WO2001059023A1

WO2001059023A1 - Adhesive film and method for manufacturing multilayer printed wiring board

Info

Publication number: WO2001059023A1
Application number: PCT/JP2000/005166
Authority: WO
Inventors: Shigeo Nakamura
Original assignee: Ajinomoto Co., Inc.
Priority date: 2000-02-08
Filing date: 2000-08-02
Publication date: 2001-08-16

Abstract

An adhesive film for inter-layer insulation having a supporting base film and, formed thereon, a thermoplastic resin composition layer which exhibits a property of the diagonally shaded area (S) in Fig. 1 with respect to the relationship of temperature vs. melt viscosity and thus is flowable when heated and solid at an ordinary temperature, characterized in that (1) the supporting base film has a metal foil having a thickness of 1 to 10 νm and a releasing carrier having a thickness of 10 to 100 νm on the other face, (2) the supporting base film has a metal foil having a thickness of 3 to 20 νm and, formed thereon, a heat-resistan t film layer having a glass transition temperature of 200 °C or higher and a thickness of 3 to 30 νm, or (3) the adhesive film has a structure wherein the thermoplastic resin composition layer is sandwiched by sheets of glass cloth or organic non-woven fabric. The adhesive film for inter-layer insulation can be used for manufacturing with ease a multilayer printed wiring board of build-up type being excellent in mechanical strength or smoothness of its surface.

Description

Adhesive film and method for manufacturing multilayer printed wiring board using the same (Technical field)

First, the present invention relates to a method for producing a build-up type multilayer printed wiring board in which a conductive circuit layer and an insulating layer are alternately stacked, a film-like adhesive with an ultrathin metal foil, and a multilayer printed wiring board using the same. It concerns the manufacturing method.

The present invention also relates to a method for manufacturing a build-up type multilayer printed wiring board in which conductive circuit layers and insulating layers are alternately stacked, the method comprising manufacturing a film adhesive with a metal foil and a multilayer printed wiring board using the same. It is about the law.

The present invention still further relates to a method for manufacturing a build-up type printed wiring board in which conductive circuit layers and insulating layers are alternately stacked, wherein a laminated board using a film adhesive and glass cloth, glass paper or organic nonwoven fabric is provided. The present invention relates to a method for manufacturing a multilayer printed wiring board.

(Background technology)

In recent years, attention has been focused on a build-up type multilayer printed wiring board manufacturing technique in which organic insulating layers are alternately stacked on conductor layers of an inner circuit board.

Tokudokidaira 8—6 4 960, an undercoat adhesive is applied, preliminarily dried, a film-like additive adhesive is applied, heated and cured, roughened with an alkaline oxidizing agent, and a conductive layer is formed by plating. A method for manufacturing a multilayer printed wiring board is known. Also, the present inventor has disclosed in Japanese Patent Application Laid-open No. Hei 11-87979 (Japanese Patent Application No. Hei 9-135 7420) simultaneous coating of the inner layer circuit pattern and resin filling in the surface via holes and / or through holes. Adhesive film for multi-layer printed wiring board, which can be collectively carried out in one step, and this

1 Discloses a method for manufacturing a multilayer printed wiring board using the same. Further, in Japanese Patent Application Laid-Open Nos. Hei 11-343710 (Japanese Patent Application No. Hei 10-342413) and Japanese Patent Application No. Hei 1-1699994, this adhesive film is vacuum-cleaned with a smooth surface. Although a method of laminating is disclosed, when a metal foil is used as a supporting base film and a conductor layer, even if the surface is smoothed by the method of the present invention, the metal foil is not more than 12 zm in production of the adhesive film. Because of the above requirements, there was a limit to fine patterning of the upper layer pattern due to the conductor thickness. Also, the method of manufacturing multilayer printed wiring boards by vacuum lamination press using copper foil with thermosetting resin has become widely used for portable electronic devices. Also, as mentioned above, the present inventor also disclosed in Japanese Patent Application Laid-Open No. 11-87927 that the coating of the inner layer circuit pattern and the filling of the resin in the surface via holes and / or through holes are simultaneously performed simultaneously. It discloses an interlayer adhesive film for a multilayer printed wiring board, and a method for manufacturing a multilayer printed wiring board using the same. In these build-up methods, since the resin containing no glass cloth or the like is used as the insulating layer, the thin multilayer wiring board, which has low rigidity and meets the demand for light weight, has a drawback of poor mechanical strength. On the other hand, although a build-up method using copper foil with a heat-resistant film using thermoplastic polyimide, etc., has been developed, its high glass transition point makes it difficult to use it on general printed circuit boards because of its high lamination temperature. It was difficult.

Furthermore, as mentioned above, the method of manufacturing multilayer printed wiring boards by vacuum lamination using copper foil with thermosetting resin has become widely used for portable electronic devices. On the other hand, the present inventor also disclosed in Japanese Patent Application Laid-Open No. 11-87927 a multi-layer printed wiring board that can simultaneously coat the inner layer circuit pattern and fill the surface via holes and / or through holes with resin at the same time. It demonstrates the method of manufacturing an interlayer adhesive film and a multilayer printed wiring board using the same. In these build-up methods, the resin that does not contain glass cloth, glass paper, etc. is used as the insulating layer.Therefore, thin wiring boards that have poor rigidity and meet the demand for light weight have poor mechanical strength. There were drawbacks.

(Indication of invention)

Under the background of the prior art described in the preceding paragraph, the present inventor has conducted intensive studies to solve the problems of the prior art, and as a result, has found a group of inventions linked to form a single general inventive concept. It was completed. Hereinafter, these will be sequentially described. First, the first invention will be described.

In view of the above problems, the present invention relates to a film-like adhesive with an ultrathin metal foil for build-up having excellent surface smoothness after lamination, and a method for producing a multilayer printed wiring board using the same.

That is, the present invention relates to a supporting base film and a surface thereof, which are laminated on the surface thereof, have the same or smaller area as the supporting base film, and have a relationship between temperature and melt viscosity in a hatched area S in FIG. 1 of the accompanying drawings. In an adhesive film comprising a thermosetting, room temperature solid thermosetting resin composition layer having physical properties, a supporting base film has a metal foil having a thickness of 1 to 1 on the surface of the resin composition and 10 on the opposite surface. An adhesive film for interlayer insulation characterized by having a structure having a peeling carrier having a thickness of 10 to 10; and (a) placing the resin composition layer on one or both sides of a patterned circuit board. At least the pattern-processed portion is directly covered with the resin composition layer, and then, these are partially temporarily bonded, and then sheet-fed, (b) temporarily bonded to one or both surfaces of the circuit board. On the adhesive film, the resin set The protective film having an area larger than the area of the material layer is sandwiched between the adhesive film and the center thereof at substantially the same position, and is heated from the protective film side under a vacuum condition of 2 mbar or less. Pressurizing and laminating; and (c) a method for producing a multilayer printed wiring board, comprising a step of thermally curing and integrating the circuit board; and (a) a supporting base film and peeling thereof. Laminated on a possible surface, having the same or smaller area as the supporting base film, and having the physical properties of the hatched area S in FIG. 1 of the accompanying drawings in relation to the temperature and the melt viscosity. After laminating the resin composition layer of the adhesive film composed of the thermosetting resin composition layer on one side or both sides of a patterned circuit board, at least the pattern processed portion is directly covered with the resin composition layer. (B) a protective film having an area larger than the area of the resin composition layer on the adhesive film temporarily bonded to one or both surfaces of the circuit board; (C) laminating by heating and pressing from the protective film side under a vacuum condition of 2 mbar or less while sandwiching the film so that the center of the film is substantially at the same position as the center of the circuit board; Support After peeling the film, a metal foil having a thickness of 10 to 100 mm, which is larger than the area of the resin composition and having a thickness of 10 to 100 mm and a release carrier of 1 to 10 zm, is placed on the resin composition. And (d) a step of thermosetting and integrating the circuit board to produce a multilayer printed wiring board. Hereinafter, the present invention will be described in detail.

The thermosetting resin composition used in the present invention, which forms a resin composition layer that is solid at room temperature and has a fluidity, is softened by heating and has the ability to form a film. There is no particular limitation as long as the characteristics required for the interlayer insulating material such as the characteristics are satisfied. The thickness of the resin composition layer is generally equal to or greater than the conductor thickness of the inner circuit board to be laminated, and is generally in the range of conductor thickness + (10 to 120) // in.

Examples of the resin composition include an epoxy resin, an acrylic resin, a polyimide resin, a polyamide resin, a polyacrylate resin, a polyester resin, and a thermosetting polyphenylene ether resin. Combination of two or more It is also possible to use an adhesive film layer having a multilayer structure. Among them, an epoxy resin composition described in JP-A-11-87927 is preferable for an epoxy resin system having excellent reliability and cost as an interlayer insulating material.

Desirable physical properties of the resin composition layer can be measured by measuring a dynamic viscoelastic modulus, and can be shown by a relationship between the temperature and the melt viscosity. A hatched area S in FIG. Is a preferable range. The dynamic viscoelasticity measurement is a curve measured using a model IUiesol-G3000 manufactured by UBM Co., Ltd. The upper limit of the dynamic viscoelasticity curve is at an average drying temperature of 100 ° C. The curve at the lower limit for 10 minutes also shows the physical properties of the resin composition layer treated at an average drying temperature of 100 ° C. for 4 minutes. The region between the curves experimentally and having a melt viscosity of 100,000 Poise or less and a temperature of 140 ° C. or less represents the physical properties of the resin composition layer preferably used in the practice of the present invention. When the melt viscosity is 100,000 Poise or more, the resin composition layer becomes hard, and when the adhesive film of the present invention is vacuum-laminated, the resin composition layer is poorly embedded in a pattern on a circuit board and has poor adhesion. Inferior. Manufacturing at a temperature exceeding 140 ° C. is not preferable because wrinkles are likely to occur after vacuum lamination due to a difference in thermal expansion coefficient between the support base film and the resin composition.

The dynamic viscoelasticity measurement shown in FIG. 1 of the accompanying drawings of this specification was measured at a heating rate of 5 ° C./min. However, when the heating rate is different, the shape of the curve is different. FIG. 2 shows dynamic viscoelasticity measurement curves measured at different heating rates for the resin composition layer obtained in Production Example 1 of the adhesive film described below. Therefore, the preferable range of the physical properties of the resin composition layer is that the dynamic viscoelasticity measurement curve must be measured by adjusting the measurement conditions to chitin. The support base film used in claims 1 to 3 of the present application has a metal foil of 1 to 10 zm thick on the surface of the resin composition, and has a metal foil of 10 to 100 zm on the opposite surface for protecting the metal foil. This is a structure provided with a thick release carrier. Use copper foil and aluminum foil as metal foil, and use polyester such as polyethylene terephthalate, polycarbonate, release paper, and metal foil such as copper foil and aluminum box as carrier for peeling. Can be used. The carrier for peeling may be of a type that peels off from a metal box by chemical etching, or may be of a type that peels off mechanically via a release layer. According to the present invention, the use of an ultra-thin metal foil of 1 or less facilitates the subsequent formation of a fine pattern, and the surface smoothness after vacuum lamination is improved due to the thickness and stiffness of the peeling carrier.

Examples of the peelable support base film used in claim 4 of the present invention include polyethylene, polyolefins such as polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonate, and metal foils such as release paper and aluminum foil. No. The thickness of the supporting base film is generally 10 to 150 m. The support film may be subjected to a mold treatment, a corona treatment, or a release treatment.

The adhesive film used in the present invention comprising the resin composition and the support base film is obtained by applying the resin composition varnish dissolved in a predetermined organic solvent on a support base film, and then drying the solvent by heating and / or hot air blowing. Then, it can be produced by a known and commonly used method. Thereafter, a release film is further laminated as it is or on the surface of the resin composition layer, and stored in a roll shape. At this time, the area of the resin composition layer can be the same as the support base film or a small area having a resin uncoated portion on the support base film.

Next, a method of vacuum laminating the adhesive film on a pattern-processed circuit board can be easily performed using a commercially available roll-type continuous vacuum laminator. However, with current vending machines, the degree of vacuum is only about 40 mbar and does not decrease, so it is difficult to carry out continuous continuous lamination without involving voids. Although it seems that this is possible by improving the degree of vacuum, the methods described in claims 3 and 4 of the present application described below are preferred at present.

Apply the resin composition layer surface of the adhesive film, which has almost the same area as the circuit board, to one side of the circuit board. Alternatively, a commercially available auto-cut lamina for dry film can be used as a method of partially sheeting each piece in a temporary adhesive state so as not to cause displacement on both sides. The roll-shaped adhesive film having a width of about the width of the substrate is heated and pressurized only in the temporarily attached portion by means of an auto-cut laminator, and the laminate roll is pressed to a desired size without being subjected to temperature and pressure. To use.

Next, a protective film larger than the resin composition layer area is sandwiched on the adhesive film temporarily bonded to the circuit board so that the center of the protective film is substantially at the same position as that of the adhesive film. Heating and pressurization from the press plate side under vacuum conditions and laminating are performed using, for example, a vacuum applicator manufactured by Nichigo-I-Morton Co., Ltd. and a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd. A laminating machine can be used. By laminating under the condition that the resin flow during lamination is not less than the conductor thickness of the inner layer circuit, the inner layer circuit pattern can be covered well. By heating and pressing under vacuum conditions of 2 mbar or less, vacuum lamination can be performed without voids.

Examples of the protective film include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, and release paper and metal foil such as aluminum foil. The protective film is used for the purpose of preventing the press surface from being scratched by foreign matters and preventing stains due to adhesive stains, and the thickness is preferably in the range of 5 to 100 μm. In addition, if the protective film has been subjected to a matting process and / or an embossing process, air escape in a vacuum state is good, and if the release film has been subjected to a mold releasing process, the press plate and the slip are good, so that the productivity of the laminating process is improved. .

After vacuum lamination, the supporting base film has a structure in which a metal foil of 1 to 10 // m thickness is provided on the surface of the resin composition, and a release carrier of 10 to 10 thickness is provided on the opposite surface. In some cases, it is possible to manufacture a multilayer printed wiring board by heat curing and integrating. Can be. When the supporting base film is releasable from the other resin composition, after the vacuum lamination, the supporting base film is peeled off, and the area is larger than the area of the resin composition. The metal foil surface of a metal foil having a peeling carrier having a thickness of 10 to 100 / m on a metal foil having a thickness of 10 to 100 / m is arranged on the resin composition by heating and pressure lamination. Thus, a circuit board having the same configuration as that of the present invention can be manufactured. In the present lamination, since the metal foil is laminated on a substantially smooth resin surface, it can be a continuous laminating roll system under normal or reduced pressure, or a vacuum lamination similar to the process of the present invention. good. Thereafter, the circuit board is similarly thermally cured and integrated to produce a multilayer printed wiring board. The conditions of thermosetting differ depending on the resin, but are selected within a range of 100 to 200 minutes at 100 to 200 ° C.

After obtaining the laminated circuit board according to the method of the present invention, the carrier for peeling is peeled off according to the required process step, and a hole is drilled with a laser and / or drill at a predetermined through hole and / or via hole. After the inside of the hole is cleaned by a dry and / or wet method as necessary, a conductor layer is formed by dry plating such as vapor deposition, sputtering and ion plating and / or wet plating such as electroless plating and electrolytic plating. At this time, a plating resist that is reverse to the conductive layer may be formed, and the conductive layer may be formed by a semi-additive method. In any case, the use of ultra-thin copper foil makes it easy to form a fine pattern. Next, the second invention will be described.

In view of the above problems, the present invention relates to a film-form adhesive with a metal foil for build-up having excellent mechanical strength and a method for producing a multilayer printed wiring board using the same. That is, the present invention relates to a support base film and a layer laminated on a surface thereof, which has the same or smaller area as the support base film, and has a relationship between a temperature and a melt viscosity. Thermo-fluidity, room temperature solid thermosetting resin composition with physical properties Heat-resistant film with a metal foil having a support base film of 3 to 2 thick and a heat-resistant film layer of 3 to 30 / m thick with a glass transition point of 200 ° C or more and a temperature of 200 ° C or more An adhesive film for eyebrow insulation characterized by having a structure in which the resin composition layer is formed on a heat-resistant film surface; and heating the film on one or both surfaces of a patterned circuit board by heating, A method for producing a multilayer printed wiring board, comprising: laminating under vacuum under pressure, heat-curing and integrating; and (a) laminating on a supporting base film and a peelable surface thereof; It consists of a thermo-fluid, room-temperature solid thermosetting resin composition layer having the same or smaller area as that of the lum and the physical properties of the shaded area S in Fig. 1 of the attached drawing in relation to temperature and melt viscosity. The adhesive film (B) a step of directly laminating a resin composition layer on at least one side or both sides of the pattern-processed circuit board by directly covering at least the pattern-processed portion with the resin composition layer, and then applying heat, pressure, and vacuum lamination; After peeling off the supporting base film of the circuit board, a glass transition point of not less than 200 ° C. and a thickness of 3 to 30 m is formed on a metal foil having an area larger than the area of the resin composition and having a thickness of 3 to 20 zm. A step of heating and pressurizing the film surface of the heat-resistant film with a metal foil provided with a heat-resistant film layer on the resin composition and laminating; and (c) a step of thermally curing and integrating the circuit board. A method for manufacturing a multilayer printed wiring board. Hereinafter, the present invention will be described in detail.

The thermosetting resin composition which forms a resin composition layer of a thermo-fluidity and a room temperature solid used in the present invention is softened by heating and has a film-forming ability. There is no particular limitation as long as the characteristics required for the interlayer insulating material such as the characteristics are satisfied. The thickness of the resin composition layer is generally equal to or more than the conductor thickness of the inner circuit board to be laminated, and is generally in the range of conductor thickness + (10 to 120) / m. Examples of the resin composition include an epoxy resin, an acrylic resin, a polyimide resin, a polyamide resin, a polycarbonate resin, a polyester resin, and a thermosetting polyphenylene ether resin. It is also possible to use them in combination, or to form an adhesive film layer having a multilayer structure. Above all, epoxy resin compositions described in Tokiwahei 11-87972 are preferred for epoxy resin systems having excellent reliability and cost as interlayer insulating materials.

The preferred physical properties of the resin composition layer can be determined by measuring the dynamic viscoelastic modulus and showing the relationship between the temperature and the melt viscosity in the same manner as described above in relation to the first invention. A hatched area S in FIG. 1 of the drawing is a preferable range of the resin composition layer. The dynamic viscoelasticity measurement is a curve measured using a model Rheosol-G3000 manufactured by UBM Co., Ltd. The upper limit of the dynamic viscoelasticity curve is at an average drying temperature of 100 ° C. The curve at the lower limit for 0 minutes also shows the physical properties of the resin composition layer treated at an average drying temperature of 100 ° C. for 4 minutes. The region sandwiched between the curves experimentally and having a melt viscosity of 100,000 Poise or less and a temperature of 140 ° C. or less represents the physical properties of the resin composition layer preferably used in the practice of the present invention. If the melt viscosity is 100,000 Poise or more, the resin composition layer becomes hard, and when vacuum lamination of the adhesive film of the present invention is carried out, the resin composition layer is poorly embedded in a pattern on a circuit board and adheres well. Poor nature. Manufacturing at a temperature exceeding 140 ° C. is not preferred because wrinkles are likely to occur after vacuum lamination due to a difference in thermal expansion coefficient between the supporting base film and the resin composition. This is also the same as that described above with respect to the first invention.

The dynamic viscoelasticity measurement shown in FIG. 1 of the accompanying drawings of this specification was measured at a heating rate of 5 ° C./min. However, when the heating rate is different, the shape of the curve is different. FIG. 2 shows dynamic viscoelasticity measurement curves measured at different heating rates for the resin composition layer obtained in Adhesive Film Production Example 1 according to the present invention. Therefore, the preferable range of the physical properties of the resin composition layer is that the dynamic viscoelasticity measurement curve must be measured while keeping the measurement conditions constant. Absent.

The supporting base film used in claims 5 and 6 of the present application is a heat-resistant metal box with a heat-resistant film layer having a glass transition point of 200 ° C. or more and a thickness of 3 to 30 zin on a metal foil of 3 to 2 thickness. Film. Heat-resistant resin varnish such as polyimide is coated on metal foil such as copper foil and aluminum foil, dried and heat-cured cast type, heat-resistant film such as thermoplastic polyimide and liquid crystal polymer is used as copper foil, A laminate type in which aluminum foil or the like is bonded to a metal foil, or a spatter type in which a metal layer such as copper is formed on a heat-resistant film such as polyimide or liquid crystal polymer by vapor deposition, sputtering, etc. Is mentioned. The metal foil may have a structure in which a protective film, a carrier foil and the like are held on the opposite surface of the heat-resistant film layer. Specifically, commercially available products such as those using Neoflex Petrochemical Flex manufactured by Mitsui Chemicals, Inc., Upisel manufactured by Ube Industries, Ltd., and liquid crystal polymer films manufactured by Kuraray Co., Ltd. can be used. The heat-resistant film layer is not particularly limited as long as it has a glass transition point of 200 ° C. or more. When the glass transition point is lower than 200 ° C., the solder heat resistance is poor, and it is difficult to use in the present invention. Further, a structure in which an adhesive is interposed between the heat-resistant film and the metal foil may be used, but a two-layer type is preferable in terms of performance. Regarding the thickness, if the thickness of the metal foil layer is less than 3 zm, it may be lost during the subsequent substrate manufacturing process, and if it exceeds 2, it is not suitable for forming a fine pattern. On the other hand, if the heat-resistant film layer is less than 3 / zm, the effect of improving the mechanical strength is diminished, and if it exceeds 3, the cost is high, and the insulating layer portion is too thick, and the fineness of later via formation is reduced. It becomes difficult and unsuitable for fine patterns. The peelable support base film used in claim 7 of the present invention includes polyethylene, polyolefin such as polyvinyl chloride, polyester such as polyethylene terephthalate, polycarbonate, and metal foil such as release paper and aluminum box. And the like. The thickness of the supporting base film is generally 10 to 150 m It is a target. The support film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

The adhesive film used in the present invention comprising the resin composition and a support base film, after applying the resin composition varnish dissolved in a predetermined organic solvent on a support base film, heating and / or hot air spraying the solvent. It can be dried and produced by a known and commonly used method. Thereafter, a release film is further laminated as it is or on the surface of the resin composition layer, and stored in a roll shape. At this time, the area of the resin composition layer can be the same as that of the support base film or a small area having a resin uncoated portion on the support base film.

Next, a method of vacuum laminating the adhesive film on a pattern-processed circuit board can be easily performed using a commercially available vacuum laminator. For example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurized laminator made by Meiki Seisakusho Co., Ltd., a roll-type dry coater manufactured by Hitachi Techno Engineering Co., Ltd., etc. can do. By laminating under the condition that the resin flow at the time of lamination is not less than the conductor thickness of the inner layer circuit, the inner layer circuit pattern can be covered well.

If the supporting base film is a heat-resistant film with a metal foil after vacuum lamination, it can be thermoset as it is and integrated to produce a multilayer printed wiring board. When the support base film is peelable from the rest of the resin composition, after laminating the support base film after vacuum lamination, the area is larger than the area of the resin composition; The glass surface of a heat-resistant film with a metal foil provided with a heat-resistant film layer having ^a glass transition point of 200 aC or more and a heat-resistant film layer having a thickness of 300 m or more in ^a metal box having a thickness of 3 to 20 m is placed on the resin composition. A circuit board having the same configuration as that of the present invention can be manufactured by arranging, heating, and pressing and laminating. In this lamination, a heat-resistant film with metal foil is laminated on a substantially smooth resin surface, so it can be rolled continuously under normal conditions or under reduced pressure. It may be a laminate or a vacuum laminate similar to the process of the present invention. Thereafter, the circuit board is similarly cured by heat and integrated to produce a multilayer printed wiring board. The conditions for thermosetting differ depending on the resin, but are selected in the range of 100 to 200 ° C. for 10 to 90 minutes.

After obtaining a laminated circuit board according to the method of the present invention, predetermined through holes and / or via holes are drilled with a laser and / or a drill, and if necessary, the inside of the holes is cleaned by a dry method, a Z method, or a wet method. After that, the conductor layer is formed by dry plating such as vapor deposition, sputtering and ion plating and / or wet plating such as electroless plating and electrolytic plating. At this time, a mask resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed by a semi-additive method or the like. Finally, the third invention will be described.

In view of the above problems, the present invention relates to a simple method for producing a laminate using a film-like adhesive for build-up having excellent mechanical strength and glass cloth, glass paper or organic nonwoven fabric.

That is, the present invention relates to a supporting base film and a surface thereof, which are laminated on the surface thereof, have the same or smaller area as the supporting base film, and have a relationship between temperature and melt viscosity in a hatched area S in FIG. 1 of the accompanying drawings. An adhesive film comprising a thermosetting, room-temperature solid thermosetting resin composition layer having physical properties, and further comprising a glass cloth or an organic nonwoven fabric layer provided on the surface of the resin composition, characterized by having a structure between eyebrows. A method for producing a laminated plate, comprising: laminating an adhesive film for use on one or both sides of a base material under vacuum under heating and pressurizing conditions, and then thermosetting and integrating the laminated film; or a support base Heat fluidity which is laminated on the film and the surface thereof, has the same or smaller area as the support base film, and has the physical properties of the shaded area S in FIG. 1 of the accompanying drawings in relation to temperature and melt viscosity; Always The insulating layer using an adhesive film made of a thermosetting resin composition layer of a solid In the method of forming, a glass cloth or an organic nonwoven fabric is sheeted on one side or both sides of the base material, and the resin composition layer of the adhesive film is directly overlaid thereon. A method of manufacturing a laminated plate that requires a step of pressing and laminating;

(a) a step of heating and pressurizing and laminating the resin composition layer of the adhesive film directly on one side or both sides of the base material under vacuum conditions, and (b) a supporting base film. In a state in which a glass cloth, a glass paper or an organic nonwoven fabric is sheeted on the upper layer of the substrate on which the resin composition layer has been transferred, and the resin composition layer of the adhesive film is directly overlaid thereon. A method for producing a laminate, which requires a step of laminating by heating and pressing under vacuum conditions. Hereinafter, the present invention will be described in detail.

The thermosetting resin composition which forms a resin composition layer of a thermo-fluidity and a room temperature solid used in the present invention is softened by heating and has a film-forming ability. There is no particular limitation as long as it satisfies the characteristics required for the inter-glove insulation, such as the characteristics. The thickness of the resin composition layer is generally equal to or greater than the conductor thickness of the inner circuit board to be laminated, and is generally in the range of (conductor thickness + (10 to 120) m). In addition, in the case of claims 1 to 3 of the present application, the resin thickness is preferably in the range of glass cloth or organic nonwoven fabric thickness + (10 to 120) / m.

Examples of the resin composition include an epoxy resin, an acrylic resin, a polyimide resin, a polyamideimide resin, a polyisocyanate resin, a polyester resin, and a thermosetting polyphenylene ether resin. It is also possible to use them in combination, or to form an adhesive film layer having a multilayer structure. Above all, epoxy resin compositions described in Tokiwahei 11-87972 are preferred for epoxy resin systems having excellent reliability and cost as interlayer insulating materials.

Preferred physical properties of the resin composition layer are as described above with respect to the first invention. Similarly, the dynamic viscoelastic modulus can be measured and represented by the relationship between the temperature and the melt viscosity. The hatched area S in FIG. 1 of the attached drawings of the present specification is a preferable range of the resin composition layer. The dynamic viscoelasticity measurement is a curve measured using a model manufactured by U.B.I.M. Co., Ltd., Rheosol-G3000. The upper limit of the dynamic viscoelasticity curve is at an average drying temperature of 100 ° C. The curve at the lower limit for 10 minutes also shows the physical properties of the resin composition layer treated at an average drying temperature of 100 ° C. for 4 minutes. The region sandwiched between the curves experimentally and having a melt viscosity of 100,000 Poise or less and a temperature of 140 ° C. or less represents the physical properties of the resin composition layer preferably used in the practice of the present invention. When the melt viscosity is 100,000 Poise or more, the resin composition layer becomes hard, and when the adhesive film of the present invention is vacuum-laminated, the resin composition is poorly embeddable into a substrate and a glass cloth or an organic nonwoven fabric, and adheres well. Poor nature. Manufacturing at a temperature exceeding 140 ° C. is not preferred because wrinkles are likely to occur after vacuum lamination due to the difference in the thermal expansion coefficient between the supporting base film and the resin composition.

The dynamic viscoelasticity measurement shown in FIG. 1 of the accompanying drawings of this specification was measured at a heating rate of 5 ° C./min. However, when the heating rate is different, the shape of the curve is different. FIG. 2 shows dynamic viscoelasticity measurement curves measured at different heating rates for the resin composition layer obtained in Adhesive Film Production Example 1 according to the present invention. Therefore, the range of preferable physical properties of the resin composition layer must be measured under a constant measurement condition to measure a dynamic viscoelasticity measurement curve.

Examples of the support base film used for the adhesive film of the present invention include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonates, and metal such as release paper, copper foil, and aluminum foil. Foil and the like. The thickness of the supporting base film is generally from 10 to 150 m. Note that the support film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

The adhesive film comprising the resin composition of the present invention and a support base film is as follows: The resin composition varnish dissolved in a given organic solvent is applied onto a support base film, and then the solvent is dried by heating and / or hot air spraying to prepare the resin composition by a known and common method. Thereafter, a glass cloth or an organic nonwoven fabric is heat-laminated on the surface of the resin composition layer, and the laminate is wound into a roll and stored. Alternatively, in the case of claims 10 and 11 of the present application, the surface of the resin composition layer is stored as it is or a release film is laminated thereon and wound into a roll. At this time, the area of the resin composition layer can be the same as the supporting base film or a small area having a resin uncoated portion on the supporting base film.

Commercially available glass cloth, glass paper, and organic nonwoven fabric used in the present invention can be used, but a thin material of 20 to 100 m is preferable. Among them, it is preferable to use a type having a small filament diameter, a fine mesh and good flatness, and an organic nonwoven fabric typified by an aramide nonwoven fabric because it is excellent in laser-workability.

Next, a specific construction method will be described.

When the adhesive film has a structure having a glass cloth or an organic nonwoven fabric on the surface of the resin composition, the glass cloth or the organic nonwoven fabric surface is vacuum-laminated on one or both surfaces of the substrate under heating and pressure. Lamination can be performed using a commercially available vacuum lamination press, Vacuum Lamine Ichiichi. Among them, Nichigo's Morton Co., Ltd. Vacuum Appliqué Ichiichi, Meiki Seisakusho Co., Ltd. Vacuum Pressurized Lamine Ichiichi, Hitachi Techno Engineering Dryco Ichiyu, etc. By using, it is possible to easily perform vacuum lamination without voids. This makes it possible to easily produce a laminate having excellent rigidity with a configuration of base resin / glass cloth or organic nonwoven cloth / resin. As for the base material, in addition to pre-preda and unclad substrates, it is possible to manufacture multilayer printed wiring boards using flexible films such as polyimide and polyethylene naphthalate, and circuit boards that have been processed into printed circuits. is there.

When using an adhesive film without glass cloth or organic nonwoven fabric, The resin composition surface is vacuum-laminated similarly under heating and pressing conditions with a glass cloth or an organic non-woven fabric interposed on a substrate. This makes it possible to produce a laminate having the same structure as the above-mentioned base material / resin / glass cloth or organic nonwoven fabric / resin. Further, in the present invention, first, the adhesive film is vacuum-laminated on a substrate, and then the supporting base film is peeled off. Thereafter, a glass cloth, a glass paper or an organic nonwoven fabric is sheet-fed on the substrate on which the resin composition has been transferred, and the resin composition layer of the adhesive film is directly covered again, and the vacuum conditions are applied. Underneath, heating and pressurizing can be used for lamination. Thereby, even when the resin composition layer of the adhesive film is thin, it is possible to easily produce a laminated board with the structure of the base material / resin / glass cloth, glass paper or organic nonwoven fabric / resin. .

After the vacuum lamination, when the supporting base film is a metal foil such as a copper foil, the support base film can be thermoset as it is and integrated to produce a laminated board. When the support base film is peelable from the other resin composition, after vacuum lamination, the support base film is peeled off, and then heat-cured similarly to be integrated to produce a laminated board. can do. The thermosetting condition varies depending on the resin, but is 100 to 200 °. Is selected in the range of 10 to 90 minutes.

After obtaining a laminated board according to the method of the present invention, a predetermined through hole and / or via hole portion is drilled with a laser and / or a drill, and if necessary, the inside of the hole is dry and / or dry. Alternatively, after cleaning by a wet method, a conductor layer is formed by dry plating such as vapor deposition, sputtering and ion plating and / or wet plating such as electroless plating and electrolytic plating, and a printed wiring board can be manufactured.

(Brief description of drawings)

FIG. 1 shows a dynamic viscoelasticity measurement, which is a curve measured using a model Rhesol-G 3000 manufactured by U.B.M. Co., Ltd. The upper limit curve of the dynamic viscoelasticity (1) Average drying temperature Curve (2) at 100 ° C for 10 minutes and the lower limit curve also shows the physical properties of the resin composition treated at an average drying temperature of 100 ° C for 4 minutes. The measurement conditions were as follows: a heating rate of 5 ° C / min, a starting temperature of 60 ° C, a measuring temperature interval of 2.5 ° C, and a vibration of lHz / deg.

FIG. 2 shows a dynamic viscoelasticity measurement, which is a curve measured using a model Rhesol-G 3000 manufactured by UBM Corporation. This shows the physical properties of the resin composition obtained by treating the obtained resin composition layer at an average drying temperature of 100 ° C. for 5 minutes. The heating rates are 5 ° C / min (curve III), 10 ° C (curve II) and 20 ° C (curve I). The measurement conditions were as follows: the starting temperature was 60 ° C and the measuring temperature interval was 2.5. The vibration is lHz / deg.

FIG. 3 shows a dynamic viscoelasticity measurement, which is a curve measured using a model Rhesol-G3000 manufactured by UM Co., Ltd. The obtained resin composition layer was dried at an average drying temperature of 100 ° C. for 2 minutes (curve A) and 8 minutes.

(Curve B) and the physical properties of the resin composition treated for 15 minutes (Curve C). The measurement conditions were as follows: a temperature rise rate of 5 ° C / min, a starting temperature of 60 ° C, a measurement temperature interval of 2.5 ° C, and a vibration of lHz / deg.

(Best mode for carrying out the invention)

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. First, embodiments of the first invention will be described. Adhesive film production example 1

20 parts of liquid bisphenol A type epoxy resin (Epicoat 82 8 EL manufactured by Yuka Shell Epoxy Co., Ltd.), brominated bisphenol A type epoxy resin (Toto Kasei 20 parts, Cresol monovolak type epoxy resin (epoxy equivalent: 21.5, softening point: 78 ° C, Epiclon N-673, manufactured by Dainippon Ink & Chemicals, Inc.) 20 parts, terminal 15 parts of epoxidized polybutadiene rubber (Denalex R-45EPT, manufactured by Nagase Kasei Kogyo Co., Ltd.) is heated and dissolved in MEK with stirring, and then a brominated phenoxy resin varnish (non-volatile content: 40% by weight, bromine content) 25% by weight, solvent composition, xylene: methoxypropanol: methyl ethyl ketone = 5: 2: 8, Toto Kasei Co., Ltd. YPB-40-PXM40) 50 parts, epoxy curing agent 2,4-diamino-6- 2-Methyl-1-imidazolylethyl) _ 1,3,5-triazine / isocyanuric acid adduct 4 parts, finely divided silica 2 parts, antimony trioxide 4 parts, calcium carbonate 5 parts Make a varnish . Apply the varnish on a 5 m copper foil with an aluminum foil carrier with a thickness of 40 zm at Daiko Yuichi so that the resin thickness after drying is 70 m, 80 to 120 ° C (average 100 ° C), and slit to a width of 507 mm to obtain a roll-shaped adhesive film. The dynamic viscoelastic modulus of the resin composition layer of the adhesive film obtained as described above was measured using a model Rhesol-G3000 manufactured by BM Corporation. Figure 1 shows that the upper limit of the dynamic viscoelasticity curve is 10 minutes at an average drying temperature of 100 ° C, and the lower limit curve is the average drying temperature.

It shows the physical properties of the resin composition treated at 100 ° C. for 4 minutes. FIG. 2 shows dynamic viscoelasticity measurement curves when the heating rate was set to 5 ° C./min, 10 ° C./min, and 20 C / min. Adhesive film manufacturing example 2

A roll-shaped adhesive film was obtained in exactly the same manner except that the aluminum foil-carrying copper foil of Adhesive Film Production Example 1 was changed to a 3-polyethylene terephthalate film. Comparative adhesive film production example 1 A roll-shaped adhesive film was obtained in exactly the same manner as in Adhesive Film Production Example 1, except that the copper foil with an aluminum foil carrier was changed to a 12-m thick copper foil. Comparative Example 1

The rolled adhesive film obtained in Comparative Production Example 1 was applied to a patterned 50 × 340 mm glass epoxy inner layer circuit board (conductor thickness: 35 zm),

The sheets were cut on both sides of the substrate at a size of 507 x 33 36 mm using Auto Cut Laminate overnight manufactured by Co., Ltd. The conditions were as follows: 70 ° C at the temporary attachment part, 5 seconds of pressure bonding, lamination at room temperature, without load. Next, a protective film for the upper and lower sides of a vacuum applicator made by Morton Inn Yuichi National Co., Ltd., made of polyethylene terephthalate having a width of 540 mm and a thickness of 25 zm, was set. Both sides were simultaneously laminated by a press of 15 msec at a vacuum of 1 mbar and a temperature of 80 ° C. Thereafter, the laminated circuit board was taken out of the protective film and heat-cured at 120 ° C. for 30 minutes and at 170 ° C. for 30 minutes. Line / space after cooling to around room temperature = 6400 /

When the surface of the copper foil on the 640 m circuit was measured with a surface roughness tester manufactured by Tokyo Seimitsu Co., Ltd., the maximum height was 1. Example 1

In the same manner as in Comparative Example 1, the roll-shaped adhesive film obtained in Production Example 1 was placed on a patterned 5110 x 34 mm glass epoxy inner layer circuit board, and the width was 507 x 33 mm. Sized sheets on both sides of the substrate. Next, a vacuum protection film is placed on a vacuum applicator made by Morton Ink-National-Ink-Polytide, a polyethylene terephthalate film with a width of 540 mm and a thickness of 25 πι. Laminated at the same time on both sides with a vacuum of 1 mbar, a temperature of 80 ° C and a press of 15 seconds. After that, remove the laminated circuit board from the protective film and leave it at 130 ° C for 30 minutes. Furthermore, it was thermally cured at 170 ° C for 3 °. Next, after the aluminum foil carrier was removed by chemical etching, the copper foil surface on the circuit with a line space of 640 / 640〃m was measured with a surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd. Maximum height was 5 / m. Example 2

In the same manner as in Comparative Example 1, the roll-shaped adhesive film obtained in Production Example 2 was applied to a patterned 50 × 340 mm glass epoxy inner-layer circuit board in a size of width 507 × 336 mm. Sheets were formed on both sides of the substrate. Next, a polyethylene terephthalate film having a width of 540 mm and a thickness of 25 μ.το was set as a protective film on both base rolls of a vacuum press machine MV LP manufactured by Meiki Seisakusho Co., Ltd. The substrate was loaded from the vicinity of the center, and the two sides were simultaneously laminated by a press of 1 mbar, a temperature of 80 ° C, a pressure of 5 kg and a press of 15 seconds. After cooling to near room temperature, the polyethylene terephthalate film was peeled off. Next, an ultra-thin copper foil surface of a copper foil in which a 3 / zm copper foil was formed on a copper foil carrier having a thickness of 35 m via a release layer with a thickness of 5 10 x 340 mm Similarly, the substrate was put in the vicinity of the center of the protective film, and simultaneously laminated on both sides by pressing at a degree of vacuum of 1 mbar, a temperature of 80 ° C., a pressure of 5 kg, and a pressure of 15 kg for 15 seconds. Thereafter, the laminated circuit board was heat-cured at 120 ° C. for 30 minutes and further at 170 ° C. for 30 minutes, and after the copper foil carrier was mechanically removed, line / space = 640Z64 0 / The maximum height of the copper foil on the circuit was 4 zm when measured with a surface roughness tester manufactured by Tokyo Seimitsu Co., Ltd.

As is evident from the results of Examples 1 and 2, according to the method of the present invention, a laminated circuit board having an ultra-thin copper foil of 10 zm or less was used in comparison with the conventional thin-film limit of using 12 2πι copper foil. Compared with Comparative Example 1, the layers can be efficiently laminated with excellent surface smoothness, and a multilayer printed wiring board having a fine pattern can be easily manufactured. Comparative Example 2

FIG. 3 shows a dynamic viscoelasticity measurement curve of the resin composition layer obtained by drying the resin composition layer obtained in Adhesive Film Production Example 1 at an average drying temperature of 100 ° C. for 2 minutes. This is clearly outside the shaded area S shown in FIG. The adhesive film obtained by laminating this resin composition layer on a supporting base film could be subjected to a laminating step, but resin dripping occurred in the next thermosetting step, and as a result, the layer thickness of the resin composition layer was reduced. It could not be used for the purpose of the present invention due to the non-uniformity. Comparative Example 3

FIG. 3 shows a dynamic viscoelasticity measurement curve of the resin composition layer obtained by drying the resin composition layer obtained in Adhesive Film Production Example 1 at an average drying temperature of 100 ° C. for 15 minutes. Obviously, the viscosity shifted to the higher viscosity side outside the shaded area S shown in FIG. This resin composition layer was laminated on a supporting base film to produce an adhesive film. An attempt was made to laminate the resin composition layer of the adhesive film on the pattern portion of the circuit board, but could not find conditions for vacuum lamination without voids. Next, an embodiment of the second invention will be described. Adhesive film production example 1

Liquid bisphenol A-type epoxy resin (Epicoco 828 EL) manufactured by Yuka Shell Epoxy Co., Ltd. 20 parts, brominated bisphenol A-type epoxy resin (08-500) manufactured by Toto Kasei Co., Ltd. 2 0 parts, cresol nopolak type epoxy resin (epoxy equivalent: 21.5, softening point: 78 ° C, Epiclone N—673, manufactured by Dainippon Ink & Chemicals, Inc.) 20 parts, epoxidized polybutadiene rubber ( Denase from Nagase Kasei Kogyo Co., Ltd. 15 parts of Rex R-45EPT) were dissolved in MEK with stirring and heated, and the brominated phenoxy resin varnish (non-volatile content 40% by weight, bromine content 25% by weight, solvent composition, xylene: methoxypropanol: methyle) Tylketone = 5: 2: 8, 50 parts of YPB-40-PXM40 manufactured by Toto Kasei Co., Ltd., 2,4-Diamino 6- (2-methyl-1-Imidazolylethyl) 1,3,3 as epoxy curing agent A resin composition varnish was prepared by adding 4 parts of 5-triazine / isocyanuric acid adduct, 2 parts of finely ground silica, 4 parts of antimony trioxide, and 5 parts of calcium carbonate. The varnish was placed on a 12-m-thick copper foil / polyimide layer 25 m thick polyimide layer of Ube Industries, Ltd. Upisel Co., Ltd., and the whole resin was dried overnight so that the resin thickness after drying was 70 m. Coating, 80 ~: L After drying at 20 ° C (average 100 ° C), slit to 507 mm width to obtain a roll-shaped adhesive film. After that, it was formed into a sheet of 507 x 336 mm size.

The dynamic viscoelastic modulus of the resin composition layer of the adhesive film obtained as described above was measured using a model Rheosol-G3000 manufactured by UB Corporation. Fig. 1 shows that the upper limit of the dynamic viscoelasticity curve is 10 minutes at an average drying temperature of 100 ° C, and the lower limit curve is the physical properties of a resin composition treated at an average drying temperature of 100 ° C for 4 minutes. Figure 2 shows the dynamic viscoelasticity measurement curves when the heating rate was 5 ° C / min, 10 ° C / min, and 20 ° C / min. Adhesive film manufacturing example 2

Adhesive film production example The sheet was made in exactly the same manner except that the polyimide film with copper foil in 1 was replaced with a 5 zm copper foil / polyimide layer 25 / m Etchflex manufactured by Mitsui Chemicals, Inc. An adhesive film was obtained. Comparative adhesive film production example 1

Adhesive film production example 1 Polyimide film with copper foil of 38 mm thick A sheet-like adhesive film was obtained in exactly the same manner, except that the rate was changed to Tylene terephthalate. Comparative Example 1

On a glass epoxy inner-layer circuit board with a patterned thickness of 0.2 mm and a size of 5110 x 34 Omm (conductor thickness: 35Π1), the sheet-like adhesive film obtained in Comparative Production Example 1 was applied on both sides of the board did. Next, both sides were simultaneously laminated using a vacuum press machine MVLP manufactured by Meiki Seisakusho Co., Ltd. with a vacuum of 1 mbar, a temperature of 100 ° C, and a pressure of 6 kg / c for 15 seconds. Thereafter, the supporting pace film was peeled off, and the laminated circuit board was heat-cured at 170 ° C. for 30 minutes to obtain a four-layer board. The elastic moduli of the four-layer plate obtained from a universal hardness tester (FIS CHER S COPE H100) were 5.0 GPa at room temperature and 3.5 GPa at 150 ° C. Example 1

As in Comparative Example 1, a sheet-like adhesive obtained in Production Example 1 was applied to a patterned 0.2 mm thick, 51 O x 34 Omm glass epoxy inner layer circuit board (conductor thickness: 35 zm). The films were sheeted on both sides of the substrate. Then, both sides were simultaneously laminated using a vacuum press machine MV LP manufactured by Meiki Seisakusho Co., Ltd. with a vacuum of 1 mbar, a temperature of 100 ° C, a pressure of 6 kg / cm ² , and 15 seconds. Thereafter, the laminated circuit board was thermally cured at 120 ° C. for 30 minutes and further at 170 ° C. for 30 minutes to obtain a four-layer board. The modulus of elasticity of the four-layer plate obtained from the universal hardness tester after the copper foil etching was 6. OGPa at room temperature and 4.5 GPa at 150 ° C. Example 2

As in Comparative Example 1, the patterned thickness was 0.2 mm, and the size was 51 O x On a 340 mm glass epoxy inner layer circuit board (conductor thickness: 35 m), the sheet-like adhesive film obtained in Production Example 2 was sheeted on both sides of the board. Next, both sides were simultaneously laminated with a vacuum press of 1 mbar, a temperature of 100 ° C, a pressure of 6 kg / cm ² and a 15-second press using a vacuum press machine MV LP manufactured by Meiki Seisakusho Co., Ltd. Thereafter, the laminated circuit board was heat-cured at 12 CTC for 30 minutes and then at 17 (TC for 30 minutes to obtain a four-layer board. The elastic modulus of the four-layer board obtained from the universal hardness tester after the copper foil etching was determined. It was 7.2 GPa at room temperature and 5.4 GPa at 150 ° C.

As is clear from the results of Examples 1 and 2, according to the method of the present invention, it is possible to easily manufacture a multilayer printed wiring board having excellent mechanical strength by a build-up method. Comparative Example 2

FIG. 3 shows a dynamic viscoelastic modulus measurement curve of the resin composition layer obtained in Production Example 1 of the adhesive film, which was dried at an average drying temperature of 100 ° C. for 2 minutes. This is clearly outside the shaded area S shown in FIG. Although the adhesive film formed on the supporting base film with the resin composition layer could be subjected to the laminating step, resin sagging occurs in the next thermosetting step, and the thickness of the resin composition layer is not sufficient. Since it became uniform, it could not be used for the purpose of the present invention. Comparative Example 3

FIG. 3 shows a dynamic viscoelasticity measurement curve of the resin composition layer obtained in Production Example 1 of the adhesive film obtained by drying the resin composition layer at an average drying temperature of 100 ° C. for 15 minutes. Obviously, the viscosity shifted to the higher viscosity side outside the shaded area S shown in FIG. An adhesive film was produced by laminating the resin composition layer on a support base film. An attempt was made to laminate the resin composition layer of this adhesive film on the pattern portion of the circuit board. It was not possible to find the conditions under which vacuum lamination was possible without any problems. Finally, an embodiment of the third invention will be described. Adhesive film production example 1

20 parts of liquid bisphenol A-type epoxy resin (Epicoat 82 8 EL manufactured by Yuka Shell Epoxy Co., Ltd.), brominated bisphenol A-type epoxy resin (Toto Kasei

20 parts of YDB-500 manufactured by Co., Ltd., 20 parts of cresol novolak type epoxy resin (epoxy equivalent: 215, softening point 78 ° C, Epiclone N-67 3 manufactured by Dainippon Ink & Chemicals, Inc.), terminal epoxidation 15 parts of polybutadiene rubber (Denalex R-45EPT, manufactured by Nagase Kasei Kogyo Co., Ltd.) is dissolved by heating in MEK with stirring. , Solvent composition, xylene: methoxypropanol: methyl ethyl ketone = 5: 2: 8, Toto Kasei Co., Ltd. YPB-40-PXM40) 50 parts, epoxy curing agent 2,4-diamino-1-6- —Methyl-1—imidazolylethyl) 1,1,3,5-Triazine / isocyanuric acid adduct 4 parts, 2 parts of finely ground silica, 4 parts of antimony trioxide, 5 parts of calcium carbonate are added to the resin composition. Make a varnish . The varnish is applied on a 38 mm thick polyethylene terephthalate film using a die coater so that the resin thickness after drying is 70 // m. (° C), apply a 0.05mm thick glass cloth to the resin surface at a temperature of 50 ° C and a linear pressure.

Heat lamination was performed under the condition of 2 kg / cm. Then, it was slit to a width of 507mni to form an adhesive adhesive film, and further formed into a sheet of 507 x 336mm size. The dynamic viscoelasticity of the resin composition layer of the adhesive film obtained as described above was measured using a model Rheosol-G3000 manufactured by UBM Corporation. Figure 1 shows that the upper limit of the dynamic viscoelasticity curve is 10 minutes at an average drying temperature of 100 ° C, and the lower limit curve is the average drying temperature. It shows the physical properties of the resin composition treated at a temperature of 100 ° C for 4 minutes. Figure 2 shows the dynamic viscoelasticity measurement curves when the heating rate was 5 ° C / min, 10 ° C / min, and 20 ° C / min. Adhesive film manufacturing example 2

A sheet-like adhesive film was obtained in exactly the same manner except that the glass cloth of Adhesive Film Production Example 1 was changed to a polypropylene film having a thickness of 15 mm. Adhesive film production example 3

A roll-shaped adhesive film was obtained in exactly the same manner except that the polyethylene terephthalate film as the support base film of Adhesive Film Production Example 1 was changed to a copper foil having a thickness of 18 m. Comparative Example 1

On a patterned 0.2mm thick, 510 x 34 Omm glass epoxy inner layer circuit board (conductor thickness 35 // m), peel off the polypropylene film of the sheet adhesive film obtained in Production Example 2, Sheets were formed on both sides of the board with the resin side as the pattern side. Next, both sides were simultaneously laminated by a vacuum press machine MV LP manufactured by Meiki Seisakusho Co., Ltd. with a vacuum of 1 mbar, a temperature of 100 ° C, a pressure of 6 kg / cm ² and a 15-second press. Thereafter, the supporting base film was peeled off, and the laminated circuit board was thermoset at 170 ° C. for 30 minutes to obtain a four-layer board. The 4-layer universal hardness tester (FI SCHERS

The elastic modulus determined from COPE H 100) was 5.0 GPa at room temperature and 3.5 GPa at 150 ° C. Example 1

As in Comparative Example 1, the patterned thickness was 0.2 mm, and the size was 51 O x The sheet-like adhesive film obtained in Production Example 1 was sheet-patterned on both sides of the glass epoxy inner layer circuit board with the glass cloth surface of the adhesive film obtained in Production Example 1 as the pattern side. next

Using a vacuum press machine MV LP manufactured by Meiki Seisakusho, both sides were simultaneously laminated by a press of 1 mbar, a temperature of 110 ° C, a pressure of 6 kg / cm ² , and a pressure of 30 seconds. Thereafter, the supporting base film was peeled off, and the laminated circuit board was thermally cured at 100 ° C. for 30 minutes to obtain a four-layer board. The elastic modulus obtained from the universal hardness tester of the four-layer plate is 7.

It was 6.6 GPa at 4 GPa and 150 ° C. Example 2

In the same manner as in Comparative Example 1, the polypropylene film of the sheet-like adhesive film obtained in Production Example 2 was peeled off on both sides of a patterned glass epoxy inner layer circuit board having a thickness of 0.2 mm and a size of 51 O x 34 Omm as in Comparative Example 1. After that, the resin surface was turned into the pattern side and the wafer was sheet-fed on both sides of the substrate. The vacuum press machine MVLP manufactured by Meiki Seisakusho Co., Ltd., vacuum 1 mbar, temperature 100 ° C, pressure 6 kg / cm ² , 15 seconds The two sides were simultaneously laminated by a press. Thereafter, the supporting base film was peeled off, and a 0.05 mm thick non-woven fabric of the same size as the substrate was sandwiched on the laminated circuit board. Further, the resin surface of the sheet-like adhesive film obtained in Production Example 2 was further removed. Was turned to the nonwoven fabric side and the sheets were sheeted on both sides. Using a vacuum press machine MV LP manufactured by Meiki Seisakusho Co., both surfaces were simultaneously laminated by a vacuum of 1 mbar, a temperature of 100 ° C, a pressure of 6 kg / cm ² , and a 30-second press. Thereafter, the support base film was peeled off, and the laminated circuit board was thermoset at 170 ° C. for 30 minutes to obtain a four-layer board. The elastic modulus obtained from the universal hardness tester of the four-layer plate was 5.9 GPa at room temperature and 4.4 GPa at 150 ° C. Example 3

Production example 3 using a 0.1 mm thick polyethylene naphtholate film as the base material Using the roll-type dry roll manufactured by Hitachi Techno Engineering Co., Ltd., the mouth-like adhesive film obtained in the above was vacuum-laminated on both sides simultaneously with the glass cloth side as the base material side. The conditions were as follows: temperature 110 ° C, linear pressure 2kg / cm, 50cm / min. Then, it was heat-cured at 120 ° C for 30 minutes and further at 170 ° C for 30 minutes to obtain a double-sided board. The modulus of elasticity of the double-sided board measured by a universal hardness tester after copper foil etching was 6.4 GPa at room temperature and 5.OGPa at 150 ° C.

As is clear from the results of Examples 1 to 3, according to the method of the present invention, it is possible to easily produce a laminated board and a multilayer printed wiring board having excellent mechanical strength. Comparative Example 2

FIG. 3 shows a dynamic viscoelastic modulus measurement curve of the resin composition layer obtained in Production Example 1 of the adhesive film, which was dried at an average drying temperature of 100 ° C. for 2 minutes. This is clearly outside the shaded area S shown in FIG. Although the laminating process could be performed on the adhesive film having the resin composition layer formed on the supporting base film, resin sagging occurred in the next thermosetting process, and thus the thickness of the resin composition layer was uneven. Therefore, it could not be used for the purpose of the present invention. Comparative Example 3

FIG. 3 shows a dynamic viscoelasticity measurement curve of the resin composition layer obtained in Production Example 1 of the adhesive film obtained by drying the resin composition layer at an average drying temperature of 100 ° C. for 15 minutes. Obviously, the viscosity shifted to the higher viscosity side outside the shaded area S shown in FIG. This resin composition layer was laminated on a supporting pace film to produce an adhesive film. An attempt was made to laminate the resin composition layer of the adhesive film on the pattern portion of the circuit board, but could not find conditions for vacuum lamination without voids. (Industrial applicability)

According to the method of the present invention, it is possible to easily manufacture a laminated circuit board having an extremely thin copper foil while having excellent surface smoothness.

Further, according to the method of the present invention, it is possible to easily manufacture a multilayer printed wiring board having excellent mechanical properties by a build-up method.

Furthermore, according to the method of the present invention, it is possible to easily produce a laminated board and a multilayer printed wiring board having excellent mechanical strength by a build-up method.

Claims

' The scope of the claims

1. The support base film and the surface thereof are laminated and have the same or smaller area as the support base film, and the physical properties of the hatched area S in FIG. An adhesive film comprising a thermosetting, room-temperature solid thermosetting resin composition layer having a support base film having a metal foil having a thickness of 1 to 10 / m on the resin composition surface, and an opposite surface. An adhesive film for interlayer insulation, characterized in that it has a structure provided with a release carrier having a thickness of 10 to 100 m.

2. The resin composition layer of the adhesive film for interlayer insulation according to claim 1 is vacuum-laminated on one or both sides of a patterned circuit board under heating and pressure conditions, and then thermally cured to be integrated. A method for manufacturing a multilayer printed wiring board, characterized in that:

3. (a) The resin composition layer of the adhesive film for interlayer insulation according to claim 1 is coated on one or both sides of a patterned circuit board, and at least the pattern processing portion is formed of the resin composition layer. (B) a step of: (b) temporarily bonding these to a single sheet or two sides on a circuit board, and then temporarily bonding them to one side or both sides of the circuit board. Heating and pressurizing from the side of the protective film under a vacuum condition of 2 mbar or less while sandwiching the protective film having a large area so that the center of the protective film and the center of the protective film are substantially at the same position, and (C) a step of thermally curing and integrating the circuit board; and a method for producing a multilayer printed wiring board.

4. (a) Laminated on a supporting base film and a peelable surface thereof, having the same or smaller area as the supporting base film, and having a relationship between temperature and melt viscosity as shown in FIG. The resin composition layer of an adhesive film composed of a thermosetting, room temperature solid thermosetting resin composition layer having the properties of the shaded region S is placed on at least one side or both sides of the patterned circuit board. Patterned part directly with the resin composition layer (C) a step of temporarily adhering and partially sheeting these pieces after covering, and (b) an area larger than the area of the resin composition layer on the adhesive film temporarily adhered to one or both sides of the circuit board. (C) laminating the protective film having an area from the protective film side under a vacuum condition of 2 mbar or less under a vacuum condition of 2 mbar or less while sandwiching the protective film with the adhesive film and the center thereof at substantially the same position. After peeling the support base film of the circuit board, a peeling carrier having a thickness of 10 to 100 m thick, which is larger than the area of the resin composition and has a thickness of 1 to 10 / zm, is provided. A method for producing a multilayer printed wiring board, comprising: a step of heating and pressurizing the provided metal foil on the resin composition to laminate the same; and (d) a step of thermally curing and integrating the circuit board.

5. Laminated on the supporting base film and its surface, has the same or smaller area as the supporting base film, and has the properties of the shaded area S in FIG. 1 of the accompanying drawings in relation to the temperature and the melt viscosity. In an adhesive film composed of a thermosetting resin composition layer that is heat-fluid and solid at room temperature, the supporting base film has a glass transition point of at least 200 ° C and a thickness of 3 to 3 on a metal foil having a thickness of 3 to 20 m. An adhesive film for interlayer insulation, comprising: a heat-resistant film with a metal foil provided with the heat-resistant film layer described above; and a structure in which the resin composition layer is formed on the heat-resistant film surface.

6. The resin composition layer of the adhesive film for interlayer insulation according to claim 5 is vacuum-laminated on one or both sides of a pattern-processed circuit board under heating and pressure conditions, and then thermally cured to be integrated. A method for manufacturing a multilayer printed wiring board, characterized in that:

7. (a) Laminated on a supporting base film and its peelable surface, having the same or smaller area as the supporting base film, and oblique lines in FIG. 1 of the accompanying drawings in relation to temperature and melt viscosity. The resin composition layer of an adhesive film composed of a thermosetting, room temperature solid thermosetting resin composition layer having the physical properties of the region S is provided on at least one side or both sides of a patterned circuit board by at least the pattern A step of directly covering the processed portion with the resin composition layer and then heating and pressurizing to laminate by vacuum; (b) a support base for the circuit board After peeling the film, a metal having a heat-resistant film layer having a glass transition point of 200 ° C. or more and a thickness of 3 to 30 m on a metal foil larger than the area of the resin composition and having a thickness of 3 to 20 zm. A step of heating and pressurizing the film surface of the heat-resistant film with a foil on the resin composition to laminate, and (c) a step of thermally curing and integrating the circuit board. Manufacturing method.

8. The support base film and the surface of the support base film are laminated and have the same or smaller area as the support base film, and the properties of the hatched area S in FIG. An adhesive film comprising a thermosetting resin composition layer having a thermofluidity and a solid at room temperature, further comprising a glass cloth or an organic nonwoven fabric layer provided on the surface of the resin composition; the film.

9. The glass cloth or the organic nonwoven fabric surface of the adhesive film for eyebrows insulation according to claim 8 is vacuum-laminated on one or both surfaces of the base material under heating and pressurizing conditions, and then thermally cured and integrated. A method for producing a laminate, characterized by the following.

10. Laminated on the supporting base film and its surface, has the same or smaller area as the supporting base film, and has the physical properties of the hatched area s in FIG. 1 of the accompanying drawings in relation to the temperature and the melt viscosity. In a method of forming an insulating layer using an adhesive film formed of a thermosetting resin composition layer having a thermofluidity and a solid at room temperature, a glass cloth or an organic nonwoven fabric is formed on one or both surfaces of a substrate, and A method of manufacturing a laminated board that requires a process of heating and pressing under vacuum conditions and laminating the resin composition layer of the adhesive film directly on top of it.

11. The support base film and the surface thereof are laminated, have the same or smaller area as the support base film, and have the properties of the shaded area S in FIG. 1 of the accompanying drawings in relation to the temperature and the melt viscosity. In a method of forming an insulating layer using an adhesive film comprising a thermosetting resin composition layer of a thermo-fluidity and a solid at room temperature, (a) directing the resin composition layer of the adhesive film directly on one side or both sides of a substrate In a vacuum condition, Heating, pressing and laminating, and (b) peeling off the supporting base film, and sheeting a glass cloth, glass paper or organic nonwoven cloth on the upper layer of the substrate on which the resin composition layer has been transferred, And a step of heating and pressurizing and laminating under a vacuum condition in a state where the resin composition layer of the adhesive film is directly overlaid thereon.

12. A method for producing a laminate, wherein the substrate according to any one of claims 9 to 11 is a pre-preda or a flexible film.

13. A method for producing a multilayer printed wiring board, characterized in that the substrate according to claim 9 is a circuit board subjected to pattern processing.