JP5724503B2 - Resin film for printed wiring board and method for producing the same - Google Patents

Description

  The present invention relates to a resin film for printed wiring boards and a method for producing the same.

  In mobile communication devices typified by mobile phones, communication base station devices and peripheral devices (antennas, power amplifiers, filters, etc.), high-speed and large-capacity signals are being used. Along with this, it is necessary to cope with higher frequency signals of printed wiring boards mounted on these devices, and there is a need for a substrate material that can reduce transmission loss of printed wiring boards. In recent years, practical applications and practical plans for systems that handle millimeter-wave (30 GHz ~) signals in the ITS field (related to automobiles and transportation systems) and indoor short-range communication fields are particularly popular as wireless applications that handle such high-frequency signals. In the future, it is expected that further reduction of transmission loss will be required for printed wiring boards mounted on these devices.

  Conventionally, in order to obtain a printed wiring board with a low transmission loss, a fluorine-based resin having a low relative dielectric constant and dielectric loss tangent has been used as a substrate material. However, the fluororesin is not only high in cost, but also has a problem that it is necessary to perform press molding under high temperature and high pressure conditions because of high melting temperature and melt viscosity and relatively low fluidity. In addition, there is a problem that the processability, thermal expansion characteristics, dimensional stability, and adhesion to metal plating are insufficient for use in printed wiring board applications. In addition, it is difficult to bond or combine with other resin materials, and its application is limited. Furthermore, since the fluororesin is basically a thermoplastic resin, it is difficult to use it in applications requiring heat resistance and applications requiring dielectric property stability with respect to temperature.

  On the other hand, with the downsizing and high functionality of electronic devices, there has been a demand for substrate materials that are thin, lightweight, and capable of high-density wiring. In recent years, a build-up lamination type printed wiring board having an inner via hole (IVH) structure in which only a necessary layer is connected with a non-through hole has been developed and is rapidly spreading. Resin films that do not contain a glass cloth (glass cloth) base material are often used for the insulating layer of build-up laminated printed wiring boards, and the holes for IVH are photolithography or thermosetting using a photosensitive resin. It is formed by a method such as thermally decomposing a functional resin with a laser processing machine.

  As the material of the resin film described above, an epoxy resin material having heat resistance is applied to the build-up wiring board, and a polyimide material having film forming ability is applied to the flexible printed wiring board. Yes. However, printed wiring boards provided with these resin films have high relative dielectric constant and dielectric loss tangent, and are insufficient in high-frequency characteristics (low transmission loss). In addition, liquid crystal polymers (LCPs) of wholly aromatic polyesters have recently attracted attention as materials for resin films with excellent high-frequency characteristics. Although printed wiring boards equipped with LCP have a low dielectric loss tangent, they have a relative dielectric constant of 3 As above, it is higher than fluororesin-based materials. Further, LCP is not only costly but also a thermoplastic resin having a high melting temperature like a fluororesin, and its application is limited because of poor workability and adhesion to metals and other resin materials.

  Therefore, a polyphenylene ether (PPO or PPE) resin of a heat-resistant thermoplastic resin (engineering plastics) is known as a material for a resin film exhibiting a low dielectric constant, although it does not reach that of a fluororesin. However, in order to apply to an insulating layer of a printed wiring board, heat resistance that can withstand a solder connection process at the time of mounting is required. As a method for improving the heat resistance and solvent resistance, a method of modifying a polyphenylene ether resin with a thermosetting resin has been proposed. For example, as a resin film using a cyanate ester resin having a low dielectric constant among thermosetting resins, there is a polyphenylene ether resin film using a curable resin composition in which a cyanate ester resin is blended with a polyphenylene ether resin (Patent Document 1). reference).

  In addition, a metal-clad laminate (see Patent Document 2) prepared using a resin composition containing a polyphenylene oxide resin composition, a crosslinkable polymer and a crosslinkable monomer, a flame retardant or a flame retardant aid, and an unsaturated group A film obtained by appropriately crosslinking a specific cured polyphenylene ether resin is also disclosed (see Patent Document 3). The present inventors have also proposed a modified cyanate ester resin film using a polyphenylene ether resin and a cyanate ester resin (see Patent Document 4). A resin film in which an elastomer is blended with a polyphenylene ether-containing modified cyanate ester resin or the like is also disclosed (see Patent Document 5).

  Further, Patent Document 6 discloses a thermosetting containing an uncured semi-IPN type composite obtained by compatibilizing a polyphenylene ether and a prepolymer formed from a butadiene polymer and a crosslinking agent, and a saturated thermoplastic elastomer. A copper-clad laminate produced using the resin composition and the resin composition are disclosed.

  On the other hand, in Patent Document 7, in a connection member including an adhesive composition in which cyanate ester resin / epoxy resin / latent curing agent is essential, various thermoplastic resins such as styrene elastomer are blended in the adhesive composition. Is disclosed.

Japanese Patent Publication No. 1-53700 Japanese Patent Publication No. 5-77705 JP-A-7-188362 Japanese Patent Laid-Open No. 11-124451 JP 2003-138133 A JP 2007-302877 A JP-A-9-279121

  However, even the resin compositions described in Patent Documents 1 to 7 achieve dielectric properties (low relative dielectric constant and low dielectric loss tangent) in a high frequency region required for printed wiring boards for millimeter wave applications. Is not necessarily enough. In particular, in a resin composition containing an acrylic rubber or a modified polybutadiene-based elastomer as described in Patent Document 5, the adverse effect in the high frequency region becomes significant. Further, even when blended with a styrene elastomer as described in Patent Document 7, since the elastomer used is only a polar group-containing type, not only high frequency characteristics but also moisture resistance, heat discoloration resistance, etc. Slightly insufficient. Further, according to the study by the present inventors, in the case of the resin compositions described in Patent Documents 1 to 6, from the viewpoint of ensuring compatibility with the main component polyphenylene ether, Since the blending amount is limited, it has also been found that the degree of freedom of composition that can be practically used is small.

  The present invention has been made in view of such circumstances, and a printed wiring capable of imparting good dielectric properties in a high frequency region to a printed wiring board while sufficiently ensuring compatibility of resin components. It aims at providing the resin film for boards, and its manufacturing method.

In order to solve the above-mentioned problems, a method for producing a resin film for a printed wiring board of the present invention includes (A) a saturated thermoplastic elastomer having a styrene unit, (B) an epoxy resin, a cyanate ester resin, a polybutadiene resin, and a maleimide. A thermosetting resin component containing at least one or more thermosetting resins selected from the group consisting of compounds, and a thermosetting resin curing agent and a curing accelerator, which are blended as necessary, (B) The mass ratio W _A / W _B of the content W _A of the component (A) to the content W _B of the component is 0.430 to 5.000, and the content of polyphenylene ether is the component (A) and (B ) A resin composition that is 10 parts by mass or less with respect to 100 parts by mass in total of the components is cast-applied on one side of a support substrate, and the resin composition is semi-cured or cured by heat drying. Including the.

In the method for producing a resin film for a printed wiring board of the present invention, (A) a saturated thermoplastic elastomer having a styrene unit, and (B) at least selected from the group consisting of an epoxy resin, a cyanate ester resin, a polybutadiene resin, and a maleimide compound It contains the kind of thermosetting resin, and a thermosetting resin component comprising a curing agent and curing accelerator for the thermosetting resin to be incorporated as required, 0.430～ mass ratio W _{a /} W _B A resin composition having a polyphenylene ether content of 5.000 and 10 parts by mass or less with respect to a total of 100 parts by mass of the component (A) and the component (B) is cast on one side of the support substrate. The process of apply | coating and semi-hardening or hardening | curing a resin composition by heat drying is included. When the resin film thus obtained is used in the production of a printed wiring board, the printed wiring board can be provided with dielectric properties equivalent to or higher than those of a printed wiring board made of a resin film containing a certain amount or more of polyphenylene ether. In addition, the inventors of the present invention are a metal-cure cured resin film in which a metal foil (copper foil) is laminated on both surfaces of a resin film obtained by the production method of the present invention. components and the mass ratio W _{a /} W _B are compared to the metal-clad cured resin film of a different resin film, the ratio in the high frequency range the dielectric constant and dielectric loss tangent are both low, make sure that the dielectric properties are excellent Yes. In addition, although the metal-clad cured resin film in this specification refers to the resin film with metal foil obtained by laminating | stacking metal foils, such as copper foil, on the surface (one side or both sides) of a resin film, and heating and pressurizing, this book In the specification, for the convenience of explanation, the description of the dielectric property of the resin film means the dielectric property of the insulating layer portion obtained by removing the metal foil of the metal-clad cured resin film by etching or the like.
In addition, the above-described metal-clad cured resin film is obtained by applying a resin composition to one side of a supporting base material and then drying by heating, and does not impregnate a glass cloth with the resin composition. The inventors consider that the point that the resin composition is not impregnated into the glass cloth in the present invention is also one of the reasons why the effect of improving the low dielectric properties is exhibited.

Further, if the glass cloth is not impregnated with the resin composition as in the production method of the present invention, a resin composition having excellent handleability and strength may not be molded. Therefore, by the production method of the present invention as described above to adjust the kind of the component (A) and component (B) in the resin composition and the weight ratio W _{A /} W _B, impregnated with the resin composition to the glass cloth Even if not, it is possible to produce a resin film that is thin and excellent in handleability (tackiness, cracking, powder falling, etc.).

  In addition, the resin film obtained by the production method of the present invention achieves excellent appearance and multilayer formability at the same time. In addition, about the point which the inventors are excellent in multilayer moldability, the multilayer wiring board (printed wiring board) manufactured using the resin film obtained by the manufacturing method of the present invention is free from voids and scrapes, and the circuit. It is confirmed by observing that the resin is uniformly filled. In addition, a metal-clad cured resin film using the resin film has solder heat resistance that can withstand a solder connection process at the time of mounting, and is excellent in moisture absorption resistance. Therefore, it is also suitable for outdoor use.

  By the way, as a metal foil used for a printed wiring board for high frequency applications, it is common to use a low profile foil having a small surface roughness in order to reduce transmission loss (conductor loss) caused by a conductor. However, according to the study by the present inventors, when a laminate is formed from a low profile foil using the resin composition or film described in Patent Documents 1 to 3, a practical level of peeling strength is ensured. I found it impossible. The resin film described in Patent Document 4 can obtain sufficient adhesion and heat resistance when a low profile foil is applied, but has insufficient dielectric characteristics in a high frequency region, and transmission loss due to the dielectric characteristics. However, it is difficult to avoid an increase in transmission loss of the entire printed wiring board even if it is compensated for by applying a low profile foil.

  On the other hand, the resin film produced according to the present invention has a sufficiently high peel strength from a low profile foil or the like having a small surface roughness. For this reason, since the said resin film can suppress a conductor loss by using low profile foil with small surface roughness as a metal foil, the further reduction of the loss loss of a printed wiring board can be aimed at.

As (A) component of this invention, what contains a styrene-ethylene-butylene copolymer can be used preferably.
The component (A) preferably contains a saturated thermoplastic elastomer obtained by hydrogenation of an unsaturated double bond of a structural unit derived from butadiene of a styrene-butadiene copolymer, More preferably, the component (A) contains a non-modified saturated thermoplastic elastomer having no maleic anhydride group at the side chain or terminal.

  The component (A) preferably contains a saturated thermoplastic elastomer having a number average molecular weight of less than 60,000, and the content ratio of the saturated thermoplastic elastomer having a number average molecular weight of less than 60,000 is 50% by mass or more. Is more preferable. In this case, when the obtained resin film is adhered to a conductor or other resin substrate material, the adhesiveness between the two can be enhanced.

  It is preferable that the component (A) further contains a saturated thermoplastic elastomer having a number average molecular weight of 60,000 or more. When the component (A) includes a saturated thermoplastic elastomer having a number average molecular weight of less than 60,000 and a saturated thermoplastic elastomer having a number average molecular weight of 60,000 or more, a metal foil having a small surface roughness such as a low profile foil A resin film having a high peel strength and a tack-free resin film that is free from cracking and powder falling are obtained, and when a PET film or the like is used as a support substrate, it is excellent in releasability.

It is preferable that the component (A) contains a chemically modified saturated thermoplastic elastomer having a maleic anhydride group in the side chain or terminal, and the component (A) has no maleic anhydride group in the side chain or terminal. More preferably, it further contains a modified saturated thermoplastic elastomer.
Moreover, it is preferable that the ratio of the said chemically modified saturated thermoplastic elastomer is 20-50 mass% on the basis of the total mass of (A) component. In this case, when the obtained resin film is bonded to a conductor or another resin substrate material, the adhesiveness between the two is improved and the resin film is bonded to a circuit board or a substrate with via holes to produce a multilayer board. Multi-layer formability at the time is improved.

  (B) component contains 40 mol% or more of structural units derived from polyphenylene ether and 1,2-butadiene having a 1,2-vinyl group in the side chain, and the number average It is preferable to contain a polyphenylene ether-modified butadiene prepolymer obtained by reacting a non-chemically modified polybutadiene resin having a molecular weight of 500 to 10,000.

  In this case, the component (B) is used as an uncured polyphenylene ether-modified butadiene prepolymer obtained by prepolymerizing a polybutadiene resin. Thereby, the compatibility of (A) component and (B) component can be improved further, and heat resistance and adhesiveness can be improved more effectively.

  Polyphenylene ether-modified butadiene prepolymer is polyphenylene ether, polybutadiene resin, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) ) Selected from the group consisting of maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide and N-cyclohexylmaleimide. It is preferably obtained by reacting with at least one crosslinking agent. In this case, the prepolymerization reaction process can be controlled smoothly, and the properties of the resulting resin film (dielectric properties, heat resistance, moisture resistance, adhesiveness, multilayer formability, etc.) are excellent.

  Polyphenylene ether-modified butadiene prepolymer is polyphenylene ether, polybutadiene resin, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane It is preferably obtained by reacting with at least one crosslinking agent selected from the group consisting of: In this case, the prepolymerization reaction process can be controlled smoothly, and the properties of the resulting resin film (dielectric properties, heat resistance, moisture resistance, adhesiveness, multilayer formability, etc.) are excellent.

  The resin composition is N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethyl) Phenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide and N-cyclohexylmaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane And at least one crosslinking agent selected from the group consisting of 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane.

The component (B) includes at least one thermosetting resin selected from the group consisting of an epoxy resin, a cyanate ester resin, and a maleimide compound, and a curing agent and a curing accelerator for the thermosetting resin that are blended as necessary. containing a thermosetting resin component comprising, preferably a 0.700 to 5.000 mass ratio _W a / _{W B} content _{W a} to the content _{W B} of the component (B). Within this range, the obtained resin film has heat resistance, moisture resistance, and high adhesiveness while maintaining good film forming ability and handleability and dielectric properties in a high frequency band.

  The component (B) preferably contains a phenol-modified cyanate ester prepolymer obtained by reacting a cyanate ester resin and a monofunctional phenol compound to such an extent that they do not gel. In this case, the appearance and handleability of the uncured (B stage) film and the curability of the cured film are improved.

  A phenol-modified cyanate ester prepolymer is obtained by reacting a cyanate ester resin with at least one monofunctional phenol selected from the group consisting of pt-octylphenol, p-phenylphenol, and p- (α-cumyl) phenol. It is preferable.

  And at least one maleimide compound selected from the group consisting of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane. Furthermore, it is preferable to contain. When bis (3-ethyl-5-methyl-4-maleimidophenyl) methane is used, the hygroscopicity and the thermal expansion coefficient can be further reduced. On the other hand, when 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane is used, the fracture strength and the metal foil peeling strength can be further increased.

  As the component (C), it is preferable to further contain at least one selected from the group consisting of specific phenolic antioxidants represented by the following formulas (1) to (3). As a result, it is possible to impart an effect of suppressing secular change with respect to the dielectric characteristics and an effect of improving the insulation reliability without deteriorating the dielectric characteristics, moisture resistance, heat resistance and the like.

  In the above step, the resin composition is preferably cast-applied on one side of the support substrate in the form of a resin varnish obtained by dissolving or dispersing in a solvent.

  Examples of the supporting substrate include a metal foil or a PET film.

  It is preferable that the film thickness of the resin film after the said process is 1-200 micrometers. In this case, when a printed wiring board is produced using this resin film, the printed wiring board can be thinned, and an insulating layer having excellent high frequency characteristics and high film thickness accuracy can be formed.

  This invention provides the resin film for printed wiring boards produced by the manufacturing method of the resin film for printed wiring boards mentioned above.

  According to the present invention, even when a resin film containing a small amount of polyphenylene ether or containing no polyphenylene ether is used, compared with the case where a resin film containing a certain amount or more of polyphenylene ether is used, the dielectric in the high frequency region is reduced. The manufacturing method of the resin film for printed wiring boards which can obtain the printed wiring board from which a characteristic becomes equivalent or more can be provided. Moreover, it becomes possible to provide the resin film obtained by the said manufacturing method.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The method for producing a resin film for a printed wiring board according to this embodiment is selected from the group consisting of (A) a saturated thermoplastic elastomer having a styrene unit, and (B) an epoxy resin, a cyanate ester resin, a polybutadiene resin, and a maleimide compound. containing a thermosetting resin component containing at least one kind of thermosetting resin, and a curing agent and curing accelerator for the thermosetting resin to be optionally added is the weight ratio W _{a /} W _B 0 One side of the supporting base material is a resin composition having a polyphenylene ether content of 430 to 5.000 and 10 parts by mass or less with respect to 100 parts by mass in total of the components (A) and (B). And a step of semi-curing or curing the resin composition by heat drying.

  The saturated thermoplastic elastomer (A) is a component that is excellent in dielectric properties, moisture absorption resistance and adhesion to a conductor, and can impart film forming ability. On the other hand, it is a component for improving the heat resistance and solvent resistance of the (B) component thermosetting resin and the (A) component. By combining these as essential components, it is possible to produce a resin film for a printed wiring board having both high frequency characteristics and moisture resistance comparable to those of a fluororesin system, and having high adhesion and high heat resistance. As a result, it can be applied to high frequency applications such as millimeter wave signals. Hereinafter, each component of the resin composition used for the manufacturing method of this embodiment is explained in full detail.

[(A) component]
The component (A) is a saturated thermoplastic elastomer having a styrene unit in the molecule. The component (A) is not particularly limited as long as it is a saturated thermoplastic elastomer having a styrene unit in the molecule, and the content ratio of the styrene block is not particularly limited. Specific examples of the component (A) preferably used in the present embodiment include a styrene-ethylene-butylene copolymer (SEBS), and the unsaturated unit contained in the structural unit derived from butadiene of the styrene-butadiene copolymer. It can be obtained by hydrogenation to the double bond. That is, the saturated thermoplastic elastomer in the present embodiment means that an aliphatic hydrocarbon portion other than the aromatic hydrocarbon portion (styrene block) is composed of a saturated bonding group.

  In addition, the component (A) preferably contains a chemically modified saturated thermoplastic elastomer having a maleic anhydride group in the side chain or terminal, and is a non-modified saturated heat having no maleic anhydride group in the side chain or terminal. It is more preferable to contain a plastic elastomer and a chemically modified saturated thermoplastic elastomer, and the proportion of the chemically modified saturated thermoplastic elastomer is 20 to 50% by mass based on the total mass of the component (A). Is preferred.

  The component (A) preferably contains a saturated thermoplastic elastomer having a number average molecular weight of less than 60,000. Further, when the proportion of the saturated thermoplastic elastomer having a number average molecular weight of less than 60,000 in the component (A) is 50% by mass or more based on the total mass of the component (A), Since adhesiveness with other resin substrate materials can be improved, it is particularly preferable. The component (A) preferably contains a saturated thermoplastic elastomer having a number average molecular weight of less than 60,000 and a saturated thermoplastic elastomer having a number average molecular weight of 60,000 or more.

  Here, examples of the chemically-modified saturated thermoplastic elastomer include SEBS (manufactured by Asahi Kasei Chemicals Corporation, Tuftec M1911, M1913, M1943, etc.) modified with maleic anhydride. On the other hand, non-modified saturated thermoplastic elastomers include non-modified SEBS (manufactured by Asahi Kasei Chemicals, Tuftec H1041, H1051, H1043, H1053, H1141, etc.).

[Component (B)]
Next, the component (B) will be described. The first aspect of the component (B) is a thermosetting resin selected from the group consisting of an epoxy resin, a cyanate ester resin, a polybutadiene resin, and a maleimide compound, or a curing agent for a thermosetting resin blended as necessary (crosslinking). A thermosetting resin component. (B) If the component is a first aspect, the weight ratio _W A / _{W B} are 0.430 to 5.000, and the content of the polyphenylene ether (A) component and the (B) component It is essential that it is 10 parts by mass or less with respect to 100 parts by mass in total. Within this range, the obtained resin film has heat resistance, moisture resistance, and high adhesiveness while maintaining good film forming ability and handleability and dielectric properties in a high frequency band. The mass ratio _W A / _{W B} is more preferably 0.430 to 1.500, more preferably 0.430 to 1.000. If it is such a thermosetting resin component, it is not particularly limited, but it is more preferable to include a polybutadiene resin from the viewpoint of dielectric properties and moisture resistance, and it is preferable to use a polybutadiene resin and a maleimide compound in combination. Particularly preferred from the viewpoints of dielectric properties, moisture resistance, heat resistance, and thermal expansion properties.

  When an epoxy resin is used as the first embodiment of the component (B), any epoxy resin having two or more epoxy groups in the molecule may be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy Resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalene skeleton type epoxy resin, bifunctional biphenyl type Epoxy resins, biphenyl aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, dihydroanthracene type epoxy resins, diglycidyl ethers of phenols, diglycidyl ethers of alcohols, and alkyl-substituted products thereof Such as a halide and the like, which may be used in combination. In consideration of high frequency characteristics, it is more preferable to use a naphthalene skeleton type epoxy resin, a bifunctional biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin, or a dicyclopentadiene type epoxy resin.

  Moreover, when using an epoxy resin, a curing agent or a curing accelerator for the epoxy resin may be included. For example, polyfunctional phenols, amines, imidazole compounds, acid anhydrides, organophosphorus compounds, and halides thereof. Etc.

  When a cyanate ester resin is used as the first embodiment of the component (B), it is not particularly limited as long as it is a cyanate ester compound having two or more cyanate groups in the molecule. For example, 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1, 1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene, cyanate ester compound of phenol-added dicyclopentadiene polymer, phenol novolac type cyanate ester Examples thereof include compounds and cresol novolac type cyanate ester compounds. Specific examples of the cyanate ester compound include a phenol novolac-type cyanate ester compound and a cresol novolac-type cyanate ester compound. These may be used alone or in combination of two or more. .

  When the cyanate ester resin is used as the first aspect of the component (B), a curing agent or a curing accelerator for the cyanate ester resin may be included. For example, monofunctional phenols, polyfunctional phenols, amines, Examples thereof include acid anhydrides and organic metal compounds such as 2-ethylhexanoate such as manganese, iron, cobalt, nickel, copper, and zinc, naphthenate, and acetylacetone complex. In consideration of high frequency characteristics, moisture resistance, etc., it is more preferable to use a monofunctional phenol and an organometallic compound in combination. In consideration of heat resistance, the epoxy resin is preferably used in combination, and the epoxy resin can be suitably used.

  When a polybutadiene resin is used as the first aspect of the component (B), the polyphenylene ether described later and a structural unit derived from 1,2-butadiene and having a 1,2-vinyl group in the side chain are molecules. It is preferable to contain a polyphenylene ether-modified butadiene polymer that is obtained by reacting with a polybutadiene resin that is contained in an amount of 40 mol% or more and that has a number average molecular weight of 500 to 10,000 and is not chemically modified. In this case, the polybutadiene resin is chemically modified, such as epoxidation, glycolation, phenolization, maleation, (meth) acrylation, and urethanization, on the side chain 1,2-vinyl group and / or one end of the molecule. More preferably, the modified butadiene resin is not a modified polybutadiene. The polybutadiene resin may contain 50 mol% or more of a structural unit derived from 1,2-butadiene and having a 1,2-vinyl group in the side chain in consideration of curability. More preferably, it is more preferably 65 mol% or more. Further, the number average molecular weight is in the range of 700 to 8000 in consideration of the balance between the curability of the resin composition and the dielectric properties when the cured product is used and the fluidity of the resin when the printed wiring board is used. More preferably, it is still more preferably in the range of 1000 to 5000.

  When a maleimide compound is used as the first aspect of the component (B), a polymaleimide compound containing two or more maleimide groups in the molecule is preferable. Specific examples of the polymaleimide compound include 1,2-dimaleimidoethane, 1,3-dimaleimidopropane, bis (4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis (3 -Ethyl-5-methyl-4-maleimidophenyl) methane, 2,7-dimaleimidofluorene, N, N '-(1,3-phenylene) bismaleimide, N, N'-(1,3- (4- Methylphenylene)) bismaleimide, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ether, 1,3-bis (3-maleimidophenoxy) benzene, 1 , 3-bis (3- (3-maleimidophenoxy) phenoxy) benzene, bis (4-maleimidophenyl) ketone, , 2-bis (4- (4-maleimidophenoxy) phenyl) propane, bis (4- (4-maleimidophenoxy) phenyl) sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, 4,4′- Bis (3-maleimidophenoxy) biphenyl, 1,3-bis (2- (3-maleimidophenyl) propyl) benzene, 1,3-bis (1- (4- (3-maleimidophenoxy) phenyl) -1-propyl ) Benzene, bis (maleimidocyclohexyl) methane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis (maleimidophenyl) thiophene Among them, bis (3-ethyl-5-methyl) is particularly preferred in terms of further reducing the hygroscopicity and the coefficient of thermal expansion. It is more preferable to use -4-maleimidophenyl) methane, and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane is used in terms of further increasing the breaking strength and the metal foil peeling strength. More preferred.

  When a polybutadiene resin is used as the first aspect of the component (B), it is particularly preferable to use a maleimide compound as a crosslinking agent from the viewpoints of dielectric properties, moisture resistance, heat resistance, and thermal expansion properties. When using a maleimide compound as a cross-linking agent for a polybutadiene resin, the above-described polymaleimide compound can be used, and a monomaleimide compound containing one maleimide group in the molecule can also be used. Specific examples of the monomaleimide compound include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2 , 6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide and the like, among which N- More preferably, phenylmaleimide is used.

  When the polybutadiene resin and the maleimide compound are used in combination, the blending ratio of the maleimide compound is 2 with respect to 100 parts by mass of the polybutadiene resin in consideration of the balance between the thermal expansion coefficient, Tg, peel strength of the metal foil, and dielectric properties. It is preferable to set it as the range of -200 mass parts, It is more preferable to set it as 5-100 mass parts, It is especially preferable to set it as 10-75 mass parts.

  As a 1st aspect of (B) component, when using a polybutadiene resin or a maleimide compound together, it is preferable to contain the radical reaction initiator as a hardening accelerator. Specific examples of the radical polymerization initiator include dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, cumene hydroperoxide, 1,1-bis (t-hexylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2 , 2-bis (4,4-di (t-butylperoxy) cyclohexyl) propane, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis (t -Butylperoxy) hexyne-3, di-t-butyl peroxide, 1,1'-bis (t-butylperoxy) Isopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, t-butylperoxyacetate, 2,2 -Bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, bis (t-butylperoxy) ) Peroxides such as isophthalate, isobutyryl peroxide, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4 -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzo Down methyl ether, methyl -o- benzoyl benzoate, but not limited thereto.

When the component (B) is the first embodiment, the resin composition may or may not contain polyphenylene ether (hereinafter, also referred to as “component (B ′)”). It is 10 mass parts or less with respect to a total of 100 mass parts of (A) component and (B) component. The content of the component (B ′) is preferably 8 parts by mass or less, and more preferably 7 parts by mass or less.
In addition, as long as content of (B ') component is 10 mass parts or less with respect to a total of 100 mass parts of (A) component and (B) component, (B') component is included in a resin composition. As a result, the compatibility, heat resistance and adhesion of the resin composition can be improved, and a high Tg can be achieved. Examples of polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6) obtained by homopolymerization of 2,6-dimethylphenol and 2,3,6, -trimethylphenol. -Trimethyl-1,4-phenylene) ether or a copolymer of 2,6-dimethylphenol and 2,3,6, -trimethylphenol. In addition, so-called modified polyphenylene ether such as an alloyed polymer of these with polystyrene or styrene-butadiene copolymer can also be used.

  Moreover, when the resin composition in this embodiment contains the polyphenylene ether which is (B ') component, it is a structural unit derived from this polyphenylene ether and 1, 2- butadiene, and a 1, 2- vinyl group is in a side chain. In the form of a polyphenylene ether-modified butadiene polymer obtained by reacting with a non-chemically modified polybutadiene resin having a number average molecular weight of 500 to 10,000. It is preferable. In particular, polybutadiene resins are poorly compatible with polyphenylene ether, and using each of these as they are can adversely affect the handling (tackiness), appearance, adhesiveness, dielectric properties, heat resistance, thermal expansion properties, etc. of the film. Is expensive. Therefore, the compatibility of the component (B ′) and the component (B) can be improved by using the polybutabutadiene resin as a polyphenylene ether-modified butadiene polymer prepolymerized to such an extent that it does not gel. In addition, by containing the polyphenylene ether-modified butadiene prepolymer, the compatibility between the component (A) and the component (B) can be further improved, and the Tg, heat resistance, and adhesiveness can be improved more effectively. Can be achieved.

  In the case of producing a polyphenylene ether-modified butadiene prepolymer in the present embodiment, for example, after the component (B ′) is developed in a medium by dissolving it in a solvent, the polybutadiene resin and, if necessary, a crosslinking agent in this solution. And a radical polymerization initiator can be dissolved or dispersed and heated and stirred at 60 to 170 ° C. for 0.1 to 20 hours. When producing a polyphenylene ether-modified butadiene prepolymer in a solution, it is preferable to adjust the amount of the solvent used so that the solid content (nonvolatile content) concentration in the solution is usually 5 to 80% by mass. In addition, after producing the polyphenylene ether-modified butadiene prepolymer, the solvent may be completely removed by concentration or the like to obtain a solvent-free resin composition, or as a polyphenylene ether-modified butadiene prepolymer solution dissolved or dispersed in the solvent as it is. Also good. Also, in the case of a solution, a solution having a solid content (nonvolatile content) concentration increased by concentration or the like may be used.

  When producing the polyphenylene ether-modified butadiene prepolymer of the present embodiment, it is possible to smoothly control the prepolymerization reaction process by using a polybutadiene resin crosslinking agent, preferably a maleimide compound, more preferably a monomaleimide compound, In addition, it is desirable from the viewpoint of the obtained film characteristics (dielectric characteristics, heat resistance, moisture resistance, adhesiveness, multilayer formability, etc.). When producing a polyphenylene ether-modified butadiene prepolymer using a maleimide compound as a crosslinking agent, it is preferable to carry out a preliminary reaction so that the conversion (reaction rate) of the maleimide compound is in the range of 5 to 100%. A more preferable range varies depending on the blending ratio of the polybutadiene resin and the crosslinking agent. When the blending ratio of the crosslinking agent is in the range of 2 to 10 parts by mass with respect to 100 parts by mass of the polybutadiene resin, the conversion rate of the crosslinking agent ( The reaction rate is more preferably in the range of 10 to 100%, and in the case of 10 to 100 parts by mass, the conversion rate (reaction rate) of the crosslinking agent is more preferably in the range of 7 to 90%. In the range of 100 to 200 parts by mass, the conversion rate (reaction rate) of the crosslinking agent is more preferably in the range of 5 to 80%. The conversion rate (reaction rate) of the crosslinking agent is obtained by conversion from the remaining amount of the crosslinking agent in the polyphenylene ether-modified butadiene prepolymer measured by gel permeation chromatography and a calibration curve of the crosslinking agent prepared in advance. .

  In this embodiment, when a polyphenylene ether-modified butadiene prepolymer is produced in the resin composition after the resin composition is prepared, a polybutadiene resin crosslinking agent may be consumed with the production of the polyphenylene ether-modified butadiene prepolymer. . Therefore, it is preferable to add a polybutadiene resin crosslinking agent to the resin composition after the production of the polyphenylene ether-modified butadiene prepolymer. By replenishing the crosslinking agent consumed during the production of the prepolymer, the reaction process between the component (A) and the component (B) can be controlled smoothly. The additional crosslinking agent may be the same as or different from the crosslinking agent used in the production of the polyphenylene ether-modified butadiene prepolymer. As the crosslinking agent, it is preferable to use a maleimide compound, and it is more preferable to use the above-described polymaleimide compound. Among them, as described above, bis (3- (Ethyl-5-methyl-4-maleimidophenyl) methane is more preferable, and 2,2-bis (4- (4-maleimidophenoxy) phenyl) is more preferable in terms of further increasing the breaking strength and the metal foil peeling strength. More preferably, propane is used. In terms of cost, it is more preferable to use N-phenylmaleimide. A crosslinking agent may be used individually by 1 type, or may be used in combination of 2 or more types.

(B) The 2nd aspect of a component is a hardening agent (crosslinking agent) of the thermosetting resin chosen from the group which consists of an epoxy resin, cyanate ester resin, and a maleimide compound, or the thermosetting resin mix | blended as needed. It is a thermosetting resin component containing. Component (B) be a second aspect, the weight ratio _W A / _{W B} are 0.7 to 5.0, and the content of the polyphenylene ether component (A) and component (B) It is essential that it is 10 parts by mass or less with respect to 100 parts by mass in total. Within this range, the obtained resin film has heat resistance, moisture resistance, and high adhesiveness while maintaining good film forming ability and handleability and dielectric properties in a high frequency band. Mass ratio _W A / _{W B} is more preferably 0.8 to 2.0, more preferably 0.9 to 1.5. Such a thermosetting resin component is not particularly limited, but among these, cyanate ester resins are preferable from the viewpoint of dielectric properties, heat resistance, and adhesiveness, and a monofunctional phenol compound is used in combination or in advance. Use as a phenol-modified cyanate ester resin modified with a functional phenol compound is particularly preferred from the viewpoints of dielectric properties, moisture resistance, and heat resistance.

  (B) When using an epoxy resin as a 2nd aspect of a component, what kind of thing may be sufficient as long as it has two or more epoxy groups in a molecule | numerator, and the case where an epoxy resin is used as a 1st aspect Similar compounds can be used.

  Moreover, when using an epoxy resin, a curing agent or a curing accelerator for the epoxy resin may be included. For example, a polyfunctional phenol compound, an amine compound, an imidazole compound, an acid anhydride, an organic phosphorus compound, and a halide thereof. Etc.

  (B) As a 2nd aspect of a component, when using cyanate ester resin, if it is a cyanate ester compound which has two or more cyanate groups in a molecule | numerator, it will not specifically limit, Cyanate ester as a 1st aspect A compound similar to the case of using a resin can be used.

  Moreover, when using cyanate ester resin, the hardening | curing agent and hardening accelerator of cyanate ester resin may be contained, for example, a monofunctional phenol compound, a polyfunctional phenol compound, an amine compound, an acid anhydride, manganese, iron, Examples include 2-ethylhexanoate such as cobalt, nickel, copper, and zinc, naphthenate, and organometallic compounds such as acetylacetone complex. In consideration of high-frequency characteristics, moisture resistance, heat resistance, etc., it is more preferable to use a monofunctional phenol compound and an organometallic compound in combination. In consideration of heat resistance, the epoxy resin is preferably used in combination, and the epoxy resin can be suitably used.

  When a cyanate ester resin and a monofunctional phenol compound are used in combination, it is necessary to react the cyanate ester resin and the monofunctional phenol compound to such an extent that they do not gel, and prepolymerize them before use. And from the viewpoint of curability of the cured film. The monofunctional phenol compound to be blended may be blended in all prescribed amounts at the time of prepolymerization, or may be blended in a prescribed amount before and after prepolymerization, but it is better to preserve the storage stability of the varnish. It is preferable from the viewpoint.

  As specific examples of the monofunctional phenol compound, pt-octylphenol, p-phenylphenol, and p- (α-cumyl) phenol are preferably used, and the compounding amount of the monofunctional phenol compound is the cyanate group of the cyanate ester resin. The equivalent ratio of the hydroxyl group of the phenol compound to 0.01 to 1.00 is preferable from the viewpoints of dielectric properties, moisture resistance, and heat resistance.

  (B) As a 2nd aspect of a component, when using a maleimide compound, the polymaleimide compound which contains two or more maleimide groups in a molecule | numerator is preferable. As a specific example of the polymaleimide compound, the same compound as in the first embodiment can be preferably used.

  As a 2nd aspect of (B) component, when using a maleimide compound, the hardening | curing agent and hardening accelerator may be contained, for example, an amine compound, an organic peroxide, etc. are mentioned.

[Component (C)]
The resin composition in this embodiment can also use a specific phenolic antioxidant as the component (C). In this case, at least one phenolic antioxidant selected from the group of antioxidants represented by formulas (1) to (3) is preferably used. In addition, it is preferable that content of (C) component contains in 0.01-5 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (B ') component. In this case, without deteriorating the dielectric properties, moisture resistance, heat resistance, etc. of the resin film, it is possible to suppress the oxidative deterioration of the dielectric properties due to the high temperature treatment and improve the insulation reliability. In particular, when chemically modified SEBS is used as the component (A), the effect of suppressing the secular change of dielectric characteristics due to thermal oxidation can be exhibited.

[Flame retardant, inorganic filler, various additives]
In addition, the resin composition in the present embodiment includes a flame retardant, an inorganic filler, and various additives as necessary, with film characteristics (handleability, dielectric characteristics, heat resistance, adhesion to conductors and other resin materials, You may mix | blend further with the compounding quantity of the range which does not deteriorate a moisture resistance, Tg, a thermal expansion characteristic, etc.).

  Although it does not specifically limit as a flame retardant, Flame retardants, such as a bromine type, a phosphorus type, and a metal hydroxide, are used suitably. More specifically, brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl). , Ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated Brominated flame retardants such as polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromide Bisphenol A dimethacrylate, and unsaturated double bond group brominated reactive flame retardants containing such pentabromobenzylacrylate and brominated styrene.

  Phosphorus flame retardants include aromatic phosphoric acids such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate and resorcinol bis (diphenyl phosphate) Esters, phosphonic esters such as divinyl phenylphosphonate, diallyl phenylphosphonate and bis (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phos Phosphinic acid esters such as faphenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Phosphorus flame retardants such as melamine phosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and red phosphorus can be exemplified, and examples of metal hydroxide flame retardants include magnesium hydroxide and aluminum hydroxide. . Moreover, the above-mentioned flame retardant may be used individually by 1 type, and may be used in combination of 2 or more types.

  The blending ratio of the flame retardant is not particularly limited, but is preferably 10 to 200 parts by mass, and preferably 15 to 150 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). Is more preferable, and it is still more preferable to set it as 20-100 mass parts. If the blending ratio of the flame retardant is less than 10 parts by mass, the flame resistance tends to be insufficient, and if it exceeds 200 parts by mass, the heat resistance, adhesiveness, film-forming ability, and moldability tend to decrease.

  The inorganic filler is not particularly limited, and specifically, alumina, titanium oxide, mica, silica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, Aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, aluminum borate, silicon carbide and the like are used. These inorganic fillers may be used alone or in combination of two or more. Moreover, there is no restriction | limiting in particular also about the shape and particle size of an inorganic filler, Usually, the particle size of 0.01-50 micrometers, Preferably 0.1-15 micrometers is used suitably.

  The blending ratio of the inorganic filler is not particularly limited, but is preferably 5 to 100 parts by mass and more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It can mix | blend according to the balance of a desired dielectric property and a film characteristic.

  Although it does not specifically limit as various additives, For example, a silane coupling agent, a titanate coupling agent, antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a coloring agent, a lubricant, etc. are mentioned. Each may be used alone or in combination of two or more.

  When preparing the resin composition in the present embodiment, the (A) component, the (B) component, and the (B ′) component, the (C) component, the crosslinking agent, the flame retardant, the inorganic filler, and the combination used as necessary. The mixing method of various additives is not particularly limited, but it is preferable to use in the form of a resin varnish which is added with an organic solvent and stirred, dissolved and dispersed by a known method. The solvent used in this case is not particularly limited, but specific examples include alcohols such as methanol, ethanol and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol and the like. Ethers, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene, xylene, mesitylene, esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, N , N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other solvents. (A) When a mixed solvent of aromatic hydrocarbons such as toluene, xylene and mesitylene or aromatic hydrocarbons and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, which is a good solvent of component (A), is used as a film Is preferable because the appearance of the is good. Moreover, these may be used individually by 1 type and may be used in combination of 2 or more types.

  Further, when the resin composition is varnished, it is preferable to adjust the amount of the solvent used so that the solid content (nonvolatile content) concentration in the varnish is 5 to 80% by mass, but the resin film is produced. In this case, by adjusting the amount of the solvent, it is possible to adjust the solid content (non-volatile content) concentration and the varnish viscosity that are optimal for the coating operation (for example, to obtain a good appearance and a desired film thickness).

[Resin film]
In the present embodiment, a resin film can be produced by a known method using the resin varnish obtained as described above. For example, after applying the above-mentioned resin composition or resin varnish to one side of a supporting substrate such as a metal foil or a heat-resistant film (PET, etc.) using a kiss coater, roll coater, comma coater, etc., in a heating and drying furnace, etc. Usually 70-250 ° C. (above the temperature at which the solvent can be volatilized when a solvent is used), preferably 70-200 ° C., for 1-30 minutes, preferably 3-15 minutes, and then semi-cured (B A staged resin film, and a cured resin film obtained by heating the resin film at a temperature of 170 to 250 ° C., preferably 185 to 230 ° C. for 60 to 150 minutes in a heating furnace, are obtained.

[Metal-clad cured resin film]
Moreover, a metal-clad cured resin film can be manufactured using the resin film with a semi-hardened metal foil, the resin film with a heat resistant film, or the heat resistant film peeled off. That is, one or a plurality of resin films are stacked, and a metal foil is disposed on one or both sides thereof, and a temperature of 170 to 250 ° C., preferably 185 to 230 ° C. and a pressure of 0.5 to 5.0 MPa, 60 to 150. A double-sided or single-sided metal-clad resin film is obtained by heating and pressurizing for a minute. The heating / pressurization is preferably performed in a vacuum, and the degree of vacuum is preferably 10 kPa or less, preferably 5 kPa or less, and it is preferably performed for 30 minutes or more to the molding end time from the start of heating / pressurization.

[Multilayer printed wiring board]
Furthermore, the resin film with a semi-cured metal foil, the resin film with a heat-resistant film, or the resin film peeled off can be used for the production of a multilayer printed wiring board such as a build-up wiring board. That is, the semi-cured resin film obtained by the manufacturing method of the present embodiment is disposed on one or both sides of the core substrate subjected to circuit formation processing, or the semi-cured resin film is disposed between a plurality of core substrates. After heat / pressure laminate molding or heat / pressure press molding and multilayer adhesive processing, laser drilling, drilling, metal plating, metal etching, etc. are performed by known methods. Thus, a multilayer printed wiring board can be manufactured.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.
[Preparation of resin varnish]

  A resin varnish was prepared according to the following procedure and the blending amounts shown in Tables 1 to 3.

(Preparation Example 1)
Into a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator and stirrer, toluene and hydrogenated styrene-butadiene copolymer as component (A) (Tuftec H1051, styrene content ratio) : 42%, Mn: 66,000, manufactured by Asahi Kasei Chemicals Corporation), the temperature in the flask was set to 80 ° C. and dissolved by stirring. Next, as a component (B), a biphenyl aralkyl type epoxy resin (NC-3000H, manufactured by Nippon Kayaku Co., Ltd.) and a cresol novolac resin (KA 1165, manufactured by DIC) were blended and dissolved, and then the flask was cooled to room temperature. Thereafter, 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei) was added as a curing accelerator, and then methyl ethyl ketone was blended and stirred to prepare a resin varnish having a solid content concentration of about 35% by mass.

(Preparation Example 2)
In Preparation Example 1, ½ amount of (A) component Tuftec H1051 was replaced with hydrogenated styrene-butadiene copolymer having a number average molecular weight of 60,000 or less (Tuftec H1031, styrene content ratio: 30%, Mn: Resin varnish was prepared in the same manner as in Preparation Example 1 except that it was replaced with 47,000 (manufactured by Asahi Kasei Chemicals).

(Preparation Example 3)
In Preparation Example 2, a part of (A) component Tuftec H1051 was added to a hydrogenated maleic acid-modified styrene-butadiene copolymer (Tuftec M1913, styrene content ratio: 30%, Mn: 55,000, manufactured by Asahi Kasei Chemicals Corporation. ), And a resin varnish was prepared in the same manner as in Preparation Example 2, except that the compounding amounts shown in Table 1 were used.

(Preparation Example 4)
Into a 1-liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator, and stirrer, toluene, and as component (B), 2,2-bis (4-cyanatophenyl) propane (BADCY, manufactured by Lonza) ), P- (α-cumyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and after confirming dissolution, the liquid temperature is kept at 110 ° C. and then manganese naphthenate (manufactured by Wako Pure Chemical Industries) is blended as a reaction accelerator. Then, a cyanate prepolymer solution was obtained by heating for about 3 hours. Next, the reaction liquid was cooled, and when the internal temperature reached 80 ° C., a hydrogenated styrene-butadiene copolymer (Tuftec H1051, styrene content ratio: 42%, Mn: 66,000, Asahi Kasei Chemicals Co., Ltd.) as component (A) ), Toluene and methyl ethyl ketone were mixed with stirring, and after dissolution was confirmed, the flask was cooled to room temperature. Then, zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.) was blended as a curing accelerator, and the solid content concentration was about 35% by mass. A resin varnish was prepared.

(Preparation Example 5)
Toluene and polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) were charged into a 1-liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator, and stirrer. The solution was stirred and dissolved. Next, as component (B), 2,2-bis (4-cyanatophenyl) propane (BADCY, manufactured by Lonza) and p- (α-cumyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the solution was confirmed after dissolution was confirmed. After maintaining the temperature at 110 ° C., manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.) was blended as a reaction accelerator and heated for about 3 hours to synthesize a polyphenylene ether-modified cyanate prepolymer solution. Next, the reaction solution was cooled, and when the internal temperature reached 80 ° C., biphenyl type epoxy resin (YX-4000, manufactured by JER) was used as component (B), and Tuftec H1051 and H1031, toluene and methyl ethyl ketone were stirred as component (A). After mixing and confirming dissolution, after cooling to room temperature, zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.) and 2-ethyl-4-methylimidazole (2E4MZ) are blended as a curing accelerator, and the solid content concentration About 35% by mass of a resin varnish was prepared.

(Preparation Example 6)
Into a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator and stirrer, toluene and hydrogenated styrene-butadiene copolymer as component (A) (Tuftec H1051, styrene content ratio) : 42%, Mn: 66,000, manufactured by Asahi Kasei Chemicals Corporation), the temperature in the flask was set to 80 ° C. and dissolved by stirring. Next, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-5100, manufactured by Daiwa Kasei) was blended as the component (B), and after confirming dissolution, the flask was cooled to room temperature. Thereafter, 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) was added as a curing accelerator, and then mixed and stirred with methyl ethyl ketone to a resin varnish having a solid content concentration of about 35% by mass. Was prepared.

(Preparation Example 7)
In Preparation Example 6, instead of BMI-5100, component (B) is a chemically modified polybutadiene resin (B-3000, manufactured by Nippon Soda, 1,2-vinyl structure: 90%) shown in Table 1. A resin varnish was prepared in the same manner as in Preparation Example 6 except that it was blended.

(Preparation Example 8)
Into a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator and stirrer, toluene and hydrogenated styrene-butadiene copolymer as component (A) (Tuftec H1053, styrene content ratio) : 29%, Mn: 68,000, manufactured by Asahi Kasei Chemicals) and a hydrogenated styrene-butadiene copolymer having a number average molecular weight of 60,000 or less (Tuftec H1031, styrene content ratio: 30%, Mn: 47,000, Asahi Kasei Chemicals) was added, and the temperature in the flask was set to 80 ° C. and dissolved by stirring. Next, as a component (B), bismaleimide (BMI-5100) and a polybutadiene resin (B-3000), manufactured by Nippon Soda Co., Ltd., 1,2-vinyl structure: 90%) were blended, and after confirmation of dissolution, the flask was cooled to room temperature. . Thereafter, 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) was added as a curing accelerator, and then mixed and stirred with methyl ethyl ketone to a resin varnish having a solid content concentration of about 35% by mass. Was prepared.

(Preparation Example 9)
Toluene and polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) are charged into a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator, and stirrer. The solution was stirred and dissolved at a temperature of C. Next, as a component (B), a polybutadiene resin (B-3000) that was not chemically modified and N-phenylmaleimide (Imirex-P, manufactured by Nippon Shokubai Co., Ltd.) were added, and stirring was continued to confirm that these were dissolved. . Thereafter, the liquid temperature was raised to 110 ° C., and 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, Nippon Oil & Fats was used as a reaction initiator while maintaining the temperature. (Product made) 0.5 part by mass was mixed and pre-reacted with stirring for about 1 hour to obtain a polyphenylene ether-modified butadiene prepolymer solution. When the conversion rate of N-phenylmaleimide in the polyphenylene ether-modified butadiene prepolymer solution was measured by gel permeation chromatography, the conversion rate was 33%.
Subsequently, after setting the liquid temperature in a flask to 80 degreeC, it concentrated so that solid content concentration of a solution might be about 45 mass%, stirring. Next, after the solution is cooled to room temperature, Tuftec H1051 is blended as component (A). After confirming dissolution, Perbutyl P is added as a curing accelerator, and toluene and methyl ethyl ketone are blended and stirred to obtain a solid concentration of about A 35% by weight resin varnish was prepared.

(Preparation Example 10)
In Preparation Example 9, ½ amount of (A) component Tuftec H1051 was replaced with hydrogenated styrene-butadiene copolymer having a number average molecular weight of 60,000 or less (Tuftec H1141, styrene content ratio: 30%, Mn: Resin varnish was prepared in the same manner as in Preparation Example 9 except that it was replaced with 41,000 (manufactured by Asahi Kasei Chemicals).

(Preparation Example 11)
A resin varnish was prepared in the same manner as in Preparation Example 10 except that instead of Tuftec H1051 as Component (A), a hydrogenated maleic acid-modified styrene-butadiene copolymer (Tuftec M1913) was used. .

(Preparation Example 12)
In Preparation Example 9, the same procedure as in Preparation Example 9 was conducted except that (A) component was replaced with Tuftec H1141 instead of Tuftec H1051, and BMI-5100 was further added as Component (B) in the amount shown in Table 1. A resin varnish was prepared.

(Preparation Example 13)
A resin varnish was prepared in the same manner as in Preparation Example 12, except that component (A) was replaced with a hydrogenated maleic acid-modified styrene-butadiene copolymer (Tuftec M1913) instead of Tuftec H1051. .

(Preparation Example 14)
In Preparation Example 12, instead of BMI-5100, it was replaced with 2-bis (4- (4-maleimidophenoxy) phenyl) propane (BMI-4000, manufactured by Daiwa Kasei Co., Ltd.), except that it was blended in the blending amounts shown in Table 1. Prepared a resin varnish in the same manner as in Preparation Example 12.

(Preparation Example 15)
Resin varnish was prepared in the same manner as in Preparation Example 12 except that (1/2) the amount of Tuftec H1141 was replaced with a hydrogenated maleic acid-modified styrene-butadiene copolymer (Tuftec M1913) in Preparation Example 12. Was prepared.

(Preparation Example 16)
In Preparation Example 4, a part of the (A) component Tuftec H1051 was replaced with Tuftec H1031, and only the toluene was used as the diluent solvent, and the materials used were blended in the blending amounts shown in Table 1. A resin varnish was prepared in the same manner as described above.

(Preparation Example 17)
In Preparation Example 4, except that a part of the (A) component Tuftec H1051 was replaced with Tuftec H1031 and M1913, the diluent solvent was only toluene, and the materials used were blended in the blending amounts shown in Table 1. A resin varnish was prepared in the same manner as in Example 4.

(Preparation Example 18)
Resin varnish was prepared in the same manner as in Preparation Example 6 except that a part of (A) component Tuftec H1051 was replaced with Tuftec H1031 and M1913 and the materials used were blended in the blending amounts shown in Table 1. Was prepared.

(Preparation Example 19)
Resin in the same manner as in Preparation Example 8 except that instead of Tuftec H1053 and H1031 as component (A) in Preparation Example 8, the materials used were blended in the blending amounts shown in Table 1 instead of Tuftech H1051 and H1141. A varnish was prepared.

(Preparation Example 20)
A resin varnish (solid content concentration of about 35) was prepared in the same manner as in Preparation Example 6 except that the ratio of the blending amount of H1051 and the total amount of BMI-5100 and Pable P was changed as shown in Table 1. % By weight) was prepared.

(Preparation Example 21)
Into a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator and stirrer, toluene and hydrogenated styrene-butadiene copolymer as component (A) (Tuftec H1051, styrene content ratio) : 42%, Mn: 66,000, manufactured by Asahi Kasei Chemicals Corporation), the temperature in the flask was set to 80 ° C. and dissolved by stirring. Next, as a component (B), a biphenyl aralkyl type epoxy resin (NC-3000H, manufactured by Nippon Kayaku Co., Ltd.) and a cresol novolac resin (KA 1165, manufactured by DIC) were blended and dissolved, and then the flask was cooled to room temperature. Thereafter, 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei) was added as a curing accelerator, and then methyl ethyl ketone was blended and stirred to prepare a resin varnish having a solid content concentration of about 35% by mass.

(Preparation Example 22)
In Preparation Example 21, ½ amount of (A) component Tuftec H1051 was replaced with hydrogenated styrene-butadiene copolymer having a number average molecular weight of 60,000 or less (Tuftec H1041, styrene content ratio: 30%, Mn: A resin varnish was prepared in the same manner as in Preparation Example 21, except that the product was replaced with 58,000 (manufactured by Asahi Kasei Chemicals Corporation).

(Preparation Example 23)
In Preparation Example 22, a part of (A) component Tuftec H1051 was mixed with a hydrogenated maleic acid-modified styrene-butadiene copolymer (Tuftec M1913, styrene content ratio: 30%, Mn: 55,000, Asahi Kasei Chemicals Corporation A resin varnish was prepared in the same manner as in Preparation Example 22 except that it was mixed in the amount shown in Table 2 instead of

(Preparation Example 24)
In Preparation Example 23, a resin varnish was prepared in the same manner as Preparation Example 23 except that a phenolic antioxidant (Adeka Stub AO-20 manufactured by Adeka Corporation) was added in the amount shown in Table 2 as the component (C). .

(Preparation Example 25)
Into a 1-liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator, and stirrer, toluene, and as component (B), 2,2-bis (4-cyanatophenyl) propane (BADCY, manufactured by Lonza) ), P- (α-cumyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and after confirming dissolution, the liquid temperature is kept at 110 ° C. and then manganese naphthenate (manufactured by Wako Pure Chemical Industries) is blended as a reaction accelerator. The mixture was heated for about 3 hours to obtain a phenol-modified cyanate prepolymer solution. Next, the reaction liquid was cooled, and when the internal temperature reached 80 ° C., a hydrogenated styrene-butadiene copolymer (Tuftec H1051, styrene content ratio: 42%, Mn: 66,000, Asahi Kasei Chemicals Co., Ltd.) as component (A) ), Toluene and methyl ethyl ketone were mixed with stirring, and after dissolution was confirmed, the flask was cooled to room temperature. Then, zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.) was blended as a curing accelerator, and the solid content concentration was about 35 mass. % Resin varnish was prepared.

(Preparation Example 26)
In Preparation Example 25, a part of (A) component Tuftec H1051 was added to a hydrogenated styrene-butadiene copolymer having a number average molecular weight of 60,000 or less (Tuftec H1043, styrene content ratio: 67%, Mn: 47, 000, manufactured by Asahi Kasei Chemicals) and a hydrogenated product of maleic acid-modified styrene-butadiene copolymer (Tuftec M1913, styrene content ratio: 30%, Mn: 55,000, manufactured by Asahi Kasei Chemicals) and shown in Table 2. A resin varnish was prepared in the same manner as in Preparation Example 25 except that it was blended in the blending amount.

(Preparation Example 27)
In Preparation Example 25, a resin varnish was prepared in the same manner as in Preparation Example 25 except that a phenolic antioxidant (Adeka Stub AO-80 manufactured by Adeka Corporation) was added in the amount shown in Table 2 as the component (C). .

(Preparation Example 28)
In Preparation Example 26, a resin varnish was prepared in the same manner as in Preparation Example 26 except that a phenolic antioxidant (Adeka Stab AO-330 manufactured by Adeka Corporation) was added in the amount shown in Table 2 as the component (C). .

(Preparation Example 29)
Into a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator and stirrer, toluene and hydrogenated styrene-butadiene copolymer as component (A) (Tuftec H1051, styrene content ratio) : 42%, Mn: 66,000, manufactured by Asahi Kasei Chemicals Corporation), the temperature in the flask was set to 80 ° C. and dissolved by stirring. Next, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-5100, manufactured by Daiwa Kasei) was blended as the component (B), and after confirming dissolution, the flask was cooled to room temperature. Thereafter, 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) was added as a curing accelerator, and then methyl ethyl ketone was mixed and stirred to obtain a resin having a solid content concentration of about 35% by mass. A varnish was prepared.

(Preparation Example 30)
In Preparation Example 29, a part of (A) component Tuftec H1051 was added to a hydrogenated styrene-butadiene copolymer having a number average molecular weight of 60,000 or less (Tuftec H1041, styrene content ratio: 30%, Mn: 58, 000, manufactured by Asahi Kasei Chemicals) and a hydrogenated product of maleic acid-modified styrene-butadiene copolymer (Tuftec M1913, styrene content ratio: 30%, Mn: 55,000, manufactured by Asahi Kasei Chemicals) and shown in Table 2. A resin varnish was prepared in the same manner as in Preparation Example 29 except that it was blended in the blending amount.

(Preparation Example 31)
In Preparation Example 30, a resin varnish was prepared in the same manner as in Preparation Example 30 except that a phenolic antioxidant (Adeka Stub AO-20 manufactured by Adeka Corporation) was added in the amount shown in Table 2 as the component (C). .

(Preparation Example 32)
In Preparation Example 25, a part of the (A) component Tuftec H1051 was replaced with Tuftec H1043, and only the toluene was used as the diluent solvent, and the materials used were blended in the blending amounts shown in Table 2. A resin varnish was prepared in the same manner as described above.

(Preparation Example 33)
In Preparation Example 29, resin varnish was prepared in the same manner as in Preparation Example 29 except that a part of (A) component Tuftec H1051 was replaced with Tuftech H1041 and M1913, and the materials used were blended in the blending amounts shown in Table 2. Was prepared.

(Comparative Preparation Example 1)
Toluene and polyphenylene ether resin (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) are charged into a 1 liter separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature in the flask is set to 90 ° C. And dissolved with stirring. Next, triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Chemical Co., Ltd.) was blended, and after confirming that it was dissolved or uniformly dispersed, it was cooled to room temperature. Next, after cooling to room temperature with stirring, 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) is added as a curing accelerator, and then methylethylketone is blended for comparative preparation. The resin varnish of Example 1 (solid content concentration of about 35% by mass) was prepared.

(Comparative Preparation Example 2)
In Preparation Example 1, a resin varnish (solid content concentration of about 35% by mass) of Comparative Preparation Example 2 was prepared in the same manner as Preparation Example 1, except that polyphenylene ether resin (S202A) was used instead of Tuftec H1051. .

(Comparative Preparation Example 3)
In Comparative Preparation Example 1, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-5100, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was blended in the blending amounts shown in Table 3 instead of triallyl isocyanurate. Except that, a resin varnish (solid content concentration of about 35% by mass) of Comparative Preparation Example 2 was prepared in the same manner as Comparative Preparation Example 1.

(Comparative Preparation Example 4)
In Comparative Preparation Example 1, in place of triallyl isocyanurate, a polybutadiene resin (B-3000, manufactured by Nippon Soda Co., Ltd., 1,2-vinyl structure: 90%) was compared except that it was blended in the blending amounts shown in Table 3. In the same manner as in Preparation Example 1, a resin varnish of Comparative Preparation Example 1 (solid content concentration of about 35% by mass) was prepared.

(Comparative Preparation Example 5)
Toluene and polyphenylene ether resin (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) are charged into a 1 liter separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature in the flask is set to 90 ° C. And dissolved with stirring. Subsequently, 2,2-bis (4-cyanatophenyl) propane (BADCY, manufactured by Lonza) and p-tert-octylphenol (manufactured by Wako Pure Chemical Industries) were added and dissolved, and then manganese naphthenate (manufactured by Wako Pure Chemical Industries). Were mixed and allowed to react by heating for about 3 hours. Next, after mixing toluene and methyl ethyl ketone with stirring, the flask was cooled to room temperature, then zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.) was blended as a curing accelerator, and resin varnish (solid content concentration = 35% by mass) Manufactured.

(Comparative Preparation Example 6)
Resin varnish (solid content concentration of about 35) was prepared in the same manner as in Preparation Example 6 except that the ratio of the blending amount of H1051 and the total amount of BMI-5100 and perbutyl P was changed as shown in Table 3. % By weight) was prepared.

(Comparative Preparation Example 7)
In Preparation Example 6, instead of H1051, the unsaturated double bond group of the butadiene portion of the styrene-butadiene copolymer was changed to an unsaturated thermoplastic elastomer (Tufprene 125, manufactured by Asahi Kasei Chemicals) without hydrogenation. Except for the above, a resin varnish (solid content concentration of about 35% by mass) was prepared in the same manner as in Example 6.

(Comparative Preparation Example 8)
Toluene and polyphenylene ether resin (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) are charged into a 1-liter separable flask equipped with a thermometer, a reflux condenser, and a stirring device, and the temperature in the flask is set to 90 ° C. And dissolved with stirring. Subsequently, triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Co., Ltd.) was blended, and after confirming that it was dissolved or uniformly dispersed, it was cooled to room temperature. Next, after cooling to room temperature with stirring, 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) is added as a curing accelerator, and then methyl ketones are added to the resin varnish. (Solid content concentration of about 35% by mass) was prepared.

(Comparative Preparation Example 9)
In Preparation Example 21, a resin varnish (solid content concentration of about 35% by mass) was prepared in the same manner as Preparation Example 21 except that polyphenylene ether resin (S202A) was used instead of Tuftec H1051.

(Comparative Preparation Example 10)
In Preparation Example 25, a resin varnish (solid content concentration of about 35% by mass) was prepared in the same manner as in Preparation Example 25 except that M1913 was used instead of H1051 in the amount shown in Table 3.

(Comparative Preparation Example 11)
In Comparative Preparation Example 23, except that it was blended in the blending amounts shown in Table 3 using 2,2-bis (4-cyanatophenyl) propane (BADCY, manufactured by Lonza) instead of the phenol-modified cyanate ester prepolymer, In the same manner as in Comparative Preparation Example 23, a resin varnish (solid content concentration of about 35% by mass) was prepared.

(Comparative Preparation Example 12)
Toluene and polyphenylene ether resin (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) are charged into a 1-liter separable flask equipped with a thermometer, a reflux condenser, and a stirring device, and the temperature in the flask is set to 90 ° C. And dissolved with stirring. Next, 2,2-bis (4-cyanatophenyl) propane (BADCY, manufactured by Lonza) and p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved, and then manganese naphthenate (Wako Pure Chemical Industries, Ltd.). And the mixture was reacted by heating for about 3 hours. Next, after mixing toluene and methyl ethyl ketone with stirring, the flask was cooled to room temperature, then zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.) was blended as a curing accelerator, and resin varnish (solid content concentration = 35% by mass) Manufactured.

(Comparative Preparation Example 13)
In Comparative Preparation Example 12, a resin varnish (solid content) was obtained in the same manner as in Comparative Preparation Example 12, except that an epoxy-modified polybutadiene elastomer (manufactured by Daicel Chemical Industries, Ltd., PB-3600) was additionally added in the amounts shown in Table 3. A concentration of about 35% by weight) was prepared.

(Comparative Preparation Example 14)
A resin varnish (solid content concentration of about 35) was prepared in the same manner as in Preparation Example 29 except that the ratio of the blending amount of H1051 and the total amount of BMI-5100 and perbutyl P was changed as shown in Table 3 in Preparation Example 29. % By weight) was prepared.

(Comparative Preparation Example 15)
A resin varnish (solid content concentration of about 35) was prepared in the same manner as in Preparation Example 29 except that the ratio of the blending amount of H1051 and the total amount of BMI-5100 and perbutyl P was changed as shown in Table 3 in Preparation Example 29. % By weight) was prepared.

(Comparative Preparation Example 16)
In Preparation Example 29, instead of H1051, the unsaturated double bond group in the butadiene portion of the styrene-butadiene copolymer was changed to an unsaturated thermoplastic elastomer (Tufprene 125, manufactured by Asahi Kasei Chemicals Corporation) without hydrogenation. Except for this, a resin varnish (solid content concentration of about 35% by mass) was prepared in the same manner as in Preparation Example 29.

  The amount of each raw material used for the preparation of the resin varnishes of Preparation Examples 1 to 33 and Comparative Preparation Examples 1 to 16 is summarized in Tables 1 to 3.

[Preparation of semi-cured (B stage) resin film]
The resin varnishes obtained in Preparation Examples 1 to 33 and Comparative Preparation Examples 1 to 16 were coated on a 38 μm-thick PET film (G2-38, manufactured by Teijin) using a comma coater (dried). (Temperature: 130 ° C.), and a resin film with a PET film having a thickness of 50 μm was produced. In addition, the semi-hardened resin films produced using the resin varnishes of Preparation Examples 1-33 are Examples 1-33, and the semi-cured resin films produced using the resin varnishes of Comparative Preparation Examples 1-16 are Comparative Examples 1-16. Respectively.

[Evaluation of semi-cured resin film]
The appearance and handleability of the semi-cured resin films of Examples 1 to 33 and Comparative Examples 1 to 16 were evaluated. The evaluation results are shown in Tables 4-6. The appearance was evaluated by visual observation, and the surface of the resin film had some unevenness, streaks, and the like. In addition, the handling property was evaluated as x when the surface was somewhat sticky (tack) at 25 ° C., or when the resin was cracked or crushed even when cut with a cutter knife, and otherwise.

  A glass cloth base epoxy resin copper-clad laminate having a circuit pattern formed thereon is used as an inner circuit board, and one of the above-mentioned semi-cured resin films from which a PET film has been peeled is placed on both surfaces thereof, and electrolytic copper having a thickness of 12 μm is placed thereon. A foil (YGP-12, manufactured by Nippon Electrolytic Co., Ltd.) was placed, a mirror plate was placed thereon, and heat-press molding was performed under press conditions of 200 ° C./3.0 MPa / 70 minutes to produce a four-layer wiring board. The copper foil of the outermost layer of this four-layer wiring board was etched to evaluate circuit embedding property (multilayered formability). The evaluation results are shown in Tables 4-6. The multilayer formability was evaluated by visual observation. The case where there were some voids and scumming was rated as x, and the circuit was uniformly filled with resin, and the uniformity was marked as ◯.

[Production of double-sided metal-clad cured resin film]
The PET film of the semi-cured resin film described above is peeled off, two of them are stacked, and a low profile copper foil (F3-WS, M surface Rz: 3 μm, manufactured by Furukawa Electric Co., Ltd.) with a thickness of 18 μm is roughened on both surfaces. (M) It arrange | positions so that a surface may contact | connect, it mounts a mirror plate on it, heat-press-molds on the press conditions of 200 degreeC / 3.0MPa / 70 minutes, double-sided metal-clad cured resin film (thickness: 0.00. 1 mm).

[Characteristic evaluation of double-sided metal-clad cured resin film]
The metal-clad cured resin films of Examples 1 to 33 and Comparative Examples 1 to 16 described above were evaluated for handleability, dielectric properties, copper foil peeling strength, solder heat resistance, thermal expansion coefficient, and water absorption rate. The evaluation results are shown in Tables 4-6. The characteristic evaluation method of the metal-clad cured resin film is as follows.

[Evaluation of handleability]
The handleability was evaluated by bending a cured resin film obtained by etching the outer layer copper foil by 180 degrees. When bending, cracks or cracks that occurred somewhat were marked with ×, and when bending was stopped, those with no change were marked with ○.

[Measurement of dielectric properties (dielectric constant, dielectric loss tangent)]
Dielectric properties were measured by etching the outer layer copper foil of the cured resin film using the cavity resonator perturbation method. The conditions were a frequency of 1 GHz and a measurement temperature of 25 ° C. Moreover, about Examples 21-33 and Comparative Examples 8-16, it measured similarly about the sample after leaving to stand in a 105 degreeC thermostat for 1000 hours. In addition, after the heat processing in a table | surface, the fluctuation | variation amount from a normal state was shown.

[Measurement of peeling strength of copper foil]
The copper foil peeling strength was measured in accordance with the copper clad laminate test standard JIS-C-6481.

[Evaluation of solder heat resistance]
The solder heat resistance is determined by etching a copper foil on one side of the above-mentioned cured resin film cut to a 50 mm square, and in a normal state and a pressure cooker test (PCT) apparatus (conditions: 121 ° C., 2.2 atm) for a predetermined time ( After processing for 1, 3 and 5 hours, the product was floated on a molten solder at 288 ° C. for 20 seconds, and the appearance was visually examined. In addition, the number in a table | surface means the number of the thing in which the generation | occurrence | production of a swelling and a measling was not recognized among the inside of a film and between a film and copper foil among three cured resin films after a solder float.

[Measurement of thermal expansion coefficient]
The thermal expansion coefficient was measured in a tensile direction (30 to 100 ° C.) using TMA by etching a copper foil on both sides and cutting it to 5 mm × 30 mm as a test piece.

[Measurement of water absorption rate]
The water absorption is determined by etching the copper foils on both sides of the above cured resin film cut to a 50 mm square, and in a normal time and pressure cooker test (PCT) apparatus (conditions: 121 ° C., 2.2 atm) for a predetermined time (5 Time) It was calculated from the difference in mass after the treatment.

[Evaluation of insulation reliability]
Insulation reliability is obtained by etching a copper foil on one side to form a comb pattern of L / S = 100/100 (μm), and applying 100 V under a constant temperature and high humidity of 85 ° C./85% RH before and after treatment for 1000 hours. The insulation resistance between the lines was measured. The numbers in Tables 5 and 6 indicate the number of resistances with a resistance value of 1 × 10 ¹³ Ω or more among the evaluated numbers n (n = 5).

As is clear from the results shown in Tables 4 to 6, according to the semi-cured resin films (Examples 1 to 33) of the present invention, compared with the resin films of Comparative Examples 1 to 16, the appearance (surface uniformity) ) And handleability (tackiness, cracking, powder falling, etc.) were confirmed, and it was confirmed that the multilayered formability was also good.
Moreover, all the cured resin films produced using the semi-cured resin film of the present invention were excellent with a relative dielectric constant of 2.6 or less and a dielectric loss tangent of 0.009 or less. Moreover, the soldering heat resistance, the copper foil peeling strength, the thermal expansion coefficient, and the water absorption rate satisfied the practical characteristics. Furthermore, the system in which the component (C) was blended was excellent in insulation reliability, and the heating drift property of the dielectric characteristics was improved as compared with the similar blend system that was not blended.

On the other hand, in Comparative Examples 1 to 16, there are problems in appearance and handling, and the results are relatively inferior in dielectric properties, solder heat resistance, copper foil peeling strength, water absorption, and the like as compared with Examples. It was done.
For example, by comparing Comparative Examples 2 to 5 with Example 1, Example 6, Example 7, and Example 4, respectively, the properties of the semi-cured resin film, the handleability of the cured resin film, the dielectric properties, and the solder heat resistance It was confirmed that the properties, copper foil peeling strength, water absorption, etc. were relatively inferior.

  The resin film using the manufacturing method of the present invention has a relative dielectric constant of about 2.6 or less, which is equivalent to that of a fluororesin substrate material, while maintaining film forming ability and handleability suitable for manufacturing a build-up wiring board. In addition, since it has a low dielectric loss tangent, it exhibits transmission loss characteristics even in a high frequency band exceeding the millimeter wave band, and also has good low moisture absorption, solder heat resistance, and copper foil peeling strength. Therefore, components and parts for printed wiring boards used in mobile communication devices that handle high-frequency signals of 1 GHz or higher, base station devices, network-related electronic devices such as servers and routers, and various electric and electronic devices such as large computers. Useful as.

Claims (23)

(A) a saturated thermoplastic elastomer having a styrene unit, (B) at least one thermosetting resin selected from the group consisting of epoxy resins, cyanate ester resins, polybutadiene resins and maleimide compounds, and blended as necessary. that contains a thermosetting resin component comprising a curing agent and curing accelerator for the thermosetting resin, the component (B) weight ratio W _{a /} W _B content W _a to the content W _B 0 And a resin composition having a polyphenylene ether content of 10 parts by mass or less with respect to a total of 100 parts by mass of the component (A) and the component (B). A method for producing a resin film for a printed wiring board, comprising a step of cast-coating on one side of the film and semi-curing or curing the resin composition by heat drying.   The manufacturing method of the resin film for printed wiring boards of Claim 1 in which the said (A) component contains a styrene-ethylene-butylene copolymer.   The component (A) contains a saturated thermoplastic elastomer obtained by hydrogenation of an unsaturated double bond of a structural unit derived from butadiene of a styrene-butadiene copolymer. The manufacturing method of the resin film for printed wiring boards of description.   The method for producing a resin film for a printed wiring board according to any one of claims 1 to 3, wherein the component (A) contains a saturated thermoplastic elastomer having a number average molecular weight of less than 60,000.   5. The resin film for a printed wiring board according to claim 4, wherein the content ratio of the saturated thermoplastic elastomer having a number average molecular weight of less than 60,000 is 50% by mass or more based on the total mass of the component (A). Production method.   The method for producing a resin film for a printed wiring board according to claim 4 or 5, wherein the component (A) further contains a saturated thermoplastic elastomer having a number average molecular weight of 60,000 or more.   The production of the resin film for a printed wiring board according to any one of claims 1 to 6, wherein the component (A) contains a chemically modified saturated thermoplastic elastomer having a maleic anhydride group at a side chain or at a terminal. Method.   The method for producing a resin film for a printed wiring board according to claim 7, wherein the component (A) further contains a non-modified saturated thermoplastic elastomer having no maleic anhydride group at a side chain or at a terminal.   The manufacturing method of the resin film for printed wiring boards of Claim 7 or 8 whose ratio of the said chemical modification | denaturation type | mold thermoplastic elastomer is 20-50 mass% on the basis of the total mass of the said (A) component. Said resin composition, and the polyphenylene ether, (B) the as component, a structural unit derived from 1,2-butadiene structural units having a 1,2-vinyl group in the side chain in the molecule 40 The polyphenylene ether-modified butadiene prepolymer obtained by reacting with a polybutadiene resin that is not chemically modified and contains at least mol% and has a number average molecular weight of 500 to 10,000. The manufacturing method of the resin film for printed wiring boards as described in a term.
  The polyphenylene ether-modified butadiene prepolymer includes the polyphenylene ether, the polybutadiene resin, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2, 6 -Dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide and N-cyclohexylmaleimide The manufacturing method of the resin film for printed wiring boards of Claim 10 obtained by making it react with the at least 1 sort (s) of crosslinking agent chosen from more.   The polyphenylene ether-modified butadiene prepolymer includes the polyphenylene ether, the polybutadiene resin, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and 2,2-bis (4- (4-maleimidophenoxy). The method for producing a resin film for a printed wiring board according to claim 10 or 11, which is obtained by reacting at least one crosslinking agent selected from the group consisting of phenyl) propane.   The resin composition is N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6- Diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide and N-cyclohexylmaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) The printed wiring according to any one of claims 10 to 12, further comprising at least one crosslinking agent selected from the group consisting of methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane. Manufacturing method of resin film for board. The component (B) is at least one thermosetting resin selected from the group consisting of an epoxy resin, a cyanate ester resin and a maleimide compound, and a curing agent and a curing accelerator for the thermosetting resin blended as necessary. Containing a thermosetting resin component containing
(B) the weight ratio _W A / _{W B} content _{W A} to the content _{W B} component is 0.700 to 5.000, printed wiring board according to any one of claims 1 to 9 For producing a resin film for an automobile.   The method for producing a resin film for a printed wiring board according to claim 14, wherein the component (B) contains a phenol-modified cyanate ester prepolymer obtained by reacting a cyanate ester resin with a monofunctional phenol compound.   The phenol-modified cyanate ester prepolymer is obtained by reacting a cyanate ester resin with at least one monofunctional phenol selected from the group consisting of pt-octylphenol, p-phenylphenol, and p- (α-cumyl) phenol. The manufacturing method of the resin film for printed wiring boards of Claim 15 which is what is obtained.   The maleimide compound is at least one maleimide compound selected from the group consisting of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane. The manufacturing method of the resin film for printed wiring boards of Claim 14 which contains further. The component (C) further contains at least one selected from the group consisting of specific phenolic antioxidants represented by the following formulas (1) to (3): The manufacturing method of the resin film for printed wiring boards of description.

  The resin for printed wiring boards according to any one of claims 1 to 18, wherein the resin composition is cast and applied to one side of the support base material in the form of a resin varnish obtained by dissolving or dispersing the resin composition in a solvent. A method for producing a film.   The manufacturing method of the resin film for printed wiring boards as described in any one of Claims 1-19 whose said support base material is metal foil.   The manufacturing method of the resin film for printed wiring boards as described in any one of Claims 1-20 whose said support base material is a PET film.   The manufacturing method of the resin film for printed wiring boards as described in any one of Claims 1-21 whose film thickness of the said resin film after the said process is 1-200 micrometers.   The resin film for printed wiring boards produced by the manufacturing method of the resin film for printed wiring boards as described in any one of Claims 1-22.