JP2005041148A - Stage b resin composition sheet having film substrate in it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an adhesive sheet for producing a high density printed circuit board in which the thickness of a molded insulating layer is 30 μm or below and warpage/torsion are suppressed and which is excellent in thickness precision, heat resistance after moisture absorption, modulus of elasticity, and reliability. <P>SOLUTION: A stage B resin composition sheet having a heat resistant film substrate in it is used, which is obtained by making a thermosetting resin composition at least 180°C in glass transition temperature after curing adhere to the heat resistant film substrate subjected to surface treatment by plasma treatment. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a B-stage resin composition sheet containing a heat-resistant film substrate for a multilayer printed wiring board, and by using this sheet, a high-density multilayer printed wiring excellent in copper adhesive strength, heat resistance, reliability, and the like. A board can be produced, and the obtained multilayer printed wiring board is used mainly as a high-density small printed wiring board on which a semiconductor chip is mounted and used for a new small and light semiconductor plastic package. Moreover, this invention is not limited to a rigid wiring board, It is used also for a flexible wiring board, a rigid-flexible wiring board, etc.

In recent years, high-density multilayer printed wiring boards have been used in electronic devices that are becoming smaller, thinner, and lighter. The B-stage resin composition sheet used for this multilayer printed wiring board is a release film such as a polyester film or a metal foil for laminating or adding a large amount of rubber in an epoxy resin (semi) additive B-stage resin composition Adhesive sheets and the like to which a physical layer is attached are known (for example, refer to Patent Documents 1 and 2). However, when the insulating layer is thin, these are inferior in reliability such as migration resistance in the Z direction, and moreover electric Inferior in mechanical properties and heat resistance, there was a limit to use as a high-density printed wiring board. Also, when the inner layer board is thin, if a (semi) additive adhesive sheet with no base material reinforcement is used on both sides, the printed wiring board that has been built up and made into multilayers has mechanical strength such as bending strength and tensile strength, elasticity The rate (rigidity) is inferior and warpage is likely to occur, causing defects in assembly and other processes (see, for example, Patent Document 3). Further, the B-stage resin composition sheet in which the resin layer was adhered to the untreated surface of the heat-resistant film base material was swollen when subjected to heat treatment after absorbing moisture even when it was a multilayer board.
JP-A-8-231940 JP 2000-17148 A JP-A-5-267840

  The present invention solves the above problems, has high mechanical strength such as elastic modulus of multilayer printed wiring board, excellent thickness accuracy after lamination molding, heat resistance after moisture absorption, migration resistance in the Z direction, etc. The present invention provides a B-stage resin composition sheet containing a heat-resistant film substrate for producing a high-density multilayer printed wiring board having excellent insulation reliability.

  In the present invention, a conductor circuit and an interlayer resin insulating layer are sequentially laminated on a substrate, and are arranged between an adhesive sheet for manufacturing a multilayer printed wiring board by a subtractive method or a (semi) additive method, or between inner layers and on a surface layer. It is to be used as an adhesive sheet for producing a multilayer board using the same as a general glass cloth base prepreg that is integrally laminated, and first the surface of the heat-resistant film is subjected to plasma treatment, Thereafter, a B-stage resin composition sheet containing a heat-resistant film substrate obtained by forming a B-stage resin composition layer on at least one surface of the substrate is used as an adhesive sheet for multilayer printed wiring boards.

  As the plasma treatment for treating the surface of the heat-resistant film, a normal plasma treatment method can be applied and the productivity is high. Further, the surface treatment with plasma provides finer irregularities than the chemical solution treatment, and has a strong adhesive force with the resin composition.

  A sheet having a metal foil attached to one side of the B-stage resin composition sheet containing the heat-resistant film substrate can be used, and this can be suitably used as an adhesive sheet for build-up and the like. Although the resin composition adhering to both surfaces of a heat-resistant film does not have limitation in particular, it selects and uses suitably according to the objective. Moreover, when making a resin composition adhere on both surfaces, the upper and lower resin composition may use a different thing. For example, a (semi) additive insulating layer on one side and a generally known resin composition layer for lamination on the opposite side may be used.

  Since this B-stage resin composition sheet with a heat-resistant film substrate contains a heat-resistant film substrate, the printed wiring board obtained by building up using a particularly thin inner layer board contains the substrate. Compared to a conventional printed wiring board using a B-stage resin composition sheet, it has a high mechanical strength, a small warp and twist, and an excellent molding thickness at the time of lamination. ) Additive method Suitable for high-density printed wiring boards. Moreover, since the Z direction is blocked by the heat resistant film, a printed wiring board having high insulation reliability in the Z direction and extremely excellent migration resistance was obtained.

  Usually, a sheet having a B-stage resin composition layer attached to a heat-resistant film often contains a lot of soft components such as rubber components in the B-stage resin in order to impart flexibility. Those with low heat resistance are common. In addition, there are sheets using resins with excellent heat resistance such as polyimide for the adhesive layer, but these generally have a high temperature when molding, and it is not possible to use materials with low heat resistance such as general FR-4 There is. Therefore, as a result of earnestly researching the B-stage resin composition layer to be attached to the heat-resistant film, as a result of attaching a thermosetting resin composition having a glass transition temperature of 180 ° C. or higher after curing, the temperature during molding It was found that the heat-resistant film and the resin are more firmly bonded even at high temperatures and the moisture absorption heat resistance is greatly improved under the same conditions as for ordinary laminates.

  A B-stage resin containing a heat-resistant film substrate obtained by adhering a thermosetting resin composition having a glass transition temperature of 180 ° C. or higher after curing to at least one surface of a heat-resistant film substrate surface-treated by plasma treatment The composition sheet can reduce the thickness after molding between insulating layers to 30 μm or less, further reduce the thickness variation after molding, and is excellent in heat resistance especially after moisture absorption, and further has electrical insulation in the Z direction, etc. A high-density printed wiring board having excellent reliability and good elastic modulus could be obtained.

The heat-resistant film substrate of the present invention is subjected to plasma treatment before the resin composition is attached. This heat-resistant film substrate is not particularly limited in type and thickness, and known ones can be used. Specifically, a polyimide film, a polyparabanic acid film, a liquid crystal polyester film, a wholly aromatic polyamide film or the like is used, and a wholly aromatic polyamide film having a small coefficient of thermal expansion is preferably used. The thickness is appropriately selected according to the purpose. In order to reduce the thickness between insulating layers after laminate molding to about 15 to 30 μm, a heat resistant film having a thickness of 4 to 20 μm is preferably used. Before the adhesive resin layer is formed on the surface of the heat-resistant film, the surface of the heat-resistant film is subjected to plasma treatment, and the surface is treated, and at the same time, fine irregularities are formed and the surface is activated. The gases used for plasma treatment are helium, argon, krypton, xenon, neon, radon, nitrogen, oxygen, air, carbon monoxide, carbon dioxide, carbon tetrachloride, chloroform, hydrogen, ammonia, carbon tetrafluoride, trichlorofluoro. Known materials such as ethane and trifluoromethane can be used, and these gases may be used alone or may be mixed appropriately. The processing power density is not particularly limited, but preferably 0.1 W · sec / cm ² or more, more preferably a 10～80W · sec / cm ^2. The pressure for the plasma treatment may be normal pressure or reduced pressure, but is preferably 0.01 to 100 Torr, more preferably 0.05 to 10 Torr. In the present invention, the processing power density is determined by the power source (W), the processing area (cm ² ), and the processing time (seconds). For example, the processing power density of 10 W · sec / cm ² corresponds to the processing amount processed for 1 ^second at 10 W per processing area of 1 cm ² . The same processing can be performed by processing for 10 seconds with a power of 1 W per 1 cm ² of processing area.

  In the present invention, known resin compositions can be used for the plasma-treated heat-resistant film substrate surface, and preferably a thermosetting resin composition having a glass transition temperature after curing of 180 ° C. or higher. Is used. If the glass transition temperature is low, various problems occur, such as the resin softening due to heat applied when the semiconductor chip is mounted and the like, causing a defect. This resin composition has a (semi) additive resin composition on one side of a heat-resistant film substrate, a laminate resin composition on the opposite side, and a (semi) additive resin composition on both sides. Or a laminate having a resin composition for lamination attached to both sides. The thickness of the resin layer is not particularly limited and is appropriately selected according to use. When the thickness of the insulating layer after lamination molding is 30 μm or less, for example, when the thickness of the heat-resistant film is 5 μm, the thickness of the resin layer on the front side is 5 μm, and the thickness of the resin layer on the lamination side is about 25 μm. Depending on the copper foil thickness of the inner layer plate and the copper foil remaining rate, the insulating interlayer thickness is set to 30 μm or less after lamination.

  As a resin composition in which a circuit can be formed by the (semi) additive method in the resin composition layer of the B-stage resin composition sheet containing the heat-resistant film substrate of the present invention, a thermosetting type, a photocuring and thermosetting combined type, etc. A well-known thing is mentioned. The resin composition layer of the B-stage resin composition sheet containing the heat-resistant film substrate is not particularly limited, and generally known ones are used. This resin layer contains a component that is soluble in the roughening solution when cured and a resin component that is hardly soluble in the roughening solution, and the soluble component is uniformly dispersed in the resin component that is hardly soluble. Is. Here, the meanings of “soluble” and “slightly soluble” used in the present invention are “soluble” and “slow” when the dissolution rate is relatively high when immersed in the same roughening solution for the same time after the curing treatment. The thing is expressed as “slightly soluble”.

  The soluble resin of the present invention includes generally known resins. This resin is soluble in a solvent or liquid, and is blended in a hardly soluble resin. These are not particularly limited. Specifically, polybutadiene rubber, acrylonitrile-butadiene rubber, epoxidized products, maleated products, imidized products, carboxyl group-containing products, (meth) acrylated products, styrene-butadiene rubbers, and the like are known. Things. In particular, those containing a butadiene skeleton in the molecule are preferably used from the viewpoints of solubility in the roughening solution, electrical characteristics, and the like. Further, those containing a functional group rather than a non-functional one are preferable because they react with a functional group of other unreacted resin in the post-curing treatment to crosslink and improve characteristics.

  Examples of the soluble organic powder of the present invention include known ones. Specific examples include epoxy resins, polyimide resins, polyphenylene ether resins, polyolefin resins, silicone resins, phenol resins, acrylic rubber, polystyrene, MBS rubber, Examples thereof include powders such as ABS, and multiple structure (core-shell) rubber powders thereof. One or more of these are appropriately selected and blended.

  The soluble inorganic powder of the present invention is not particularly limited. For example, aluminum compounds such as alumina and aluminum hydroxide; calcium compounds such as calcium carbonate; magnesium compounds such as magnesia; silica compounds such as silica and zeolite 1 type or 2 types or more are used in combination.

  As the hardly soluble resin of the present invention, known ones such as thermosetting resins and photosensitive resins are used alone or in combination of two or more, and there is no particular limitation. Specifically, epoxy resins, polyimide resins, Examples of the polyfunctional cyanate resin, maleimide resin, double bond addition polyphenylene ether resin, polyphenylene ether resin, polyolefin resin, epoxy acrylate, unsaturated group-containing polycarboxylic acid resin, and polyfunctional (meth) acrylate. Further, these known bromides and phosphorus-containing compounds are also used. Among these, a polyfunctional cyanate ester resin is preferable from the viewpoints of migration resistance, heat resistance, etc. and heat resistance after moisture absorption.

  The polyfunctional cyanate ester compound preferably used in the present invention is a compound having two or more cyanato groups in the 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-cyanato Phenyl) 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 the reaction of novolac and cyanogen halide.

  Besides these, multifunctional cyanic acid described in JP-B-41-1928, JP-A-43-18468, JP-A-44-4791, JP-A-45-11712, JP-A-46-41112, JP-A-51-63149, etc. Ester compounds can also be used. Further, a prepolymer having a molecular weight of 400 to 6,000 having a triazine ring formed by trimerization of cyanate groups of these polyfunctional cyanate ester compounds is used. This prepolymer polymerizes the above-mentioned polyfunctional cyanate ester monomers using, for example, acids such as mineral acids and Lewis acids; bases such as sodium alcoholates and tertiary amines; salts such as sodium carbonate and the like as catalysts. Can be obtained. This prepolymer also includes a partially unreacted monomer, which is in the form of a mixture of the monomer and the prepolymer, and such a raw material is suitably used for the application of the present invention. Generally, it is used after being dissolved in a soluble organic solvent. These bromine addition compounds and liquid resins can also be used.

  Epoxy resins can be liquid or solid at room temperature, but generally known epoxy resins can be used as liquid epoxy resins at room temperature. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, diglycidylated product of polyether polyol, epoxidized product of acid anhydride, etc. alone or in combination of two or more Used. The amount used is 20 to 10,000 parts by weight, preferably 30 to 5,000 parts by weight per 100 parts by weight of the polyfunctional cyanate ester compound and the cyanate ester prepolymer. “Liquid at room temperature” means fluidity at room temperature (25 ° C.).

  In addition to these liquid epoxy compounds, the above-mentioned solid epoxy resins that can be crushed at room temperature, and further, cresol novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, etc., are used alone or in combination of two or more. used. Semi-solid materials can also be used.

  In the thermosetting resin composition of the present invention, various additives other than those described above can be blended as desired within a range where the original properties of the composition are not impaired. These additives include various resins, known bromine and phosphorus compounds of these resins, known inorganic and organic fillers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents. Various additives such as a photosensitizer, a flame retardant, a brightener, a polymerization inhibitor, and a thixotropic agent are used in combination as appropriate. If necessary, the compound having a reactive group is appropriately mixed with a known curing agent and catalyst.

  The thermosetting resin composition of the present invention is cured by heating, but has a slow curing speed and is inferior in workability, economical efficiency, etc., and therefore a known thermosetting catalyst is used for the thermosetting resin used. . The amount used is 0.005 to 10 parts by weight, preferably 0.01 to 5 parts by weight, with respect to 100 parts by weight of the thermosetting resin.

  The amount of the soluble resin, organic powder, and inorganic powder uniformly dispersed in the resin composition of the present invention is not particularly limited, but is preferably 3 to 50% by weight of the total, more preferably 5%. Use ~ 35% by weight. These components use two or more of the three components. In addition, by using particles having different particle sizes from the same particle size, the shape of the unevenness becomes more complicated, the anchor effect is increased, and a copper plating adhesive force is obtained.

  As a method for uniformly kneading each component of the present invention, generally known methods can be used. For example, after blending each component, kneaded with a three-roller at room temperature or under heating, or generally known ones such as a ball mill, a lye machine, a bead mill, and a homomixer are used. In addition, a solvent is added and used as a viscosity suitable for the processing method.

  The resin composition for lamination of the present invention is not particularly limited, and generally known resin compositions can be used. Specifically, the above hardly soluble resin is used. From the viewpoint of migration resistance, heat resistance, electrical characteristics, etc., a polyfunctional cyanate ester resin composition is preferably used. One or two or more hardly soluble resins are used in appropriate combination. Also, the above-mentioned soluble organic and inorganic powders can be added within a range that does not greatly affect the characteristics. Furthermore, the above various additives can also be added depending on the purpose.

  The method for attaching the B-stage resin composition layer to the heat-resistant film is not particularly limited, and a known method can be used. For example, apply directly on a heat-resistant film with a roll and dry to make a B-stage, or apply to a release film or metal foil and dry to make a B-stage, then place it on one or both sides of the heat-resistant film and heat The method of laminating and integrating under pressure can be used. In this case, a small amount of solvent may remain in the resin composition. The thickness of the resin composition is not particularly limited, but is generally 3 to 100 μm, preferably 4 to 50 μm, and more preferably 5 to 30 μm on the heat-resistant film. This thickness is appropriately selected depending on the desired thickness of the insulating layer. By using a heat resistant film, it is possible to produce a multilayer printed wiring board having excellent insulation in the Z direction and excellent reliability such as migration resistance.

  The copper foil used in the subtractive method in the present invention is not particularly limited, but an electrolytic copper foil having a thickness of 3 to 18 μm is preferably used. There are no particular limitations on the metal foil having irregularities on the surface that is used by adhering to the (semi) additive B-stage resin composition, and specific examples include aluminum foil and copper foil. The unevenness of the surface to which the resin is attached is not particularly limited, but preferably the average roughness Rz is 1 to 10 μm, more preferably 2 to 7 μm. If the irregularities are large before roughening, the roughening time is short and the moisture permeation is small, so that swelling of the plated copper layer can be reduced. The thickness of the metal foil is not particularly limited, but it is better that it is thin so as to be removed by etching or the like thereafter, and preferably 7 to 20 μm.

  In the case of multilayering according to the present invention, after using the inner layer plate in which a conductor circuit is formed using a copper-clad laminate or a heat-resistant film substrate-reinforced copper-clad sheet, a known surface treatment is applied to the conductor, or both sides The release film containing the heat-resistant film substrate or the B-stage resin composition sheet with metal foil is placed on the front and back of the circuit board for the inner layer using the roughened foil, and heated, pressurized, and preferably vacuumed by a known method. Under the layer molding or laminating, a curing treatment is performed, and the (semi) additive resin composition has a curing degree that can be roughened with a roughening solution. In the case with a metal foil, the metal foil is removed by etching or the like after lamination or lamination.

There are no particular limitations on the curing treatment lamination molding conditions for multi-layering of the present invention, but the 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 300 ° C., the pressure is ^{2 to} 50 kgf / cm ² , and the time is 0.5 to 3 hours. Moreover, it is preferable to laminate and form under vacuum. A known apparatus such as a vacuum laminator press or a general multistage vacuum press can be used.

  After removing the metal or release film on the surface of the metal foil-clad plate obtained in the present invention, the resin is roughened with an acid or an oxidizing agent by a known method. Examples of the acid used include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, and examples of the oxidizing agent include sodium permanganate, potassium permanganate, chromic acid, and chromic sulfuric acid. is not. Prior to this treatment, a known swelling solution is used if necessary, and after the treatment, the solution is neutralized with a neutralizing solution. The average roughness of the roughened surface formed by this roughening treatment is set to an average roughness Rz of 0.1 to 10 μm, preferably 0.2 to 5 μm, separately from the unevenness of the metal foil. In general, the average roughness Rz is 2 to 15 μm, preferably Rz 3 to 10 μm, for the roughness obtained by combining the unevenness of the metal foil and the unevenness due to roughening.

  Thereafter, electroless plating, thick electroless plating, vapor deposition, sputtering, or the like is performed by a known semi-additive method, full additive method, or the like, and electroplating is performed as necessary to thicken the conductor. Although it differs depending on the resin composition, in general, the degree of cure that can be roughened with a chemical solution is inferior in heat resistance, reliability, etc. if used as a printed wiring board, and cannot be used as a high-density printed wiring board. Therefore, it is generally post-cured before circuit formation. Although it depends on the resin composition, it is generally post-cured at a temperature of 100 to 250 ° C. for 30 minutes to 5 hours. Next, a circuit is formed by a known method to obtain a printed wiring board. This same process is repeated sequentially to build up multiple layers.

  This B-stage resin composition sheet containing a heat-resistant film substrate can also be used as a prepreg for general copper-clad laminates and multilayer boards, and can be laminated using copper foil to produce printed wiring boards by the subtractive method. Possible and used in a known manner.

The present invention will be specifically described below with reference to examples and comparative examples. Unless otherwise specified, “parts” represents parts by weight.
(Example 1)
2,2-bis (4-cyanatophenyl) propane monomer was melted in 400 parts at 150 ° C. and reacted for 4 hours with stirring to obtain a prepolymer having an average molecular weight of 1,900. This was dissolved in methyl ethyl ketone to obtain varnish A. As a liquid epoxy resin at room temperature, 100 parts of bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol F type epoxy resin (trade name: EXA830LVP, Dainippon Ink & Chemicals, Inc.) 50 parts <made by Co., Ltd.>, 50 parts novolak type epoxy resin (trade name: DEN438, manufactured by Dow Chemical Co., Ltd.), 400 parts bisphenol A type epoxy resin (trade name: Epicoat 1001, manufactured by Japan Epoxy Resin Co., Ltd.) And 0.3 part of zinc octylate dissolved in methyl ethyl ketone was added as a thermosetting catalyst. Liquid epoxidized polybutadiene resin (trade name: E-1000-8.0, manufactured by Nippon Petrochemical Co., Ltd.), epoxy group-modified acrylic multilayer structure powder (trade name: Staphyloid IM-203, average particle size) 0.2 μm) was added, and stirred and mixed well to obtain a uniform varnish B.

  This varnish B was continuously applied to a 18 μm thick copper foil mat surface (concave / convex 3.0 to 5.9 μm, average roughness Rz: 4.6 μm) and dried to a height of 5.5 μm from the tip of the convex portion of the copper foil. A B stage resin composition layer (gelation time at 170 ° C. of 48 seconds) is formed, and when it comes out of the drying zone, a protective polypropylene film with a thickness of 20 μm is placed on the resin side, and 100 ° C., 4 kgf / Lamination was performed at a linear pressure of cm to prepare a B-stage resin composition sheet C with copper foil. It was 185 degreeC when the glass transition temperature (Tg) after hardening of the resin composition used for this sheet C was measured by DMA.

  Also, in the above varnish B, a varnish D that does not use a liquid epoxidized polybutadiene resin or an epoxy group-modified acrylic multilayer structure powder is prepared, and this varnish D is continuously applied to one side of a release PET film having a thickness of 25 μm. After drying, a B-stage resin layer with a gelation time of 67 seconds and a thickness of 20 μm is formed, and when it comes out of the drying zone, a polypropylene protective film with a thickness of 20 μm is applied to the resin surface, 100 ° C., linear pressure 4 kgf / cm And a B-stage resin composition sheet E with a release film was produced. The Tg after curing of the resin composition used for this sheet E was 201 ° C. This is a 4.5 μm thick wholly aromatic polyamide film that has been plasma treated on both sides under the conditions shown in Table 1 and placed on one side while peeling off the protective film, and on the other side the B-stage resin with copper foil Composition sheet C was placed while peeling off the protective film, and laminated and integrated continuously at 90 ° C. with a linear pressure of 7 kgf / cm. B-stage resin composition sheet F with copper foil containing heat-resistant film substrate Produced. The insulating layer thickness was 30 μm from the tip of the copper foil convex portion.

On the other hand, a circuit is formed on a BT resin copper-clad laminate (product name: CCL-HL830, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with an insulation layer thickness of 0.2mm and 12μm double-sided copper foil as the inner layer board, and treated with black copper oxide The B-stage resin composition sheet F with the heat-resistant film base material and the copper foil is placed on both sides of the plate made of copper foil so that the release PET film is peeled off and the resin layer faces the inner plate side, After charging the press machine, the temperature was raised from room temperature to 170 ° C in 25 minutes, the pressure was 15 kgf / cm ² from the beginning, the vacuum degree was 3 mmHg or less and held at 170 ° C for 30 minutes, cooled and taken out, A four-layer multilayer board G was obtained. After removing the copper foil on the surface by etching, a blind via hole having a hole diameter of 95 μm was formed by irradiating one shot at a carbon dioxide laser output of 10 mJ. It was swollen, desmeared (dissolved), and neutralized with a potassium permanganate desmear solution (Nippon McDermid Co., Ltd.) to give a total roughness of 3.8 to 6.0 μm (average roughness Rz: 5.1 μm). At the same time, the resin layer remaining at the bottom of the blind via hole was dissolved and removed. Next, an electroless copper plating layer of 0.5 μm and electrolytic copper plating of 20 μm are attached to this roughened surface, put in a heating furnace, gradually increase the temperature from 100 ° C. to 150 ° C. in 30 minutes, and further gradually increase the temperature. It was heated and cured at 190 ° C. for 60 minutes. When the thickness between the insulating layers was measured with a cross section, it was approximately 25 μm. Using this, a copper conductor circuit was formed by a semi-additive method, and then the surface of the conductor circuit was treated with black copper oxide, and the same process was repeated to produce a six-layer multilayer printed wiring board. The results of measuring this characteristic are shown in Table 1.

(Table 1)
Example 1-1 Example 1-2 Example 1-3
Plasma processing conditions
Oxygen gas He gas Nitrogen gas
60W ・ sec / cm ² 30W ・ sec / cm ² 70W ・ sec / cm ²
0.10Torr 0.10Torr 0.10Torr
Copper adhesive strength (kgf / cm) 1.07 1.05 1.07
Solder heat resistance after moisture absorption
PCT-0hrs. No blisters No blisters No blisters
PCT-1hrs. No blisters No blisters No blisters
PCT-3hrs. No blister No blister No blister Glass transition temperature DMA (℃)
195 195 195
Elastic modulus 25 ° C (kgf / mm ² )
1577 1573 1575
Warp and twist (mm) 1.2 1.2 1.2
Thickness variation (μm) 3.0 3.1 3.0
Z-direction migration resistance (Ω)
Normal 6x10 ¹³ 6x10 ¹³ 6x10 ¹³
200hrs. 6x10 ¹¹ 6x10 ¹¹ 6x10 ¹¹
1000hrs. 3x10 ¹⁰ 3x10 ¹⁰ 3x10 ¹⁰

(Example 2)
400 parts of 2,2-bis (4-cyanatophenyl) ether monomer was melted at 150 ° C. and reacted for 4 hours with stirring to obtain a prepolymer having an average molecular weight of 1,900. This was dissolved in methyl ethyl ketone to obtain Varnish H. As a liquid epoxy resin at room temperature, 100 parts of bisphenol A type epoxy resin (product name: Epicoat 828), 150 parts of bisphenol F type epoxy resin (product name: EXA830LVP), 150 novolak type epoxy resin (product name: DEN438) 150 Part, 200 parts of cresol novolac type epoxy resin (trade name: ESCN220F, manufactured by Sumitomo Chemical Co., Ltd.), 0.3 parts of acetylacetone iron dissolved in methyl ethyl ketone as a thermosetting catalyst, and mixed well with stirring Varnish I.

  This varnish I was continuously applied to one side of a 25 μm thick smooth surface release PET film and dried to form a B stage resin layer having a gel time of 60 seconds and a thickness of 18 μm. Further, a B-stage resin layer having a gel time of 64 seconds and a thickness of 5 μm was formed to obtain a sheet K. At the time of exiting the drying zone, a protective polyethylene film having a thickness of 20 μm was adhered to the resin surface and integrated. Tg of these sheets J and K after curing was 210 ° C. A 12μm thick polyimide film was plasma treated under the conditions shown in Table 2 and the protective polyethylene films of the above-mentioned sheets J and K were peeled and placed on both sides, laminated at 100 ° C with a linear pressure of 4kgf / cm, and a total thickness of 35μm A B-stage resin composition sheet L containing a heat-resistant film substrate was prepared.

On the other hand, a circuit with 30% copper residue was formed on a BT resin copper clad laminate (trade name: CCL-HL830, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with an insulation layer thickness of 0.2 mm and double-sided copper foil as the inner layer plate. The release layer PET film on one side of the B-stage resin composition sheet L containing the heat-resistant film base material is peeled on both sides of the inner layer plate that has been subjected to black copper oxide treatment on the copper foil so that the resin layer faces the inner layer plate side. Placed on both sides and laminated and bonded to the inner layer plate at 100 ° C and a linear pressure of 5 kgf / cm, then the release PET film on the surface layer was peeled off, and a general electrolytic copper foil with a thickness of 3 μm was formed on this copper foil adhered to 35μm copper carrier sheet (trade name: Super Thin foil, Mitsui Mining and Smelting <strain> Ltd.) place, 110 ° C. · 30 min + 200 ° C. · 90 minutes, 5kgf / cm ² · 20 minutes + 20 kgf / Laminate molding was performed for 2 hours at a degree of vacuum of 30 mmHg or less until cm ² · last. The thickness between the insulating layers was approximately 23 μm. After peeling off the copper carrier sheet on this surface, a blind via hole having a hole diameter of 100 μm was made by directly irradiating one shot at a carbon dioxide laser output of 13 mJ from above. After the desmear treatment, 0.5 μm of electroless copper plating and 10 μm of electrolytic copper plating are adhered, and a circuit is formed by a conventional method. After the black copper oxide treatment, the B-stage resin composition sheet L containing the heat-resistant film substrate is similarly separated. The mold film was peeled and arranged, and processed in the same manner to produce a 6-layer printed wiring board. The evaluation results are shown in Table 2.

(Table 2)
Example 2-1 Example 2-2 Example 2-3
Plasma processing conditions
Oxygen gas Ar gas Oxygen / Ar mixed gas
20W ・ sec / cm ² 40W ・ sec / cm ² 70W ・ sec / cm ²
0.20Torr 0.10Torr 10Torr
Solder heat resistance after moisture absorption
PCT-0hrs. No blisters No blisters No blisters
PCT-1hrs. No blisters No blisters No blisters
PCT-3hrs. No blister No blister No blister Glass transition temperature DMA (℃)
216 213 215
Thickness variation (μm)
3.3 3.3 3.2
Z-direction migration resistance (Ω)
Normal 6x10 ¹³ 6x10 ¹³ 6x10 ¹³
200hrs. 5x10 ¹¹ 5x10 ¹¹ 5x10 ¹¹
1000hrs. 2x10 ¹¹ 2x10 ¹¹ 2x10 ¹¹

(Comparative Example 1)
500 parts of bisphenol A type epoxy resin (trade name: Epicote 1001), 450 parts of phenol novolac type epoxy resin (trade name: DEN438), 1 part of imidazole curing agent (trade name: 2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) Then, 30 parts of dicyandiamide was added and uniformly dispersed with three rolls to obtain Varnish M. This varnish M was continuously applied to a 25 μm thick smooth PET release film and dried to prepare a B stage resin composition layer sheet N having a resin composition thickness of 20 μm and a gel time of 68 seconds. Tg of this sheet N after curing was 160 ° C. Plasma treatment is performed on both sides of a 4.5 μm thick wholly aromatic polyamide film under the conditions shown in Table 3, sheet N is placed on both sides, and continuously laminated with a heating roll at a temperature of 100 ° C. and a linear pressure of 5 kgf / cm. A B-stage resin composition sheet O with a release film containing a heat-resistant film substrate was prepared. The insulating layer thickness was approximately 45 μm.

On the other hand, a circuit with 30% copper residue was formed on an epoxy-based copper-clad laminate (trade name: CCL-EL170, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a thickness of 0.2mm and double-sided copper foil. After the copper-treated inner layer plate P is prepared, the both sides of the B-stage resin composition sheet O with the heat-resistant film base material and the release film are placed so that the resin surface faces, and the linear pressure is 100 ° C. and 5 kgf / cm. The substrate Q was produced by laminating. In addition, the substrate R was made to adhere to one side of the inner layer plate P in the same manner. The release PET film of the substrates Q and R is peeled off, the substrate Q is arranged on the surface of the substrate R where the sheet O is not attached, and a general electrolytic copper having a thickness of 12 μm is formed on both sides of the combination of the substrates Q and R. Place the foil, and laminate it at 110 ° C for 30 minutes + 180 ° C for 90 minutes, 5 kgf / cm ^{2 for} 15 minutes + 20 kgf / cm ^{2 for the} last 2 hours at a vacuum of 30 mmHg or less to make a 6-layer board. A printed wiring board was obtained by a conventional method. The inner interlayer insulating layer thickness was about 20 μm. The evaluation results are shown in Table 3.

(Table 3)
Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3
Plasma processing conditions
Oxygen gas Ar gas Oxygen / Ar mixed gas
70W ・ sec / cm ² 50W ・ sec / cm ² 70W ・ sec / cm ²
0.10Torr 0.10Torr 0.10Torr
Solder heat resistance after moisture absorption
PCT-0hrs. No blisters No blisters No blisters
PCT-1hrs. No blisters No blisters No blisters
PCT-3hrs. Swelling Swelling Swelling Swelling Glass transition temperature DMA (℃)
165 165 165
Thickness variation (μm)
5.7 5.2 5.5
Z-direction migration resistance (Ω)
Normal 5x10 ¹³ 5x10 ¹³ 5x10 ¹³
200hrs. 5x10 ¹⁰ 5x10 ¹⁰ 5x10 ¹⁰
1000hrs. 8x10 ⁹ 8x10 ⁹ 8x10 ⁹

(Comparative Example 2)
In Example 2, 400 parts of a liquid epoxidized polybutadiene resin (trade name: E-1000-8.0, manufactured by Nippon Petrochemical Co., Ltd.) was added to Varnish I, and the mixture was well stirred uniformly to obtain Varnish S. This varnish S was applied and dried in the same manner to prepare a B stage resin composition sheet T. The Tg of this sheet T after curing was less than 170 ° C. Both surfaces of a 4.5 μm-thick wholly aromatic polyamide film were subjected to plasma treatment under the conditions shown in Table 4, and similarly, a B-stage resin composition sheet containing a heat-resistant substrate was prepared to obtain a 6-layer printed wiring board. The evaluation results are shown in Table 4.

(Table 4)
Comparative Example 2-1 Comparative Example 2-2 Comparative Example 2-3
Plasma processing conditions
Oxygen gas Ar gas Oxygen / Ar mixed gas
20W ・ sec / cm ² 40W ・ sec / cm ² 70W ・ sec / cm ²
0.20Torr 0.10Torr 10Torr
Solder heat resistance after moisture absorption
PCT-0hrs. No blisters No blisters No blisters
PCT-1hrs. Swelling Swelling Swelling Swelling
PCT-3hrs. Swelling Swelling Swelling Swelling Glass transition temperature DMA (℃)
<170 ° C <170 ° C <170 ° C

(Comparative Example 3)
The B-stage resin composition sheet U with metal foil was prepared by attaching the thickness of the B-stage resin layer attached to the concavo-convex part of the copper foil in Example 1 to 30 μm from the tip of the convex part. Using only this B-stage resin composition sheet U with metal foil, without using a base material, it was similarly laminated and cured, and the roughening treatment was performed in the same manner. The total was almost the same, and a multilayer printed wiring board with 6 layers was similarly formed. The evaluation results are shown in Table 5.

(Table 5)
Comparative Example 3
Copper adhesive strength (kgf / cm) 1.08
Solder heat resistance after moisture absorption
PCT-0hrs. No blister
PCT-1hrs. No blister
PCT-3hrs. No blistering glass transition temperature DMA (℃) 192
Elastic modulus 25 ℃ (kgf / mm ² ) 995
Warp and twist (mm) 5.3
Thickness variation (μm) 6.5
Z-direction migration resistance (Ω)
Normal 5x10 ¹³
200hrs. 6x10 ¹⁰
1000hrs. <10 ⁸

<Measurement method>
1) Solder heat resistance after moisture absorption: Six layers of printed wiring boards were subjected to moisture absorption treatment in a normal state or with a pressure cooker test machine, and immersed in 260 ° C. solder for 30 seconds.
PCT-0hrs .: No pressure cooker test. Shows normal.
PCT-1hrs .: Treated in a pressure cooker tester in an environment of 121 ° C./203 kPa for 1 hour.
PCT-3hrs .: Treated in a pressure cooker tester at 121 ° C./203 kPa for 3 hours.
2) Copper adhesion strength: Measured according to JIS C6481.
3) Glass transition temperature: A plurality of B-stage resin composition sheets containing a heat-resistant substrate were laminated and formed to a thickness of approximately 0.8 mm, and measured by the DMA method.
4) Elastic modulus: The elastic modulus at 25 ° C of the DMA chart measured in 3) is shown.
5) Warp and twist: A 6-layer printed wiring board made with 250 x 250 mm was placed on a surface plate, and the maximum values of warp and twist were measured.
6) Thickness variation: The variation in thickness per layer of the 6 layers of printed wiring board of 250x250mm in 1) was measured with a thickness meter and expressed as (maximum value-minimum value).
7) Migration resistance: 100 pieces of 10mm square copper foil were left in the same position on the second and third layers of the 6-layer board of each example and comparative example, and the insulation resistance value between the insulation layers in the Z direction was determined. Measurement was performed by applying 70 VDC at 85 ° C. and 85% RH.

Claims (4)

A B-stage resin containing a heat-resistant film substrate obtained by adhering a thermosetting resin composition having a glass transition temperature of 180 ° C. or higher after curing to at least one surface of a heat-resistant film substrate surface-treated by plasma treatment Composition sheet. The B-stage resin composition sheet with a metal foil containing a heat-resistant film substrate according to claim 1, wherein a metal foil is attached to one side of the B-stage resin composition sheet containing the heat-resistant film substrate. The B-stage resin composition sheet containing a heat-resistant film substrate according to claim 1 or 2, wherein the heat-resistant film substrate is a wholly aromatic polyamide film. 4. The B-stage resin composition sheet with a heat-resistant film substrate according to claim 1, wherein the B-stage resin composition of the B-stage resin composition sheet with a heat-resistant film substrate is a polyfunctional cyanate ester resin composition. .