JP2020050797A - Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board - Google Patents

Abstract

An object of the present invention is to provide a resin composition capable of forming a cured product having good surface appearance and high adhesion to a substrate.
The resin composition comprises (A) an epoxy resin, (B) a curing agent, (C) a phenoxy resin having a weight average molecular weight in the range of 30,000 to 100,000, and (D) a surface conditioner. , (E) an antifoaming agent. (D) The surface conditioner contains a polyether-modified polydimethylsiloxane. (E) The antifoaming agent contains an acrylic copolymer.
[Selection diagram] Fig. 1

Description

  The present invention relates to a resin composition, a prepreg, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a printed wiring board.

  Conventionally, a prepreg used for manufacturing a printed wiring board or the like is formed by impregnating a fiber base material with a resin composition containing a thermosetting resin, and heating and drying the fiber base material to a semi-cured state. Then, after cutting the prepreg to a predetermined size, a required number of sheets are stacked, and a metal foil is stacked on one or both sides of the prepreg, and heated and pressed to form a laminate, thereby forming a metal-clad laminate used for manufacturing a printed wiring board. Has been produced.

  However, since the prepreg is in a semi-cured state, it is brittle, and powder is likely to fall when cutting or laminating the prepreg. There is a possibility that the produced laminated plate may be dented like a dent due to powder dropping generated when handling the prepreg, and a dent defect may occur.

  For example, Patent Document 1 discloses a resin composition containing an epoxy resin, a curing agent such as dicyandiamide, and a crosslinked rubber having a particle diameter of 1 μm or less in order to reduce the occurrence of powder dropping from a prepreg. I have. Patent Document 2 discloses an epoxy resin composition containing an epoxy resin and a phenoxy resin modified with an acid anhydride.

JP 2001-302813 A JP 2000-336242 A

  However, in the prepregs prepared from the resin compositions described in Patent Documents 1 and 2, although the occurrence of powder drop is reduced to some extent, foaming occurs in the varnish due to components such as cross-linked rubber and phenoxy resin, and The wettability to the material may be reduced. Therefore, the appearance of the prepreg may be deteriorated. In addition, the prepreg needs to have good adhesion to the base material. It is not easy to obtain a prepreg having high adhesion to a substrate, less occurrence of powder dropping, and good appearance.

  An object of the present invention is to provide a resin composition capable of forming a cured product having a good surface appearance and high adhesion to a substrate, a prepreg produced from the resin composition and having less powder falling, a resin composition or a resin composition thereof. An object of the present invention is to provide a resin-attached film and a resin-attached metal foil containing a semi-cured product, and a metal-clad laminate and a printed wiring board containing a cured product of the resin composition or a prepreg cured product.

  The resin composition according to the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a phenoxy resin having a weight average molecular weight in the range of 30,000 to 100,000, and (D) a surface conditioner. , (E) an antifoaming agent. The (D) surface conditioner contains a polyether-modified polydimethylsiloxane. The (E) antifoaming agent contains an acrylic copolymer.

  A prepreg according to the present invention has a fiber base material and the resin composition impregnated in the fiber base material or a semi-cured product thereof.

  The film with a resin according to the present invention has a support film and a resin layer provided on the support film, and the resin layer contains the resin composition or a semi-cured product thereof.

  The resin-attached metal foil according to the present invention includes a metal foil and a resin layer provided on the metal foil, and the resin layer includes the resin composition or a semi-cured product thereof.

  The metal-clad laminate according to the present invention has a metal layer and an insulating layer provided on the metal layer, and the insulating layer includes a cured product of the resin composition or a cured product of the prepreg. .

  The printed wiring board according to the present invention has an insulating layer and a conductor wiring provided on the insulating layer, and the insulating layer includes a cured product of the resin composition or a cured product of the prepreg.

  According to the present invention, a resin composition capable of forming a cured product having a good surface appearance and high adhesion to a substrate, a prepreg produced from this resin composition and having less powder falling, this resin composition or A resin-coated film and a resin-containing metal foil containing the semi-cured product, and a metal-clad laminate and a printed wiring board containing a cured product of the resin composition or a prepreg cured product can be obtained.

FIG. 1 is a sectional view of a prepreg according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of the film with resin according to one embodiment of the present invention. FIG. 3 is a cross-sectional view of the metal foil with resin according to one embodiment of the present invention. FIG. 4 is a cross-sectional view of the metal-clad laminate according to one embodiment of the present invention. FIG. 5 is a sectional view of a printed wiring board according to one embodiment of the present invention. FIG. 5A is a sectional view of a printed wiring board having a single-layer structure, and FIG. 5B is a sectional view of a printed wiring board having a multilayer structure. FIG. 6 is a sectional view of the flex-rigid printed wiring board according to the first embodiment of the present invention. FIG. 7 is a sectional view of a flex-rigid printed wiring board according to the second embodiment of the present invention. FIG. 8 is a sectional view of a flex-rigid printed wiring board according to the third embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described.

[Resin composition according to the present embodiment]
The resin composition according to the present embodiment (hereinafter, referred to as composition (X)) has (A) an epoxy resin, (B) a curing agent, and (C) a weight average molecular weight of 30,000 or more and 100,000 or less. It contains a phenoxy resin, (D) a surface conditioner, and (E) an antifoaming agent. (D) The surface conditioner contains a polyether-modified polydimethylsiloxane. (E) The antifoaming agent contains an acrylic copolymer.

  In the present embodiment, since the composition (X) has the above-described configuration, the prepreg produced from the composition (X) has a good surface appearance and a high adhesion to a base material, Low occurrence.

  The components contained in the composition (X) will be described in more detail.

<(A) Epoxy resin>
The epoxy resin (A) (hereinafter, referred to as the component (A)) can impart thermosetting properties to the composition (X). Further, when the composition (X) contains the component (A), the cured product of the composition (X) can have good heat resistance.

  The component (A) may have photocurability in addition to thermosetting properties. The polymerization reaction of the component (A) is not particularly limited. Specific examples of the polymerization reaction include chain polymerization and sequential polymerization. A typical example of the chain polymerization is a radical polymerization. A typical example of the sequential polymerization includes polyaddition.

  Examples of the component (A) include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; and novolak-type epoxy resins such as phenol novolak-type epoxy resin and cresol novolak-type epoxy resin. A biphenyl type epoxy resin, a xylylene type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl aralkyl type epoxy resin, a biphenyl novolak type epoxy resin, a biphenyl dimethylene type epoxy resin, a trisphenol methane novolak type epoxy resin, and a tetramethyl biphenyl type epoxy resin And the like. Arylalkylene-type epoxy resins such as tetrafunctional naphthalene-type epoxy resins; naphthalene skeleton-modified cresol novo Naphthalene skeleton-modified epoxy resins such as lacquer type epoxy resin, naphthalene diol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, methoxy naphthalene modified cresol novolac type epoxy resin, methoxy naphthalene dimethylene type epoxy resin; triphenylmethane type epoxy resin; Anthracene-type epoxy resin; dicyclopentadiene-type epoxy resin; norbornene-type epoxy resin; fluorene-type epoxy resin; flame-retardant epoxy resin obtained by halogenating the above epoxy resin; and phosphorus-modified epoxy resin. As the component (A), one of these may be used alone, or two or more of them may be used in combination.

  When the composition (X) contains a bisphenol A type epoxy resin having a weight average molecular weight in the range of 30,000 or more and 100,000 or less, the bisphenol A type epoxy resin is used as the composition (X) as a phenoxy resin of the component (C). It is contained in. Therefore, the bisphenol A type epoxy resin contained as the component (A) is a bisphenol A type epoxy resin having a weight average molecular weight of less than 30,000 or a bisphenol A type epoxy resin having a weight average molecular weight of more than 100,000.

  The component (A) preferably contains a phosphorus-modified epoxy resin. The phosphorus-modified epoxy resin means an epoxy resin containing a phosphorus atom. When the component (A) contains a phosphorus-modified epoxy resin, the flame retardancy can be imparted to the cured product of the composition (X) without adding a halogen-based flame retardant, so that it is environmentally friendly.

  The phosphorus-modified epoxy resin is not particularly limited. For example, a phosphorus-modified epoxy resin obtained by reacting an organic phosphorus compound with a quinone compound and reacting a reaction product generated by this reaction with the epoxy resin is used. be able to.

  When the component (A) contains a phosphorus-modified epoxy resin, the phosphorus-modified epoxy resin preferably has a structure represented by the following formula (1). In this case, the cured product of the composition (X) may have excellent flame retardancy.

  The content of the component (A) is preferably within a range from 40 parts by mass to 80 parts by mass with respect to 100 parts by mass of the composition (X). In this case, the composition (X) can have a sufficient thermosetting property. The content of the component (A) is more preferably in the range of 50 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the composition (X).

  When the component (A) contains a phosphorus-modified epoxy resin, the phosphorus-modified epoxy resin is preferably contained such that the phosphorus concentration in 100 parts by mass of the component (A) is 1% or more. In this case, the cured product of the composition (X) may have higher flame retardancy. More preferably, the phosphorus-modified epoxy resin is contained so that the phosphorus concentration in 100 parts by mass of the component (A) is 1.5% or more.

<(B) Curing agent>
The curing agent (B) (hereinafter, referred to as the component (B)) reacts with the component (A) in the composition (X) to cure the composition (X). Examples of the component (B) include an amine-based curing agent, a phenol-based curing agent, a urea-based curing agent, and an acid anhydride-based curing agent. The component (B) may contain only one of these, or two or more thereof.

  Examples of the amine-based curing agent include dicyandiamide, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, and diaminodiphenylsulfone. Examples of the phenolic curing agent include a bisphenol A type novolak resin, a phenol novolak resin, a cresol novolak resin, a phenol aralkyl resin, and a biphenyl aralkyl resin. Examples of urea-based curing agents include phenyldimethyl urea. Examples of the acid anhydride-based curing agent include phthalic anhydride, succinic anhydride, and trimellitate anhydride.

  The component (B) preferably contains an amine curing agent. In this case, powder falling of the semi-cured product and the cured product of the composition (X) can be further reduced.

  The component (B) preferably contains dicyandiamide. When the component (B) contains dicyandiamide, the curing rate when the composition (X) is heated and cured is likely to be slow, so that the semi-cured product and the cured product of the composition (X) are less likely to be brittle. . Thereby, powder dropping of the prepreg produced from the composition (X) can be particularly reduced. When the component (B) contains dicyandiamide, the semi-cured and cured products of the composition (X) may have particularly high adhesion to a polyimide substrate. Since the polyimide substrate is suitably used as a coverlay or the like of a printed wiring board, the prepreg produced from the composition (X) can be effectively used as a substrate material for producing a printed wiring board.

  The component (B) may contain only dicyandiamide, or may contain both dicyandiamide and a curing agent component other than dicyandiamide. For example, the component (B) may contain both dicyandiamide and a phenolic curing agent.

  The component (B) is contained in the composition (X) such that the active hydrogen equivalent of the component (B) is within the range of 0.3 or more and 0.8 or less with respect to 1 epoxy equivalent of the component (A). It is preferably contained, and more preferably contained in the range of 0.4 or more and 0.7 or less. Here, the epoxy equivalent is a ratio of the molecular weight of the epoxy resin to the number of epoxy groups contained in the molecule of the epoxy resin. The active hydrogen equivalent is the ratio of the molecular weight of the compound used as the curing agent to the number of active hydrogens directly connected to the nitrogen atom of the amino group in the compound used as the curing agent.

  When the component (B) contains dicyandiamide, the content of dicyandiamide is preferably 2.9% by mass or more based on the entire component (B). In this case, powder falling off of the prepreg can be satisfactorily reduced, and the adhesion of the semi-cured product and the cured product of the composition (X) to the polyimide substrate can be further increased. The content of dicyandiamide is more preferably at least 3.6% by mass based on the whole component (B).

<(C) Phenoxy resin>
The (C) phenoxy resin (hereinafter, referred to as the (C) component) is a resin that has been polymerized into a linear chain by a condensation reaction between bisphenols and epichlorohydrin. The component (C) imparts flexibility to the prepreg produced from the composition (X), and can reduce the occurrence of powder drop. In addition, when the composition (X) contains the component (C), the semi-cured product and the cured product of the composition (X) can have particularly good adhesion to a polyimide substrate.

  The component (C) may have a thermosetting property or a photosetting property. When the component (C) has polymerizability, the polymerization reaction is not particularly limited. Specific examples of the polymerization reaction include chain polymerization and sequential polymerization.

  The weight average molecular weight of the component (C) is in the range from 30,000 to 100,000. When the weight average molecular weight of the component (C) is in the range of 30,000 or more and 100,000 or less, it is possible to reduce the occurrence of powder falling of the prepreg produced from the composition (X). When the weight average molecular weight of the component (C) is within this range, the cured product of the composition (X) has good flexibility and the glass transition temperature of the cured product is not excessively low. Can be Further, the cured product may have higher adhesion to the polyimide substrate.

  As the component (C), for example, product numbers “YP-50” and “YP50S” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. can be used.

  The component (C) is preferably contained in the range of 10 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the total of the components (A) and (B). When the content of the component (C) is within this range, the occurrence of powder dropping of the prepreg produced from the composition (X) can be further reduced, and the cured product of the composition (X) can be a polyimide-based resin. It may have higher adhesion to the material. Further, the cured product has good flexibility and can prevent the glass transition temperature of the cured product from being too low.

<(D) Surface conditioner>
(D) The surface conditioner (hereinafter referred to as the component (D)) can enhance the wettability of the composition (X), so that when the composition (X) is impregnated into a glass cloth, cissing occurs. The appearance of the prepreg can be prevented from being deteriorated.

  The component (D) contains a polyether-modified polydimethylsiloxane. When the component (D) contains the polyether-modified polydimethylsiloxane, the prepreg produced from the composition (X) can have an excellent surface appearance.

  The component (D) may contain only the polyether-modified polydimethylsiloxane, or may further contain a surface conditioner other than the polyether-modified polydimethylsiloxane. Examples of the surface conditioner other than the polyether-modified polydimethylsiloxane include polyester-modified polydimethylsiloxane, hydroxyl-containing polyester-modified polydimethylsiloxane, polyaralkyl-modified polydimethylsiloxane, epoxy functional group-containing polyether-modified polydimethylsiloxane, and fluorine-containing polydimethylsiloxane. Including oligomers containing hydrophilic groups and lipophilic groups.

  The component (D) is preferably contained in the range of 0.1 part by mass or more and 0.3 part by mass or less with respect to 100 parts by mass in total of the component (A) and the component (B). When the content of the component (D) is within this range, the prepreg and the composition prepared from the composition (X) can be obtained without reducing the adhesion of the cured product of the composition (X) to the polyimide substrate. The surface appearance of the cured product of the product (X) can be improved. The component (D) is more preferably contained in the range of 0.1 part by mass or more and 0.2 part by mass or less based on 100 parts by mass of the total of the component (A) and the component (B).

<(E) Antifoaming agent>
(E) An antifoaming agent (hereinafter, referred to as a component (E)) can suppress foaming of the composition (X). Since the composition (X) contains the component (E) in addition to the component (D) as described above, foaming of the composition (X) is suppressed and wettability of the composition (X) is improved. Therefore, occurrence of poor appearance due to foaming or repelling is suppressed in the prepreg produced from the composition (X). Further, the composition (X) contains the component (D) and the component (E) together with the component (A), the component (B), and the component (C), so that the cured product of the composition (X) can be obtained. It is possible to obtain a prepreg that has a good appearance and hardly causes powder dropout without lowering the adhesion to the polyimide substrate.

  The component (E) contains an acrylic copolymer. For this reason, foaming of the composition (X) containing the component (E) is suppressed, and when the composition (X) is impregnated into a glass cloth to produce a prepreg, foaming occurs to deteriorate the appearance of the prepreg. Can be prevented.

  The component (E) may contain only an acrylic copolymer, or may further contain an antifoaming agent other than the acrylic copolymer. Examples of defoamers other than acrylic copolymers include foam-breaking polysiloxanes, fluorine-modified silicones, and vinyl polymers.

  The component (E) is preferably contained in the range of 0.1 part by mass or more and 1.0 part by mass or less based on 100 parts by mass of the total of the components (A) and (B). When the content of the component (E) is within this range, foaming of the composition (X) can be particularly suppressed. The component (E) is more preferably contained in the range of 0.1 part by mass or more and 0.4 part by mass or less based on 100 parts by mass of the total of the component (A) and the component (B).

<(F) Core shell rubber>
The composition (X) preferably contains (F) a core-shell rubber (hereinafter, referred to as a (F) component). The component (F) can impart flexibility to the prepreg and the cured product made from the composition (X) without significantly affecting the glass transition temperature of the cured product of the composition (X). For this reason, powder fall of the prepreg produced from the composition (X) is reduced. Furthermore, since the composition (X) contains the component (F), the composition (X) has a good impregnation property to the substrate, and the prepreg produced from the composition (X) has a good prepreg. It can have moldability.

  The component (F) is an aggregate of rubber particles. The rubber particles have a core portion and a shell portion surrounding the core portion. That is, the rubber particles are a composite material containing different materials for the core portion and the shell portion.

  The core portion is not particularly limited, but may include, for example, silicone / acryl rubber, acrylic rubber, silicone rubber, nitrile rubber, butadiene rubber, and the like. The core preferably contains silicone acrylic rubber or acrylic rubber. In this case, higher flexibility can be imparted to the prepreg and the cured product produced from the composition (X).

  The shell part is not particularly limited, but may be composed of, for example, a plurality of graft chains bonded to the core part. The graft chain may have a functional group. Examples of the functional group include a methacryl group, an acrylic group, a vinyl group, an epoxy group, an amino group, a ureido group, a mercapto group, and an isocyanate group. Further, the shell portion may be made of a polymer such as polymethyl methacrylate and polystyrene.

  The shape and particle size of the rubber particles are not particularly limited. The average particle size of the rubber particles is, for example, preferably in a range of 0.01 μm to 2.0 μm, and more preferably in a range of 0.1 μm to 1.0 μm. The average particle size of the rubber particles is a volume-based median diameter calculated from a measured value of the particle size distribution by a laser diffraction / scattering method, and can be obtained by using a commercially available laser analysis / scattering type particle size distribution measuring device.

  As the component (F), for example, product numbers “SRK200A”, “S2100”, “SX-005”, “S-2001”, “S-2006”, “S-2030”, “S-2030” manufactured by Mitsubishi Rayon Co., Ltd. -200 "," SX-006 "," W-450A "," E-901 "," C-223A "; product numbers" AC3816 "," AC3816N "," AC3832 "," AC4030 "manufactured by Aika Kogyo Co., Ltd. , "AC3364", "IM101"; "MX-217", "MX-153", "MX-960", etc., manufactured by Kaneka Corporation.

  The component (F) is preferably contained in a range of 5 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the total of the components (A) and (B). In this case, the prepreg produced from the composition (X) can have particularly good substrate adhesion. Furthermore, in this case, it is possible to prevent the thermal expansion coefficient of the cured product of the composition (X) from becoming too high.

<(G) Inorganic filler>
The composition (X) preferably contains (G) an inorganic filler (hereinafter, referred to as a (G) component). When the composition (X) contains the component (G), the cured product of the composition (X) may have a lower coefficient of thermal expansion. In particular, when the composition (X) contains the component (F), the cured product of the composition (X) tends to have a high coefficient of thermal expansion, but the composition (X) contains the component (F) and the component (G). When the composition contains (X), the cured product of the composition (X) can have a low coefficient of thermal expansion, so that deformation such as warpage and generation of cracks are easily suppressed even when subjected to thermal stress.

  The component (G) is not particularly limited. For example, aluminum hydroxide, silica, barium sulfate, silicon oxide powder, crushed silica, calcined talc, zinc molybdate coated talc, barium titanate, titanium oxide, clay, alumina, mica , Boehmite, zinc borate, zinc stannate, other metal oxides and metal hydrates, calcium carbonate, magnesium hydroxide, magnesium silicate, short glass fiber, aluminum borate whisker, silicon carbonate whisker, etc. . As the component (G), one type of these inorganic fillers may be used alone, or two or more types may be used in combination. The component (G) preferably contains at least one of aluminum hydroxide and silica.

  The shape and particle size of the component (G) are not particularly limited. The average particle diameter of the component (G) is preferably, for example, in the range of 0.1 μm or more and 5.0 μm or less. The average particle size of the component (G) is a volume-based median diameter calculated from a measured value of a particle size distribution by a laser diffraction / scattering method, and can be obtained by using a commercially available laser analysis / scattering type particle size distribution measuring device.

  The component (G) may be subjected to a surface treatment with a coupling agent or the like. Thereby, the adhesion of the cured product of the composition (X) to the substrate can be increased. As the coupling agent, for example, a silane coupling agent such as an epoxy silane coupling agent and a mercapto silane coupling agent can be used.

  The content of the component (G) is preferably in the range of 5 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the component (A). When the content of the component (G) is within this range, the coefficient of thermal expansion of the cured product of the composition (X) can be reduced without adversely affecting the powder-fallability of the prepreg produced from the composition (X). can do. The content of the component (G) is more preferably in the range of 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the component (A).

<Other ingredients>
When the effect of the present invention is not impaired, the composition (X) contains components other than the components (A), (B), (C), (D), and (E). Is also good. The composition (X) may contain, for example, a dispersant, a colorant, an adhesion promoter, a curing accelerator, an organic solvent, other resins, and additives.

  When the effect of the present invention is not impaired, the composition (X) may contain, for example, a resin other than the components (A) and (C). The composition (X) may contain, for example, a phenol resin, a bismaleimide resin, a cyanate resin, and the like.

[Prepreg according to the present embodiment]
A prepreg 1 according to the present embodiment will be described with reference to FIG.

  The prepreg 1 according to the present embodiment includes a fiber base material 12 and a composition (X) impregnated in the fiber base material 12 or a semi-cured product 11 of the composition (X).

  The fibrous base material 12 is not particularly limited. For example, a woven base material such as a plain woven base material in which warp yarns and weft yarns are woven so as to be substantially orthogonal can be used. As the fiber base 12, for example, a woven base made of inorganic fibers, a woven base made of organic fibers, or the like can be used. As the woven fabric base made of inorganic fibers, for example, glass cloth and the like can be mentioned. Examples of the woven fabric base made of organic fibers include aramid cloth and polyester cloth.

  When the resin component in the composition (X) undergoes chain polymerization (for example, radical polymerization), the prepreg 1 has the composition (X) impregnated in the fiber base material 12. In this case, the composition (X) impregnated in the fiber base material 12 is not originally in the B-stage state, but reaches the C-stage by heat or light to become a cured product. The B-stage refers to an intermediate stage in which the resin composition in the A-stage state (varnish state) is cured to the C-stage state (cured state).

  When the resin component in the composition (X) undergoes sequential polymerization (for example, polyaddition), the prepreg 1 has a semi-cured product 11 of the composition (X) impregnated in a fiber base material 12. In this case, the composition (X) impregnated in the fiber base material 12 is originally in a B-stage state, that is, a semi-cured state, and reaches the C-stage by heat to become a cured product.

  The prepreg 1 can be formed, for example, by impregnating the fiber base material 12 with the composition (X) and heating and drying it until it becomes a semi-cured state. The temperature condition and time for the semi-cured state can be, for example, 170 to 200 ° C. and 30 to 90 minutes. Further, the prepreg 1 can be formed by impregnating the fiber base material 12 with the composition (X) and drying it.

  Since the prepreg 1 thus formed is formed using the composition (X), it has not only high adhesion to the base material but also a good surface appearance as described above. . In addition, since the prepreg 1 is unlikely to cause powder drop during handling and production of the laminated board, it is possible to prevent the produced laminated board from being dented like a dent, and occurrence of a dent defect.

[Film with resin according to the present embodiment]
With reference to FIG. 2, the resin-attached film 2 according to the present embodiment will be described.

  The resin-attached film 2 according to the present embodiment has a support film 21 and a resin layer 13. The resin layer 13 includes the composition (X) or the semi-cured product 11 of the composition (X). In FIG. 2, the resin-attached film 2 has a two-layer configuration including the resin layer 13 and one support film 21 provided on one surface of the resin layer 13, but is not limited thereto. The resin-attached film 2 may have a three-layer configuration including a resin layer 13 and two support films 21 provided on both surfaces of the resin layer 13.

  The support film 21 is not particularly limited as long as it has a strength for supporting the resin layer 13. When the resin-attached film 2 is used as a material for producing a printed wiring board and the support film 21 and the resin layer 13 need to be separated, the support film 21 can be separated from the resin layer 13. Is preferred.

  When the resin component in the composition (X) undergoes chain polymerization (for example, radical polymerization), the resin layer 13 contains the composition (X). In this case, the resin layer 13 is not in the B-stage state from the beginning, but reaches the C-stage by heat or light and becomes a cured product.

  When the resin component in the composition (X) undergoes sequential polymerization (for example, polyaddition), the resin layer 13 includes the semi-cured product 11 of the composition (X). In this case, the resin layer 13 is originally in the B-stage state, that is, in a semi-cured state, and reaches the C-stage by heat to become a cured product.

  The resin-attached film 2 can be produced, for example, by laminating one or more prepregs 1 having a semi-cured product of the composition (X) on one side or both sides of the prepreg 1. In this case, the prepreg 1 becomes the resin layer 13.

  The resin-attached film 2 may be manufactured without using the prepreg 1. For example, it can be formed by directly applying the varnish-like composition (X) to the surface of the support film 21 and heating and drying it until it becomes a semi-cured state. The temperature condition and time for the semi-cured state can be, for example, 170 to 200 ° C. and 30 to 90 minutes. The resin-attached film 2 can be formed by directly applying the varnish-like composition (X) to the surface of the support film 21 and drying the composition.

  Since the resin-attached film 2 thus formed is formed using the composition (X), as described above, the resin layer 13 not only has high adhesion to the base material, Has good surface appearance. In addition, the resin-attached film 2 is less likely to fall off during handling and during production of the laminate.

[Resin-attached metal foil according to the present embodiment]
The metal foil 3 with resin according to the present embodiment will be described with reference to FIG.

  The metal foil 3 with resin according to the present embodiment has a metal foil 22 and a resin layer 13. The resin layer 13 includes the semi-cured material 11 of the composition (X). The resin-attached metal foil 3 has a two-layer configuration including a resin layer 13 and one metal foil 22 provided on one surface of the resin layer 13.

  When the resin component in the composition (X) undergoes chain polymerization (for example, radical polymerization), the resin layer 13 contains the composition (X). In this case, the resin layer 13 is not in the B-stage state from the beginning, but reaches the C-stage by heat or light and becomes a cured product.

  When the resin component in the composition (X) undergoes sequential polymerization (for example, polyaddition), the resin layer 13 includes the semi-cured product 11 of the composition (X). In this case, the resin layer 13 is originally in the B-stage state, that is, in a semi-cured state, and reaches the C-stage by heat to become a cured product.

  The resin-attached metal foil 3 can be formed, for example, by directly applying the varnish-like composition (X) to the surface of the metal foil 22 and heating and drying the composition to a semi-cured state. The temperature condition and time for the semi-cured state can be, for example, 170 to 200 ° C. and 30 to 90 minutes. Further, the resin-attached metal foil 3 can be formed by directly applying the varnish-like composition (X) to the surface of the metal foil 22 and drying the composition.

  The resin-attached metal foil 3 may be manufactured using the prepreg 1. For example, the prepreg 1 having a semi-cured product of the composition (X) can be produced by laminating one or more prepregs 1 with a metal foil 22 on one surface. In this case, the prepreg 1 becomes the resin layer 13.

  Since the resin-attached metal foil 3 thus formed is formed using the composition (X), as described above, the resin layer 13 not only has high adhesion to the base material, but also has , Has a good surface appearance. Further, the resin-attached metal foil 3 is less likely to fall off during handling and during production of the laminate.

[Metal-clad laminate according to the present embodiment]
The metal-clad laminate 4 according to the present embodiment will be described with reference to FIG.

  The metal-clad laminate 4 according to the present embodiment has a metal layer 20 and an insulating layer 10 provided on the metal layer 20. The insulating layer 10 includes a cured product of the composition (X) or a cured product of the prepreg 1.

  The metal layer 20 is provided on at least one surface of the insulating layer 10. That is, the configuration of the metal-clad laminate 4 may be a two-layer configuration including the insulating layer 10 and the metal layer 20 disposed on one surface of the insulating layer 10. A three-layer configuration including two metal layers 20 arranged on both surfaces may be employed. FIG. 4 is a sectional view of the metal-clad laminate 4 having a three-layer structure.

  The metal-clad laminate 4 is formed by laminating one or more prepregs 1 each having a semi-cured product of the composition (X) on one side or both sides, and molding by heating and pressing. It can be manufactured by forming The lamination molding can be performed by heating and pressing using, for example, a multi-stage vacuum press, a hot press, a double belt, or the like. In this case, the insulating layer 10 is produced by curing the prepreg 1.

  The insulating layer 10 of the metal-clad laminate 4 formed as described above has high adhesion to the base material and has a good surface appearance. Therefore, the metal-clad laminate 4 having the insulating layer 10 containing the cured product of the composition (X) can be effectively used as a substrate material for producing a printed wiring board.

[Printed wiring board according to the present embodiment]
The printed wiring boards 5 and 6 according to the present embodiment will be described with reference to FIGS. 5A and 5B.

  The printed wiring boards 5 and 6 according to the present embodiment include the insulating layer 10 and the conductor wiring 30 provided on the insulating layer 10. The insulating layer 10 includes a cured product of the composition (X) or a cured product of the prepreg 1.

  The printed wiring board 5 (hereinafter, may be referred to as a core material 500) includes one insulating layer 10 containing a cured product of the composition (X) and the conductor wiring 30 provided on one or both surfaces of the insulating layer 10. It is a printed wiring board having a single-layer structure. FIG. 5A is a cross-sectional view of the printed wiring board 5 having a single-layer structure, including one insulating layer 10 and two conductive wires 30 provided on both surfaces of the one insulating layer 10. In the printed wiring board 5 having a single-layer structure, through holes, via holes, and the like may be formed as necessary.

  The printed wiring board 6 is configured by alternately forming the insulating layers 10 and the conductor wirings 30 alternately on the surface of the core material 500 on which the conductor wirings 30 are formed, and the conductor wiring 31 is formed on the outermost layer. It is a printed wiring board having a structure. In the printed wiring board 6 having a multilayer structure, at least one of the plurality of insulating layers 10 contains a cured product of the composition (X). In the printed wiring board 6 having a multilayer structure, it is preferable that all of the plurality of insulating layers 10 include a cured product of the composition (X). FIG. 5B is a cross-sectional view of the printed wiring board 6 having a multilayer structure including three insulating layers 10 and four conductive wires 30. In the printed wiring board 6 having a multilayer structure, through holes, via holes, and the like may be formed as necessary.

  The method of manufacturing the printed wiring board 5 having a single-layer structure is not particularly limited. For example, a subtractive method of forming a conductor wiring 30 by removing a part of the metal layer 20 of the metal-clad laminate 4 by etching. Forming a thin electroless plating layer by electroless plating on one or both sides of an unclad plate comprising an insulating layer 10 containing a cured product of the composition (X), protecting a non-circuit-forming portion with a plating resist, A semi-additive method of forming a conductive wiring 30 by forming an electrolytic plating layer on a circuit forming portion by plating, removing a plating resist, and removing an electroless plating layer other than the circuit forming portion by etching. The method for manufacturing the printed wiring board 6 having a multilayer structure is not particularly limited, and includes, for example, a build-up process.

[Flex-rigid printed wiring board according to first embodiment]
A flex-rigid printed wiring board 7 according to the first embodiment will be described with reference to FIG.

  The flex-rigid printed wiring board 7 according to the first embodiment includes a plurality of rigid portions 51, a flex portion 52 connecting the plurality of rigid portions 51, and at least one of the plurality of rigid portions 51 and the flex portion 52. And a conductor wiring 30 (32) provided. At least one of the plurality of rigid portions 51 includes a cured product of the composition (X). Specifically, the flex-rigid printed wiring board 7 according to the first embodiment has two rigid portions 51, one flex portion 52, and the conductor wiring 30 (32). At least one of the plurality of insulating layers 10 provided in the rigid portion 51 includes a cured product of the composition (X).

  The rigid part 51 is a rigid part having hardness and strength that can withstand the weight of the mounted component and can be fixed to the housing. The flex portion 52 is a flexible portion having flexibility that can be bent. The flex-rigid printed wiring board 7 is used in a small and lightweight device such as a portable electronic device by being bent in the flex portion 52 and accommodated in a housing or the like. The thickness of the flex portion 52 is preferably, for example, in the range of 5 μm or more and 300 μm or less. In this case, the flex portion 52 has good flexibility.

  The flex-rigid printed wiring board 7 is formed, for example, by using a single-layer flexible printed wiring board 200 having one insulating layer 50 and two conductor wirings 30 as a core material (hereinafter, may be referred to as a core material 200). Can be manufactured. The rigid part 51 is formed by multilayering the core material 200 except for the part that becomes the flex part 52. That is, a part of the core material 200 becomes the flex part 52, and the other part of the core material 200 becomes the rigid part 51. The material of the insulating layer 50 in the core material 200 is not particularly limited as long as it is a flexible material, and may include a flexible resin such as polyimide. Further, the technique for multi-layering is not particularly limited, and a known technique is used. For example, a multilayer structure can be formed by a build-up method using the metal foil 3 with resin having the metal foil 22 and the resin layer 13 containing the semi-cured composition (X). In a plurality of regions where the rigid portion 51 is formed in the core material 200, the metal foil 3 with resin is overlapped on both surfaces of the core material 200, and the resin foil of the metal foil 3 with resin is formed by heating and pressing in this state. The layer 13 adheres to the core material 200 and the resin layer 13 is cured, so that the insulating layer 10 of the rigid portion 51 is formed. Subsequently, the metal foil 22 of the metal foil 3 with resin is subjected to an etching process or the like, so that the conductor wiring 32 is formed in the rigid portion 51. As a result, the rigid portion 51 is formed, and the flex portion 52 connecting the rigid portions 51 is formed.

  In the flex-rigid printed wiring board 7 shown in FIG. 6, the rigid part 51 includes a part of the core material 200, the insulating layer 10 provided on the core material 200, and the conductor wiring 32 provided on the insulating layer 10. , But is not limited thereto. The rigid portion 51 may include, for example, a solder resist layer provided on the outermost layer. The rigid part 51 may have a structure in which two or more insulating layers 10 and two or more conductor wirings 32 are alternately provided on both sides of the core material 200. That is, the rigid portion 51 may be further multilayered by a build-up method or the like. A through hole, a via hole, and the like may be formed in the rigid portion 51 as necessary.

  In the flex-rigid printed wiring board 7 shown in FIG. 6, the flex portion 52 includes an insulating layer 50 which is a part of the core material 200. That is, the flex portion 52 is a part of the insulating layer 50. The configuration of the flex section 52 is not limited to this, and the flex section 52 may include, for example, the conductor wiring 30. That is, the conductor wiring 30 may be formed on the insulating layer 50 of the flex portion 52. Further, a cover lay covering the conductor wiring 30 of the core material 200 may be provided. In this case, the flex portion 52 includes the insulating layer 50, the conductor wiring 30, and the cover lay. The insulating layer 50 may have a single-layer structure including one insulating layer, or may have a multilayer structure in which a plurality of insulating layers are stacked. When the flexibility of the flex portion 52 is not hindered, the flex portion 52 may have a multilayer structure. In this case, for example, by using a flexible printed wiring board having a multilayer structure as a core material, a rigid flex printed wiring board is formed. Can be produced.

  In the flex-rigid printed wiring board 7 shown in FIG. 6, at least one of the plurality of insulating layers 10 contains a cured product of the composition (X). That is, at least one of the plurality of rigid portions 51 includes a cured product of the composition (X).

[Flex-rigid printed wiring board according to second embodiment]
A flex-rigid printed wiring board 8 according to the second embodiment will be described with reference to FIG. Hereinafter, the same components as those of the flex-rigid printed wiring board 7 according to the first embodiment are denoted by the same reference numerals in the drawings, and detailed description will be omitted.

  The flex-rigid printed wiring board 8 according to the second embodiment includes a plurality of rigid portions 51, a flex portion 52 connecting the plurality of rigid portions 51, and at least one of the plurality of rigid portions 51 and the flex portion 52. And a conductor wiring 30 (32) provided. At least one of the plurality of rigid portions 51 includes a cured product of the composition (X). Specifically, the flex-rigid printed wiring board 8 according to the second embodiment has two rigid portions 51, one flex portion 52, and the conductor wiring 30 (32). At least one of the plurality of insulating layers 10 provided in the rigid portion 51 includes a cured product of the composition (X).

  In the flex-rigid printed wiring board 8 according to the second embodiment, a solder resist layer 60 is provided on the outermost layer of the rigid portion 51. Further, a cover lay 40 that covers the conductor wiring 30 of the core material 200 is provided. Further, a through-hole 101 and a buried via hole 102 are formed in the rigid portion 51. The configuration of the flex-rigid printed wiring board 8 is not limited to this, and the flex-rigid printed wiring board 8 may not have the solder resist layer 60. Further, the flex-rigid printed wiring board 8 may not have the coverlay 40. A blind via hole may be further formed in the rigid portion 51 as necessary.

  The flex-rigid printed wiring board 8 can be manufactured by using, for example, a flexible printed wiring board 200 having a single-layer structure having one insulating layer 50 and two conductor wirings 30 as a core material. The material of the insulating layer 50 in the core material 200 is not particularly limited as long as it is a flexible material, and may include a flexible resin such as polyimide. A cover lay 40 that covers the conductor wiring 30 is formed by laminating a cover lay film on both surfaces of the core material 200. Thereby, the flexible printed wiring board 300 having the core material 200 and the coverlay 40 is manufactured. The rigid portion 51 is formed by multilayering the flexible printed wiring board 300 except for the portion that becomes the flex portion 52. That is, a part of the flexible printed wiring board 300 becomes the flex part 52, and another part of the flexible printed wiring board 300 becomes the rigid part 51. The technique for multilayering is not particularly limited, and a known technique is used. For example, multilayering can be performed by the same method as the above-described flex-rigid printed wiring board 7 of the first embodiment. Specifically, it can be multilayered by a build-up method using the metal foil 3 with resin having the metal foil 22 and the resin layer 13 containing the semi-cured composition (X). In a plurality of regions of the flexible printed wiring board 300 where the rigid portions 51 are formed, the metal foil with resin 3 is overlapped on each of both surfaces of the flexible printed wiring board 300, and is heated and pressed in this state to form a metal with resin. The resin layer 13 of the foil 3 adheres to the flexible printed wiring board 300 and the resin layer 13 containing the composition (X) is cured, so that the insulating layer 10 is formed in the rigid portion 51. Subsequently, the metal foil 22 of the metal foil 3 with resin is subjected to an etching process or the like, so that the conductor wiring 32 is formed in the rigid portion 51. The formation of the insulating layer 10 and the formation of the conductor wiring 32 are alternately repeated to form the solder resist layer 60 as the outermost layer. As a result, the rigid portion 51 is formed, and the flex portion 52 connecting the rigid portions 51 is formed. The through hole 101 and the buried via hole 102 can be formed by a known method.

  As another method for manufacturing the flex-rigid printed wiring board 8, a method using a prepreg 1 having a fiber base material 12 and a semi-cured material 11 of the composition (X) impregnated in the fiber base material 12 shown in FIG. Is mentioned. An opening is formed in the prepreg 1 by punching out the prepreg 1 by die processing or the like. This opening corresponds to the flex portion 52 of the flex-rigid printed wiring board 8. The prepreg 1 having an opening is superimposed on the flexible printed wiring board 300 and is molded under heat and pressure in this state, whereby the prepreg 1 is cured, and the insulating layer 10 containing the cured product of the composition (X) is formed into the rigid portion 51. Formed. On the other hand, since the opening of the prepreg 1 corresponds to the flex portion 52, the insulating layer 10 is not formed in the flex portion 52. Subsequently, the conductor wiring 32 is formed on the insulating layer 10 by a known method. The formation of the insulating layer 10 using the prepreg 1 having the opening and the formation of the conductor wiring 32 are alternately repeated to form the solder resist layer 60 as the outermost layer. As a result, the rigid portion 51 is formed, and the flex portion 52 connecting the rigid portions 51 is formed.

[Flex-rigid printed wiring board according to third embodiment]
A flex-rigid printed wiring board 9 according to the third embodiment will be described with reference to FIG. Hereinafter, the same components as those of the flex-rigid printed wiring board 7 according to the first embodiment and the flex-rigid printed wiring board 8 according to the second embodiment are denoted by the same reference numerals in the drawings, and detailed description thereof will be omitted.

  The flex-rigid printed wiring board 9 according to the third embodiment includes a plurality of rigid portions 51, a flex portion 52 connecting the plurality of rigid portions 51, and at least one of the plurality of rigid portions 51 and the flex portion 52. And a conductor wiring 30 (32) provided. At least one of the plurality of rigid portions 51 includes a cured product of the composition (X). Specifically, the flex-rigid printed wiring board 9 according to the third embodiment has two rigid portions 51, one flex portion 52, and the conductor wiring 30 (32). At least one of the plurality of bonding sheets 70 provided on the rigid portion 51 includes a cured product of the composition (X).

  In the flex-rigid printed wiring board 9 according to the third embodiment, a cover lay 40 that covers the conductor wiring 30 of the core material 200 is provided. Further, a through hole 101 and a blind via hole 103 are formed in the rigid portion 51. The configuration of the flex-rigid printed wiring board 9 is not limited to this, and the flex-rigid printed wiring board 9 may not have the cover lay 40. Further, a buried via hole may be further formed in the rigid portion 51 as necessary. Further, the rigid portion 51 may include a solder resist layer provided on the outermost layer.

  The flex-rigid printed wiring board 9 includes, for example, a flexible printed wiring board 300 and a rigid printed wiring board 400 similar to those used for manufacturing the flex-rigid printed wiring board 8 of the second embodiment, as shown in FIG. It can be manufactured using the prepreg 1. The flexible printed wiring board 300 includes a core material 200 including one insulating layer 50 and two conductor wirings 30, and two coverlays 40. The rigid printed wiring board 400 is a multilayer printed wiring board having two insulating layers 10 and three conductor wirings 32, and has blind via holes 103 formed by a known method. First, an opening is formed in the prepreg 1 by punching out the prepreg 1 by die processing or the like. This opening corresponds to the flex portion 52 of the flex-rigid printed wiring board 9. The prepreg 1 having an opening is stacked on the flexible printed wiring board 300, and the rigid printed wiring board 400 is stacked on each of the prepregs 1. In this state, the prepreg 1 is cured by heating and pressing to form the bonding sheet 70 containing the composition (X), and the flexible printed wiring board 300 and the rigid printed wiring board 400 form the bonding sheet 70. Glued through. Thereafter, the through hole 101 can be formed by a known method. Since the opening of the prepreg 1 corresponds to the flex portion 52, the bonding sheet 70 is not formed in the flex portion 52.

  The configuration of the rigid printed wiring board 400 is not limited to the configuration shown in FIG. The rigid printed wiring board 400 may have a configuration similar to that of the single-layer printed wiring board 5 shown in FIG. 5A having one insulating layer 10 and two conductor wirings 30, for example. The rigid printed wiring board 400 may have the same configuration as the multilayer printed wiring board 6 shown in FIG. 5B having three insulating layers 10 and four conductor wirings 30. And five conductor wirings 30. Note that, in the flex-rigid printed wiring board 9 of the third embodiment, the insulating layer 10 of the rigid printed wiring board 400 may or may not include a cured product of the composition (X).

  Hereinafter, the present invention will be described specifically with reference to Examples.

1. Production of Resin Composition Of the components shown in the “Composition” column of Tables 1 and 2 below, component (A), component (B), and component (C) were prepared using a mixed solvent of methyl ethyl ketone and dimethylformamide. , Were mixed at the ratios shown in Tables 1 and 2, and the mixture was stirred for 30 minutes. Next, to this mixture, the remaining components shown in the "Composition" column of Tables 1 and 2 were added in the proportions shown in Tables 1 and 2, and dispersed by a ball mill to obtain Examples 1 to 11 and Comparative Examples 1 to 11. Thus, a resin composition (resin varnish) of No. 8 was obtained.

Details of the components in the column of “Composition” in Tables 1 and 2 are as follows.
Epoxy resin A: phosphorus-modified epoxy resin, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., part number FX-289
Epoxy resin B: polyfunctional epoxy resin, KOLON INDUSTRIES, INC. Made, product number KET-4131
-Curing agent: dicyandiamide, manufactured by Nippon Carbide Industry Co., Ltd.-Phenoxy resin A: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YP-50, weight average molecular weight 70,000, tensile elongation 33%
-Phenoxy resin B: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YP-50S, weight average molecular weight 60000, tensile elongation 30%
-Phenoxy resin C: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number ZX-1356-2, weight average molecular weight 70000, tensile elongation 12%
-Surface conditioner A: polyether-modified polydimethylsiloxane, manufactured by BYK Japan KK, part number BYK-333
Surface modifier B: hydroxyl group-containing polyester-modified polydimethylsiloxane, manufactured by BYK Japan KK, part number BYK-370
-Antifoaming agent A: acrylic copolymer solution, manufactured by BYK Japan KK, part number BYK-392
-Antifoaming agent B: foamable polysiloxane solution, manufactured by BYK Japan KK, part number BYK-066N
・ Core shell rubber: Acrylic rubber, manufactured by Aika Kogyo Co., Ltd., part number AC-3816N
-Inorganic filler A: Aluminum hydroxide, manufactured by Sumitomo Chemical Co., Ltd., part number CL-303M
-Inorganic filler B: crushed silica, manufactured by Cibelco Japan KK, part number Megasil 525RCS
・ Curing accelerator: 2-ethyl-4-imidazole, manufactured by Shikoku Chemicals Co., Ltd., product number 2E4MZ

  In addition, the tensile elongation of the phenoxy resin A, the phenoxy resin B, and the phenoxy resin C was measured as follows. A resin plate (length: 15 cm, width: 1 mm, thickness: 100 μm) of each of the phenoxy resins A to C was prepared, and the tensile elongation of the resin plate was measured using an autograph (model number AG-IS, manufactured by Shimadzu Corporation). At a temperature of 23 ± 2 ° C. and a tensile speed of 1 mm / min.

2. Preparation of Prepreg The resin varnish of each Example and Comparative Example was impregnated into a glass cloth (manufactured by Nitto Boseki Co., Ltd., # 1078 type, WEA1078) so that the thickness after curing became 80 μm, and the melt viscosity at 170 ° C. was 60000. The prepreg containing the resin composition in a semi-cured state was obtained by heating and drying until it reached １５０150,000 Poise. The melt viscosity was measured using a Koka type flow tester (CFT-100, manufactured by Shimadzu Corporation) at a temperature of 130 ° C. and a pressure of 1.96 MPa (20 kgf / cm ² ). The nozzle was 1 mm in diameter and 1 mm in thickness.

3. Evaluation test 3-1. Powder Fallability The prepregs of Examples and Comparative Examples produced in the above 2 were cut into a size of 11 × 10 cm (length × width), and a test was performed using them as test pieces. First, deposits such as powder and dust were removed from the ten test pieces using a handy mop. Next, the weight of ten test pieces was measured. Subsequently, 10 cuts each having a length of 10 cm were cut into each of the 10 test pieces at regular intervals using a cutter knife (available from NTT Corporation, A-type cutter replacement blade), and the 10 cut test pieces were cut. Deposits such as powder and dust were removed from the pieces. Then, the weight of the ten test pieces with the cuts was measured. The value obtained by subtracting the weight of the ten test pieces after making the cut from the weight of the ten test pieces before making the cut was defined as the amount of powder falling off. The percentage of the amount of powder falling with respect to the weight of the ten test pieces before making the cut was defined as the powder falling property.

3-2. Polyimide adhesion The copper foil of the flexible metal-clad laminate (Enflex (R), copper foil thickness 12 μm, polyimide thickness 20 μm, manufactured by SK Innovation Co., Ltd.) was removed by etching to obtain a polyimide sheet. Next, the obtained polyimide sheet and one of the prepregs of each of the examples and the comparative examples produced in the above 2 were laminated, and heated and applied at 190 ° C. and a pressure of 2.94 MPa (30 kgf / cm ² ) for 60 minutes. The laminate was produced by pressing. This laminate was cut into a size of 10 × 100 mm to obtain a test piece. From this test piece, the one-sided flexible metal-clad laminate was peeled off at a speed of 50 mm / min by a tensile tester, and the peel strength at that time was measured. This peel strength was defined as polyimide adhesion.

3-3. Defoaming property The resin varnish of each of Examples and Comparative Examples prepared in the above 1 was stirred at 3000 rpm for 10 minutes, and then left in a closed container for 1 hour. Thereafter, when the lid of the closed container was opened, the residual foam on the surface of the resin varnish was visually observed and evaluated as follows.
A: The portion of the surface of the resin varnish covered with bubbles is less than half the area of the surface of the resin varnish.
B: Although the surface of the resin varnish can be visually confirmed, the portion of the surface of the resin varnish covered with bubbles is larger than half the area of the surface of the resin varnish.
C: The entire surface of the resin varnish is covered with bubbles.

3-4. Surface appearance The prepregs of Examples and Comparative Examples produced in the above 2 were cut into a size of 150 × 150 mm (length × width) and used as a test piece. The cissing on the surface of the test piece was visually checked and evaluated as follows.
A: Less than 5 cissings.
B: The number of repelling is 5 or more and less than 10.
C: The number of repelling is 10 or more.

DESCRIPTION OF SYMBOLS 1 Pre-preg 2 Film with resin 3 Metal foil with resin 4 Metal-clad laminate 5, 6 Printed wiring board 11 Semi-cured material 12 Fiber base material 13 Resin layer 10 Insulation layer 20 Metal layer 21 Support film 22 Metal foil 30 Conductor wiring

Claims (13)

(A) an epoxy resin,
(B) a curing agent;
(C) a phenoxy resin having a weight average molecular weight of 30,000 or more and 100,000 or less;
(D) a surface conditioner;
(E) an antifoaming agent,
The (D) surface conditioner contains a polyether-modified polydimethylsiloxane,
The (E) antifoaming agent contains an acrylic copolymer,
Resin composition. (F) further containing a core-shell rubber;
The resin composition according to claim 1. The (F) core-shell rubber is contained in a range of 5 parts by mass or more and 25 parts by mass or less based on a total of 100 parts by mass of the (A) epoxy resin and the (B) curing agent.
The resin composition according to claim 2. (G) further containing an inorganic filler;
The resin composition according to claim 1. The (B) curing agent contains dicyandiamide,
The resin composition according to claim 1. The (C) phenoxy resin is contained in the range of 10 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the total of the (A) epoxy resin and the (B) curing agent.
The resin composition according to claim 1. The (D) surface conditioner is contained in the range of 0.1 part by mass or more and 0.3 part by mass or less based on 100 parts by mass of the total of the (A) epoxy resin and the (B) curing agent. ,
The resin composition according to claim 1. The (E) antifoaming agent is contained in the range of 0.1 part by mass or more and 1.0 part by mass or less based on 100 parts by mass of the total of the (A) epoxy resin and the (B) curing agent. ,
The resin composition according to claim 1. A fiber substrate,
A prepreg comprising: the resin composition according to claim 1 or a semi-cured product thereof impregnated in the fiber base material. A support film;
And a resin layer provided on the support film,
The resin layer contains the resin composition according to any one of claims 1 to 8 or a semi-cured product thereof.
Film with resin. Metal foil,
And a resin layer provided on the metal foil,
The resin layer contains the resin composition according to any one of claims 1 to 8 or a semi-cured product thereof.
Metal foil with resin. A metal layer,
And an insulating layer provided on the metal layer,
The insulating layer includes a cured product of the resin composition according to any one of claims 1 to 8 or a cured product of the prepreg according to claim 9.
Metal-clad laminate. An insulating layer,
And a conductor wiring provided on the insulating layer,
The insulating layer includes a cured product of the resin composition according to any one of claims 1 to 8 or a cured product of the prepreg according to claim 9.
Printed wiring board.

Images