirring and uniformly dispersed to obtain a varnish G (this solid is referred to as “Component B-5”). Add 700 parts of talc to the mixture, stir and mix well with a stirrer, and then continuously apply and dry this on a 12 μm-thick electrolytic copper foil. It was created. This is the inner layer plate P of the embodiment.
Were laminated and molded at 180 ° C., 25 kgf / cm ² , and a vacuum of 30 mmHg or less for 2 hours to produce a four-layer plate. Drill a through hole in this 4-layer plate with a mechanical drill, perform desmear processing without performing SUEP processing, attach copper plating to 15 μm,
It was a printed wiring board. Table 2 shows the evaluation results.

Comparative Example 3 A multi-layer, four-layer printed wiring board was prepared in the same manner as in Example 2 except that no organic powder having a multiple structure was used.
Table 2 shows the evaluation results. Comparative Example 4 In Example 1, the inner layer plate was previously filled with a hole-filling resin (trade name: BT-S730B, manufactured by Mitsubishi Gas Chemical Co., Ltd.) without using an organic powder having a multi-layer structure, and 110 ° C.・ 2 hours + 160 ℃ ・ 2
After curing for a time, the resin protruding from the surface is removed by polishing to make it smooth, and then a B-stage resin composition sheet is placed thereon.
Y is placed, the copper foil of Example 1 is placed, and similarly laminated and molded,
It was a printed wiring board. Table 2 shows the evaluation results.

[0044]

[Table 1]

[0045]

[Table 2]

<Measurement Method> 1) Copper foil adhesive strength Measured according to JIS C6481. 2) Printed wiring boards of 4 layers and 6 layers of Examples and Comparative Examples were 50x5
Cut to 0mm and cut it into PCT (pressure cooker; 121 ° C)
・ 203kPa, 2hrs.) After treatment, 30 seconds in solder at 260 ° C.
After immersion, abnormalities were observed. 3) Circuit pattern cut and short, 200 patterns of line / space = 50 / 50μm pattern of printed wiring board prepared in Examples and Comparative Examples were observed with a magnifying glass, and the total of pattern cut and short was observed. Is shown in the molecule. The denominator is the number of patterns observed. 4) Glass transition temperature
It was measured according to 6481. 5) Thermal shock test Copper-clad laminate (CCL-HL830 0.8mm 12μm double-sided copper foil, manufactured by Mitsubishi Gas Chemical Co., Ltd.), hole diameter of 300 mm at 1mm intervals with mechanical drill
900 μm IVHs were opened, and three blocks were prepared. After applying 15μm of copper plating, circuits are formed on the front and back,
After forming a land of 00 μm and performing black copper oxide treatment,
Each B-stage resin composition sheet was placed on the front and back, and a copper foil was placed as needed, and laminated and formed under the lamination conditions of Examples and Comparative Examples, respectively. From above, use a carbon dioxide laser
A 100 μm BVH hole was drilled, and after desmearing, copper plating was applied to 15 μm. Lands and patterns are formed on this and UV
A resist was applied to both sides to a thickness of 40 μm, UV-irradiated, thermally cured, and plated with nickel and gold to obtain a printed wiring board. The thickness of the surface semiconductor chip mounting part is 40
Die attach a 0μm semiconductor chip (product name: BT-S657
D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) at 110 ° C for 2 hours + 160 ° C for 2 hours
Time cured and bonded. Seal with potting resin (trade name: BT-S657, manufactured by Mitsubishi Gas Chemical Co., Ltd.) at 110 ° C
・ Curing for 2 hours at + 160 ° C for 3 hours. This is -65 ℃ ・ 30
Min. → room temperature 5 minutes → + 150 ℃ ・ 30 minutes per cycle 300,500,700
After the cycle test was carried out, the occurrence of cracks was observed and the number of cracks was shown as a numerator in Table 2 out of 2,700 tests in which the cross section was cut and observed. 6) Insulation resistance value after pressure cooker process A comb pattern between terminals (line / space = 50/50 μm) was created, and the B-stage resin sheet used in each of the examples and comparative examples was placed thereon. It was placed and similarly laminated and molded, and the copper foil on the surface layer was removed by etching.
After treatment at 03 kPa for a predetermined time, post-treatment was performed at 25 ° C. and 60% RH for 2 hours, and 500 VDC was applied to measure the insulation resistance between terminals. 7) Migration resistance The test piece of 6) was applied at 85 ° C and 85% RH at 50 VDC to measure the insulation resistance between terminals. 8) Tensile strength The copper foil of a 0.1 mm thick copper-clad laminate (trade name: CCL-HL830, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is removed by etching, and the B-stage resin of the above Examples and Comparative Examples is etched on both sides. The composition sheets were arranged, and laminated and formed under the respective laminating conditions. The copper foil on the surface layer is removed by etching, and the tensile strength is measured using this to JIS C648.
Measured according to 1.

[0047]

According to the present invention, an organic spherical powder having a multilayer structure in which at least a resin layer having rubber elasticity is present in the thermosetting resin composition and the outermost layer is coated with a glassy resin is blended as an essential component. By the thermal shock test IV
Crack generation of resin in H and surface layer resin is extremely small,
Good reliability was obtained. Also, by using a polyfunctional cyanate compound as an essential component as a thermosetting resin composition, a build-up printed wiring board excellent in heat resistance, migration resistance, moisture absorption heat resistance, etc. could be obtained. . Further, by adding an inorganic filler thereto, a through hole and / or a blind via hole having a small diameter and a good hole shape can be formed directly by a carbon dioxide laser, which is very suitable as a high-density printed wiring board. Things were obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/46 H05K 3/46 T // C08L 101: 00 C08L 101: 00 F term (reference) 4F071 AA03 AA12 AA22 AA33 AA42 AA51 AA59 AA60 AB17 AB26 AB28 AB29 AD01 AD02 AE17 AF20 AF43 AF58 AH13 BA03 BB02 BC01 4F100 AA01A AB17B AB33B AH00A AK01A AK25A AK53 AN00A BA02 BA07 CA23A DE04A32 J13A32 CCB JA13J12 CCB FF03 FF07 GG15 GG22 HH11

Claims (6)

[Claims] 1. A thermosetting resin composition comprising, as an essential component, a multi-structure organic spherical powder in which at least a resin layer having rubber elasticity is present and an outermost layer is coated with a glassy resin layer. B-stage resin composition sheet comprising: 2. The B-stage resin according to claim 1, wherein the multi-layered spherical powder having the rubber elastic resin layer therein is a powder obtained by coating the surface of an acrylic rubber with another glassy resin. Composition sheet. 3. The B-stage resin composition sheet according to claim 1, wherein the powder has an average particle size of 0.1 to 20 μm. 4. The B-stage resin composition sheet according to claim 1, wherein the thermosetting resin contains a polyfunctional cyanate component as an essential component. 5. The B-stage resin composition sheet with copper foil according to claim 1, wherein a copper foil is adhered to one side of the B-stage resin sheet. 6. An inorganic filler is added in the resin composition in an amount of 5 to 70% by weight.
6. The B-stage resin composition sheet according to claim 1, wherein the B-stage resin composition sheet is blended by%.