JP5552889B2 - Thermosetting resin composition for printed wiring board and varnish, prepreg and metal-clad laminate using the same - Google Patents

Description

  The present invention relates to a novel semi-IPN composite thermosetting resin composition, and a resin varnish, prepreg and metal-clad laminate using the same, and particularly a specific silane-based or silicone-based surface treatment agent. The present invention relates to a thermosetting resin composition further containing an inorganic filler surface-treated in (1). More specifically, a novel semi-IPN-type composite thermosetting resin composition suitable for an electronic device using a high frequency range in which the operating frequency exceeds 1 GHz, and a resin varnish, prepreg and metal for a printed wiring board using the same The present invention relates to a tension laminate.

  Mobile communication devices such as mobile phones, their base station devices, network-related electronic devices such as servers and routers, and large computers can transmit and process large volumes of information with low loss and high speed. It is requested. Transmission and processing of large-capacity information can be accelerated if the electrical signal has a high frequency. However, the electrical signal basically has a property of being easily attenuated as the frequency becomes high, that is, the output is likely to be weak at a shorter transmission distance and the loss is likely to be increased. Therefore, in order to satisfy the above requirement of low loss and high speed, it is necessary to further reduce the transmission loss, particularly in the high frequency band, in the characteristics of the printed circuit board mounted on the device that controls transmission and processing. .

  In order to obtain such a printed wiring board having a low transmission loss, conventionally, a substrate material using a fluorine-based resin having a low relative dielectric constant and low dielectric loss tangent has been used. However, since the fluororesin generally has a high melting temperature and melt viscosity, and its fluidity is relatively low, there is a problem that press molding conditions sometimes become high temperature and high pressure. Moreover, workability, dimensional stability, and adhesion to metal plating are not sufficient for use in the above-mentioned applications, high-layer printed wiring board applications used in communication equipment, network-related electronic equipment, large computers, and the like. There is also a problem of not.

  Therefore, resin materials for printed wiring boards for replacing high-frequency resins for high-frequency applications have been studied. Polyphenylene ether is known as one of the resins having the most excellent dielectric properties among heat resistant polymers, and the use of this is drawing attention. However, polyphenylene ether is a thermoplastic resin having a high melting temperature and high melt viscosity, similar to a fluorine-based resin. Therefore, conventionally for printed wiring board applications, the melting temperature and melt viscosity are lowered, the temperature and pressure conditions are set low during press molding, or the heat resistance at the melting temperature (230 to 250 ° C.) or higher of polyphenylene ether. For the purpose of imparting, a resin composition in which polyphenylene ether and a thermosetting resin are used in combination has been used.

  For example, a resin composition using an epoxy resin (see Patent Document 1), a resin composition using a bismaleimide (see Patent Document 2), a resin composition using a cyanate ester (see Patent Document 3), styrene-butadiene A resin composition using a copolymer or polystyrene and triallyl cyanurate or triallyl isocyanurate in combination (see Patent Documents 4 to 5), a resin composition using polybutadiene in combination (see Patent Documents 6 and 7), Resin composition obtained by pre-reaction of modified polybutadiene having a functional group such as hydroxyl group, epoxy group, carboxyl group, (meth) acryl group, and bismaleimide and / or cyanate ester (see Patent Document 8), unsaturated double bond The above-mentioned triallyl cyanu is added to a polyphenylene ether provided or grafted with a group-containing compound. Resin composition (see Patent Document 9 and Patent Document 10), a reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride, and the above bismaleimide And the like (see Patent Document 11), a resin having an unsaturated double bond group at the terminal and a polyphenylene ether oligomer of a low molecular weight (oligomer) type in combination with polybutadiene or a styrene-butadiene copolymer A composition (see Patent Document 12) has been proposed.

  In these documents, in order to improve the drawbacks of the above-mentioned thermoplastic resin composition that requires high-temperature and high-pressure conditions during press molding while maintaining the low transmission loss of polyphenylene ether, the cured thermoplastic resin composition It is disclosed that it is preferable that there are not many polar groups.

  However, it has been proposed to include a dielectric powder for the purpose of improving dielectric properties such as increasing the dielectric constant and reducing the dielectric loss tangent. In addition, it has been studied to perform surface treatment in order to control the adhesion of the surface of the dielectric powder. For specific silane coupling agents such as amino and / or acrylic silane coupling agents, the dielectric properties are It is well known that heat drift and dimensional stability can be obtained (see Patent Document 13). Moreover, it is known that a vinyl group-containing silane coupling agent can increase the peel strength between the metal foil (Patent Document 15).

  As a system containing an inorganic dielectric powder, a polyphenylene oxide resin composition (see Patent Document 13), a polyphenylene ether resin composition (see Patent Document 14), and the like have been proposed.

JP 58-69046 A JP-A-56-133355 Japanese Patent Publication No. 61-18937 JP-A-61-286130 JP-A-3-275760 JP-A-62-148512 JP 59-193929 A JP 58-164638 A JP-A-2-208355 JP-A-6-184213 JP-A-6-179734 JP 2005-105061 A JP-A-6-52716 JP 2005-105062 A JP 2008-133414 A

  Applicants of the present invention, such as those described in Patent Documents 1 to 15, such as resin compositions using polyphenylene ether and thermosetting resin in combination, for use in laminated boards for printed wiring boards We examined in detail.

  As a result, in the resin compositions shown in Patent Document 1, Patent Document 2 and Patent Document 11, the dielectric properties after curing deteriorate due to the influence of highly polar epoxy resin and bismaleimide. It was inappropriate.

  In the composition using the cyanate ester shown in Patent Document 3, the heat resistance after moisture absorption was lowered although the dielectric properties were excellent.

  In the composition using triallyl cyanurate and triallyl isocyanurate shown in Patent Documents 4 to 5, Patent Document 9 and Patent Document 10, the relative dielectric constant is slightly high, and it is accompanied by moisture absorption of dielectric characteristics. There was a tendency for large drift.

  In the resin composition combined with polybutadiene shown in Patent Documents 4 to 7 and Patent Document 10, although the dielectric properties are excellent, there is a problem that the strength of the resin itself is low and the coefficient of thermal expansion is high. It was inappropriate for printed wiring board use.

  Patent Document 8 is a resin composition in which a modified polybutadiene is used in combination for the purpose of improving adhesion to a metal or glass substrate. However, there has been a problem that the dielectric characteristics are greatly deteriorated particularly in a high frequency region of 1 GHz or more as compared with the case where unmodified polybutadiene is used.

  In the composition using the reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride shown in Patent Document 11, it is usually caused by the influence of highly polar unsaturated carboxylic acid or unsaturated acid anhydride. Dielectric properties are worse than when polyphenylene ether is used.

  In a composition having an unsaturated double bond group at the terminal and a low molecular weight (oligomer) type polyphenylene ether oligomer in combination with a thermosetting resin such as polybutadiene as shown in Patent Document 12, a curable polyphenylene ether is used. Since the oligomer itself has poor dielectric properties as compared to ordinary polyphenylene ether, as well as the cured polybutadiene resin, the good dielectric properties of polyphenylene ether are impaired. The dielectric properties of the cured composition are worse than if they were. In addition, this curable polyphenylene ether oligomer is significantly more expensive than ordinary polyphenylene ether.

  On the other hand, as shown in Patent Document 13 and Patent Document 14, a resin system in which the above-mentioned triallyl cyanurate, triallyl isocyanurate, polybutadiene or the like is used in combination with polyphenylene ether or the curable polyphenylene ether oligomer of Patent Document 12. In a composition containing an inorganic filler treated with an acrylic and / or amino silane coupling agent, control of the dielectric constant and improvement of heat resistance are expected by the combined use of the desired inorganic filler, and the above Adhesion between the resin and the inorganic filler is ensured by the addition of the silane coupling agent.

  However, since these silane coupling agents have high polarities of amino groups and acrylic groups, the present inventors have found a problem that dielectric properties (particularly after moisture absorption) deteriorate in a high frequency band exceeding 1 GHz. The inventors have also found a problem that the dielectric properties (particularly after moisture absorption) of the vinyl group-containing silane coupling agent deteriorate. Similarly, the resin composition described in Patent Document 15 is a thermosetting resin composition containing polyphenylene ether which is improved in the above-described thermoplastic defects and has excellent dielectric properties. Then, it discovered that this resin composition was not enough with respect to the request | requirement of the said moisture absorption drift.

  As for moisture absorption drift, in applications such as mobile phone base station antennas, moisture absorption is performed under a mild condition of about 85 ° C and 85% RH, and the change in dielectric constant and dielectric loss tangent (moisture absorption drift) after moisture absorption is below a certain level. There is a requirement that it must be. For example, a wiring board is usually designed in a pattern so that an electric signal resonates in a specific frequency band. When the resonance of the electric signal is taken as a signal intensity peak at a certain frequency ω with the signal intensity on the vertical axis and the frequency on the horizontal axis, the peak shifts to the left and right when the dielectric constant Dk fluctuates. By the way, the gain decreases. Further, when the dielectric loss tangent Df varies, the peak width increases, so that the peak height decreases according to the energy conservation law. That is, when Dk changes due to moisture absorption, the magnitude of resonance decreases, and the signal level that can be received decreases. Similarly, when Df changes, the magnitude of resonance decreases, the signal level that can be received decreases, the signal peak of resonance further spreads, and the attenuation of the electrical signal increases. Thus, transmission loss increases due to moisture absorption.

  However, since moisture absorption is unavoidable when used outdoors such as mobile phone base station antennas, the fluctuations in Δk and Df (ΔDk and ΔDf) due to moisture absorption are considered to be a major problem.

  Therefore, in order to solve the above-mentioned problems, the present invention has good dielectric characteristics particularly in a high frequency band, and changes in dielectric characteristics (ΔDk and ΔDf) at the time of moisture absorption are small, thereby significantly reducing transmission loss. A thermosetting resin composition capable of producing a printed wiring board that is excellent in moisture absorption heat resistance and thermal expansion properties and satisfies the peel strength between the metal foil, and It aims at providing the used resin varnish, a prepreg, and a metal-clad laminate. These properties are particularly important for outdoor use.

  As a result of intensive research on the resin composition containing polyphenylene ether so as to solve the above-mentioned problems, the polyphenylene ether, a butadiene polymer not chemically modified, and a prepolymer of a crosslinking agent have been made compatible. Heat containing a semi-IPN type composite formed from an uncured polyphenylene ether-modified butadiene polymer and an inorganic filler surface-treated with a specific silane-based surface treatment agent or silicone-based surface treatment agent having excellent moisture absorption resistance A curable resin composition was found.

  Then, the present inventors have found that when this resin composition is used for printed wiring board applications, it has excellent dielectric characteristics and low moisture absorption dependence characteristics in a high frequency band, and is excellent in reducing transmission loss. It came to be completed.

That is, the present invention
(1)
A thermosetting resin composition comprising an uncured semi-IPN composite and a surface-treated inorganic filler, wherein the uncured semi-IPN composite comprises (A) polyphenylene ether and (B) A butadiene polymer containing at least 40% of 1,2-butadiene units having 1,2-vinyl groups in the side chain in the molecule and not chemically modified, and (C) a prepolymer formed from a crosslinking agent, Compatibilized uncured semi-IPN type composite,
Surface treatment agents for treating the surface-treated inorganic filler are alkyltrialkoxysilane, alkyldialkoxysilane, cycloalkyltrialkoxysilane, cycloalkyldialkoxysilane, phenyltrialkoxysilane, tris (trialkylsiloxy) silane, Formula (D-1):

Wherein R ¹ and R ² are H, CH ₃ , C ₆ H ₅ , C _a H _{2a + 1} , C ₂ H ₄ CF ₃ , or

A is an integer of 1 or more, and n is an integer of 1 or more)
A silicone oligomer represented by formula (D-2):

Wherein R ¹ , R ² , a and n are as defined above,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are H, CH ₃ , C ₆ H ₅ , C _a H _{2a + 1} , C ₂ H ₄ CF ₃ , or

One of
And a silicone oil represented by formula (D-3):

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , a and n are as defined above,
R ⁸ and R ⁹ are H, CH ₃ , C ₆ H ₅ , C _a H _{2a + 1} , C ₂ H ₄ CF ₃ , or

And b is an integer of 1 or more, c is an integer of 1 or more, and d is an integer of 1 or more)
A thermosetting resin composition, which is at least one surface treatment agent selected from the group consisting of silicone coating agents represented by:

(2)
The uncured semi-IPN type composite consists of (A) polyphenylene ether, (B) a radical polymerizable polymer obtained by radical polymerization of a butadiene polymer and (C) a crosslinking agent,
A chemically modified butadiene polymer in which (B) is composed of — [CH ₂ —CH═CH—CH ₂ ] —unit (j) and — [CH ₂ —CH (CH═CH ₂ )] — unit (k) And the ratio of j: k is 60-5: 40-95,
The thermosetting resin composition according to (1), wherein (C) is a compound having one or more ethylenically unsaturated double bonds in the molecule.

(3)
The uncured semi-IPN type composite contains (A) polyphenylene ether in the presence of (B) 1,2-butadiene unit having a 1,2-vinyl group in the side chain in a molecule of 40% or more, The thermosetting resin composition according to (1), which is a polyphenylene ether-modified butadiene prepolymer obtained by prereacting a butadiene polymer not chemically modified and (C) a crosslinking agent.

(4)
The thermosetting resin composition according to (3), obtained by pre-reacting an uncured semi-IPN type composite so that the conversion rate of the component (C) is in the range of 5 to 100%.

(5)
(D) The inorganic filler used for the surface-treated inorganic filler is aluminum oxide, titanium oxide, mica, silicon oxide, beryllium oxide, 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, calcined clay, etc., talc, aluminum borate, aluminum borate, silicon carbide, and The thermosetting resin composition according to any one of (1) to (4), which is at least one inorganic filler selected from the group consisting of these mixtures.

(6)
The thermosetting resin composition according to any one of (1) to (5), wherein the inorganic filler is spherical silicon oxide having an average particle diameter of 0.01 to 30 μm.

(7)
(D) a surface treatment agent used in the _component, C 1 _{-C 15} alkyl _{trialkoxysilane,} C 1 _{-C 15} alkyl dialkoxy _silanes, C 1 _{-C 15} alkyl trialkoxysilane, cycloalkyl trialkoxysilane, cycloalkyl Dialkoxysilane, phenyltrialkoxysilane, tris (trialkylsiloxy) silane, silicone oligomer represented by formula (D-1) of (1), silicone oil represented by formula (D-2) of (1) And the thermosetting resin composition according to any one of (1) to (6), which is at least one selected from the group consisting of silicone coating agents represented by formula (D-3) in (1). object.

(8)
The surface treatment agent used for component (D) is hexyltrimethoxysilane, decyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, cyclohexylmethyldimethoxysilane, tris (trimethylsiloxy) silane, formula (1) ( From the group consisting of a silicone oligomer represented by D-1), a silicone oil represented by formula (D-2) in (1), and a silicone coating agent represented by formula (D-3) in (1) The thermosetting resin composition according to any one of (1) to (6), comprising at least one selected.

(9)
(D) The thermosetting resin composition according to any one of (1) to (6), wherein the surface treating agent used for the component is used in an amount of 0.01 to 20% by mass of the inorganic filler weight.

(10)
As the component (C), the general formula (C-1):

(Wherein R ¹⁰ is an m-valent aliphatic or aromatic organic group, and X ^a and X ^b are the same or different selected from a hydrogen atom, a halogen atom and an aliphatic organic group. Any one of (1) to (9), which contains one or more maleimide compounds represented by the formula: The thermosetting resin composition according to Item.

(11)
Component (C) is N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6- One or more maleimide compounds (I) selected from the group consisting of diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide, and N-cyclohexylmaleimide One or more maleimide compounds (II) containing 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, one containing bis (3-ethyl-5-methyl-4-maleimidophenyl) methane One or more maleimide compounds (III) or one or more containing divinylbiphenyl Vinyl compounds, (1) to the thermosetting resin composition according to any one claim of (10).

(12)
The blending ratio of the component (A) is in the range of 2 to 200 parts by weight with respect to 100 parts by weight of the total amount of the component (B) and the component (C), and the blending ratio of the component (C) is (B). It is the range of 2-200 mass parts with respect to 100 mass parts of components, and the mixture ratio of (D) component is with respect to 100 mass parts of total amounts of (A) component, (B) component, and (C) component. The thermosetting resin composition according to any one of (1) to (11), which is in a range of 1 to 1000 parts by mass.

(13)
Furthermore, (E) a radical reaction initiator, (F) a crosslinkable monomer or crosslinkable polymer that does not constitute an uncured semi-IPN type complex and contains one or more ethylenically unsaturated double bond groups in the molecule, (G) One or more types selected from a brominated flame retardant and a phosphorus based flame retardant, and / or (H) a thermosetting according to any one of (1) to (12), which contains a saturated thermoplastic elastomer. Resin composition.

(14)
The component (F) is one or more ethylenically unsaturated double bond group-containing crosslinkable monomers or crosslinkable polymers selected from the group consisting of butadiene polymers that are not chemically modified and maleimide compounds (1) to The thermosetting resin composition according to any one of (13).

(15)
(H) The saturated thermoplastic elastomer is one or more types including a saturated thermoplastic elastomer obtained by hydrogenating the unsaturated double bond group of the butadiene portion of the styrene-butadiene copolymer, (13) or ( The thermosetting resin composition according to 14).

(16)
A resin varnish for a printed wiring board obtained by dissolving or dispersing the thermosetting resin composition according to any one of (1) to (15) in a solvent.

(17)
(16) A prepreg obtained by impregnating a substrate with the resin varnish for printed wiring board and drying at 60 to 200 ° C.

(18)
The content ratio of the component (D), or when the substrate is an inorganic substrate, the content ratio of the component (D) and the inorganic component combined with the substrate is less than 50% by volume of the prepreg volume (17) Prepreg.

(19)
The present invention relates to a metal-clad laminate obtained by stacking one or more prepregs according to (17) or (18), placing a metal foil on one or both sides, and heating and pressing.

  According to the present invention, the printed wiring board using the resin composition of the present invention has basic characteristics such as excellent high frequency characteristics, good heat resistance (particularly moisture absorption heat resistance) and low thermal expansion characteristics, and good peel strength. Therefore, when used as a material for an electronic device, a low-loss and high-speed electronic device can be achieved.

  Moreover, the resin composition which achieves the peeling strength between metal foils on a sufficiently high level, and the resin varnish, prepreg, and metal-clad laminate using the same can be provided. Therefore, the resin composition of the present invention is used in mobile communication devices that handle high-frequency signals of 1 GHz or higher, network-related electronic devices such as base station devices, servers and routers, and various electric and electronic devices such as large computers. This is useful as a printed wiring board member or component.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The reason why the novel semi-IPN composite thermosetting resin composition of the present invention can achieve the above-mentioned object has not been clarified in detail at present. The present inventors speculate as follows, but do not exclude the involvement of other elements.

  In the present invention, essential components are polyphenylene ether which is a thermoplastic resin having good dielectric properties, and a butadiene polymer which is not chemically modified and is known as one of thermosetting resins which exhibit the most excellent dielectric properties after curing. It aims at improving a dielectric characteristic markedly by containing.

  As described above, the polyphenylene ether and the butadiene polymer that has not been chemically modified are inherently incompatible with each other, and it has been difficult to obtain a uniform resin. However, a resin having a novel structure uniformly compatible can be obtained by the method using the preliminary reaction of the present invention.

  In the present invention, the preliminary reaction means that a radical is generated at a reaction temperature, for example, 60 to 170 ° C., and the (B) component and the (C) component are reacted, and the predetermined amount in the (B) component is Crosslinking results in conversion of a predetermined amount of component (C). That is, this state is an uncured state that has not yet been gelled. Before and after this preliminary reaction, the mixture of component (A), component (B) and component (C) is easily distinguished from semi-IPN polymer by changes in the characteristic peaks such as viscosity, turbidity, and liquid chromatography. can do.

  The curing reaction generally referred to is to generate radicals at a temperature equal to or higher than the hot press or the solvent volatilization temperature and cure, and the difference from the preliminary reaction in the present invention is clear.

  In the present invention, in the presence of polyphenylene ether as component (A), the component (B) contains 1,2-butadiene units having a 1,2-vinyl group in the side chain of 40% or more in the molecule, In addition, the butadiene polymer not chemically modified and the crosslinking agent of the component (C) are pre-reacted with the component (C) at an appropriate conversion rate (reaction rate), and in an uncured state before being completely cured. Once, one linear polymer component (here, component (A) indicated by the solid line in the lower figure) and the other crosslinkable component (here, indicated by the dotted line in the lower figure (B) and (C)) A uniform resin composition is obtained by forming a polyphenylene ether-modified butadiene prepolymer in which so-called “semi-IPN” is formed (components)) (thermosetting resin composition of uncured semi-IPN type composite) Things; see below ).

In this case, the homogenization (compatibility) does not mean that (A) component and other components (partially crosslinked product of (B) component and (C) component) form a chemical bond, It is considered that the molecular chains of the component A) and the other components are oligomerized while being partially and physically entangled with each other, so that a microphase separation structure is formed and apparently uniform (compatibilized). .

  The resin composition containing this polyphenylene ether-modified butadiene prepolymer (thermosetting resin composition of an uncured semi-IPN composite) can provide a resin film having an apparently uniform appearance.

  A polyphenylene ether-modified butadiene prepolymer known in the art or a simple mixture of polyphenylene ether and polybutadiene does not form a semi-IPN, and the components are not compatibilized. It is. Therefore, unlike the composition of the present invention, a conventional polyphenylene ether-modified butadiene prepolymer or a simple mixture of polyphenylene ether and polybutadiene causes apparently non-uniform macrophase separation.

  The prepreg produced using the resin composition containing the polyphenylene ether-modified butadiene prepolymer of the present invention (thermosetting resin composition of an uncured semi-IPN composite) has a uniform appearance and to some extent The tack problem is eliminated because the cross-linked butadiene prepolymer and the originally tack-free polyphenylene ether are compatible at the molecular level.

  Furthermore, the metal-clad laminate produced using this prepreg has no problem in appearance like the prepreg, and is cured while the molecular chains are partially and physically entangled with each other. Since the crosslink density is increased in a pseudo manner as compared with the case where the composition is cured, the elastic modulus is improved and the thermal expansion coefficient is lowered.

  Furthermore, by improving the elastic modulus and forming a uniform microphase separation structure, the fracture strength and heat resistance (especially during moisture absorption) of the resin can be significantly increased.

  Furthermore, as a component (C), by selecting a specific cross-linking agent that enhances the resin strength and toughness when cured, or restricts molecular motion, the metal foil peel strength is increased. It has been found that the level of thermal expansion and thermal expansion properties can be improved.

  In addition, the polyphenylene ether-modified butadiene prepolymer of the present invention is combined with an inorganic filler surface-treated with a specific surface treatment agent as the component (D), so that the inorganic filler is generally said to be blended. In addition to lowering the coefficient of thermal expansion, further improving heat resistance, and controlling the desired relative dielectric constant, it was found that the rate of change of the dielectric property during moisture absorption can be reduced (low moisture absorption dependent property) while suppressing deterioration of the dielectric property. .

  Usually, when an inorganic filler is blended in a resin material, a coupling agent is often used in combination for the purpose of improving dispersibility and improving adhesion to the resin. However, when an additive (in this case, a coupling agent) is used in combination with a resin system having extremely good dielectric properties as in the present invention, the additive such as the coupling agent is dielectric even with a small amount. The effect on characteristics (especially in the high frequency band and moisture absorption) is not small.

  However, when an inorganic filler surface-treated with a specific surface treatment agent (silane-based surface treatment agent or silicone-based surface treatment agent) used in the present invention is used in combination, the conventional cup is used in addition to the above normal effect. Since the polarity is lower than that of the ring agent system, dielectric characteristics (particularly in a high frequency band exceeding 1 GHz) are not deteriorated. Furthermore, since the silane-based treatment agent or the silicone-based surface treatment agent is excellent in low moisture absorption, it can exhibit low moisture absorption-dependent characteristics with excellent dielectric characteristics (particularly in a high frequency band exceeding 1 GHz).

  A novel semi-IPN composite thermosetting resin composition of the present invention is a thermosetting resin composition containing an uncured semi-IPN composite and a surface-treated inorganic filler, The cured semi-IPN type composite contains (A) polyphenylene ether and (B) 1,2-butadiene unit having 1,2-vinyl group in the side chain in the molecule of 40% or more, and is chemically modified. A non-cured semi-IPN type composite that is compatibilized with a prepolymer formed from an unmodified butadiene polymer and (C) a crosslinking agent, and the surface treatment agent for treating the surface-treated inorganic filler is an alkyl Trialkoxysilane, alkyldialkoxysilane, cycloalkyltrialkoxysilane, cycloalkyldialkoxysilane, phenyltrialkoxysilane, tris (trialkylsiloxy) Run, at least one of a silicone coating agent of formula (D-1) of the silicone oligomer, silicone oil of formula (D-2), and Formula (D-3).

Hereinafter, each component of the resin composition, and a preferable method for producing the polyphenylene ether-modified butadiene prepolymer and the resin composition will be described.
In the novel semi-IPN composite thermosetting resin composition of the present invention, the component (A) used for producing the polyphenylene ether-modified butadiene prepolymer is, for example, 2,6-dimethylphenol or 2,3,6. Poly (2,6-dimethyl-1,4-phenylene) ether or poly (2,3,6-trimethyl-1,4-phenylene) ether or 2,6-dimethylphenol obtained by homopolymerization of, -trimethylphenol And a copolymer of 2,3,6, -trimethylphenol and the like.

  In addition, so-called modified polyphenylene ether such as an alloyed polymer of these with polystyrene or styrene-butadiene copolymer can also be used. In this case, poly (2,6-dimethyl-1,4-phenylene) ether component, It is a polymer containing 50% or more of a (2,3,6-trimethyl-1,4-phenylene) ether component and a copolymer component of 2,6-dimethylphenol and 2,3,6, -trimethylphenol. Is more preferable.

  The molecular weight of the component (A) is not particularly limited, but considering the balance between the dielectric properties and heat resistance when used as a printed wiring board and the fluidity of the resin when used as a prepreg, the number average molecular weight is It is preferable that it is the range of 7000-30000. In addition, the number average molecular weight here is measured by gel permeation chromatography and converted by a calibration curve prepared using standard polystyrene.

  In the present invention, the component (B) used for the production of the polyphenylene ether-modified butadiene prepolymer contains 40% or more of 1,2-butadiene units having 1,2-vinyl groups in the side chain in the molecule, and There is no particular limitation as long as it is an unmodified butadiene polymer, and epoxidation, glycolation, phenolization, maleation, or both of one or both of the side chain 1,2-vinyl group and terminal in the molecule, It is an unmodified butadiene polymer that is not chemically modified, not a chemically modified modified polybutadiene such as (meth) acrylated and urethanized. Use of modified polybutadiene is not desirable because it deteriorates dielectric properties, moisture resistance and heat resistance after moisture absorption.

  The content of 1,2-butadiene units having a side chain 1,2-vinyl group in the molecule of the component (B) is more preferably 50% or more and 65% or more in view of the curability of the resin composition. Further preferred.

  In addition, the molecular weight of the component (B) is not particularly limited, but considering the balance between the curability of the resin composition and the dielectric properties of the cured product and the fluidity of the resin of the prepreg, the number average molecular weight Is preferably in the range of 500 to 10000, more preferably in the range of 700 to 8000, and still more preferably in the range of 1000 to 5000. The number average molecular weight is the same as the definition of the number average molecular weight in the component (A).

As the component (B), - _{[CH 2} -CH = _CH-CH 2] - units (j) and - _{[CH 2 -CH (CH = CH 2} ) ] - units (k) chemically unmodified butadiene consisting A polymer having a j: k ratio of 60 to 5:40 to 95 can be used.

  Specific examples of the component (B) preferably used in the present invention include trade names: B-1000, B-2000, B-3000 manufactured by Nippon Soda Co., Ltd., and B-1000 manufactured by Shin Nippon Petrochemical Co., Ltd. B-2000, B-3000, trade names manufactured by SARTOMER: Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154 and the like can be obtained commercially.

  In the present invention, the component (C) used in the production of the polyphenylene ether-modified butadiene prepolymer is a compound having a functional group having reactivity with the component (B) in the molecule. For example, one or more components in the molecule Examples thereof include a crosslinkable monomer or a crosslinkable polymer containing an ethylenically unsaturated double bond group.

  Specific examples of the component (C) include vinyl compounds, maleimide compounds, diallyl phthalates, (meth) acryloyl compounds, and unsaturated polyesters. Among these, the component (C) preferably used includes one or more maleimide compounds or one or more vinyl compounds, and is excellent in co-crosslinking property with the component (B). Good stability and storage stability, formability when used as a printed wiring board, dielectric properties, dielectric properties after moisture absorption, thermal expansion properties, metal foil peel strength, Tg, heat resistance during moisture absorption and It is desirable from the viewpoint that the total balance such as flame retardancy is excellent.

The maleimide compound suitably used as the component (C) of the present invention is represented by the following general formula (C-1):

(In the formula, R ¹⁰ is a monovalent or polyvalent organic group that is any one of m-valent aliphatic, alicyclic, aromatic, and heterocyclic, and X ^a and X ^b are hydrogen atoms, A monovalent atom or an organic group which may be the same or different and selected from a halogen atom and an aliphatic organic group, and m represents an integer of 1 or more. If it is a compound containing the maleimide group of, it will not specifically limit.

A monomaleimide compound or the following general formula (C-2):

(Wherein R ¹¹ is —C (X ^c ) ₂ —, —CO—, —O—, —S—, —SO ₂ —, or a bond to be linked, and may be the same or different, respectively. X ^c represents an alkyl group having 1 to 4 carbon atoms, —CF ₃ , —OCH ₃ , —NH ₂ , a halogen atom or a hydrogen atom, which may be the same or different from each other. Independent, n and p each represents an integer of 0 to 10).

  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.

  Specific examples of the polymaleimide compound represented by the general formula (C-2) include 1,2-dimaleimidoethane, 1,3-dimaleimidopropane, bis (4-maleimidophenyl) methane, and 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-ma Imidophenyl) ketone, 2,2-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, the following general formula (C-3):

(In the formula, q is an average value of 0 to 10.)
And the following general formula (C-4):

(In the formula, r is an average value of 0 to 10.)
Such as aliphatic, alicyclic, aromatic and heterocyclic polymaleimides (but each includes isomers).

  Aromatic polymaleimide is preferred from the viewpoint of moisture resistance, heat resistance, breaking strength, metal foil peel strength and low thermal expansion characteristics when used as a printed wiring board, and among them, the thermal expansion coefficient is particularly further reduced. In terms of point, it is more preferable to use bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and in terms of further increasing the breaking strength and the metal foil peeling strength, 2,2-bis (4- ( More preferably, 4-maleimidophenoxy) phenyl) propane is used.

  Moreover, in order to improve the moldability when it is used as a prepreg, monomaleimide that causes a gradual curing reaction is preferable, and among these, N-phenylmaleimide is more preferable in terms of cost.

  And the said maleimide compound may be used individually or in combination of 2 or more types, or may use together these 1 or more types of maleimide compounds and the crosslinking agent shown above 1 or more types.

  In the component (C), when the maleimide compound and other crosslinking agent are used in combination, the proportion of the maleimide compound in the component (C) is preferably 50% by mass or more, more preferably 80% by mass or more. And particularly preferably 100% by mass, that is, the case where all of the component (C) are maleimide compounds.

  Examples of the vinyl compound suitably used as the component (C) include styrene, divinylbenzene, vinyltoluene, and divinylbiphenyl. Of these, divinylbiphenyl is preferred.

  As a specific example of the component (C) preferably used in the present invention, divinylbiphenyl manufactured by Nippon Steel Chemical Co., Ltd. is commercially available.

  The polyphenylene ether-modified butadiene prepolymer in the novel semi-IPN composite thermosetting resin composition of the present invention is preferably a component (B) and a component (C) in the presence of the component (A) developed in a medium. ) Component can be pre-reacted to such an extent that it does not gel.

  As a result, a semi-IPN polymer in which molecular chains are physically entangled with each other is formed between the component (A), the component (B), and the component (C), which are inherently incompatible systems, and are completely cured. An apparently uniform (compatibilized) prepolymer is obtained in an uncured state in stages.

  According to the present invention, for example, after the component (A) is developed in a medium by dissolving it in a solvent, the component (B) and the component (C) are dissolved or dispersed in this solution, It can be produced by heating and stirring at a temperature of 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.

After the polyphenylene ether-modified butadiene prepolymer is produced, the solvent may be completely removed by concentration or the like to obtain a solvent-free resin composition, or the polyphenylene ether-modified butadiene prepolymer solution dissolved or dispersed in the solvent as it is. It is 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.

  In the resin composition of the present invention, the blending ratio of the component (A), the component (B) and the component (C) used for the production of the polyphenylene ether-modified butadiene prepolymer is the blending ratio of the component (A) (B). It is preferable to set it as the range of 2-200 mass parts with respect to 100 mass parts of total amounts of a component and (C) component, It is more preferable to set it as 10-100 mass parts, It is set as 15-50 mass parts. Further preferred.

  The blending ratio of component (A) is a balance between the coefficient of thermal expansion, the dielectric properties and the coating workability resulting from the viscosity of the resin varnish, and the moldability of the printed wiring board resulting from the melt viscosity when used as a prepreg. In consideration of the above, it is preferable to blend with respect to 100 parts by mass of the total amount of component (B) and component (C).

  Moreover, it is preferable that the mixture ratio of (C) component shall be the range of 2-200 mass parts with respect to 100 mass parts of (B) component, It is more preferable to set it as 5-100 mass parts, 10-75 masses More preferably, it is a part.

  The blending ratio of the component (C) is preferably blended with respect to 100 parts by weight of the component (B) in consideration of the balance between the coefficient of thermal expansion, Tg, peel strength of the metal foil, and dielectric properties. The polyphenylene ether-modified butadiene prepolymer of the present invention is obtained by preliminary reaction so that the conversion rate (reaction rate) of the component (C) is in the range of 5 to 100% during the production thereof.

  More preferable range depends on the blending ratio of the component (B) and the component (C), and the blending ratio of the component (C) is in the range of 2 to 10 parts by weight with respect to 100 parts by weight of the component (B). More preferably, the conversion rate (reaction rate) of the component (C) is in the range of 10 to 100%, and in the range of 10 to 100 parts by mass, the conversion rate (reaction rate) of the component (C) is More preferably, it is in the range of 7 to 90%, and in the range of 100 to 200 parts by mass, the conversion rate (reaction rate) of the component (C) is more preferably in the range of 5 to 80%.

  The conversion rate (reaction rate) of component (C) is that the resin composition and prepreg have a uniform appearance and no tack, printed wiring board, heat resistance when absorbing moisture, metal foil peeling strength, thermal expansion Considering the coefficient, it is preferably 5% or more.

  In addition, the polyphenylene ether modified butadiene prepolymer in the present invention includes a state in which the component (C) is 100% converted. Moreover, the conversion of (C) component is less than 100%, and the state which does not react and remains unconverted (C) component is also included.

  The conversion rate (reaction rate) of the component (C) is based on the residual amount of the component (C) in the polyphenylene ether-modified butadiene prepolymer measured by gel permeation chromatography and the calibration curve of the component (C) prepared in advance. It is converted.

  Component (D) of the thermosetting resin composition of the present invention is an inorganic filler surface-treated with a specific surface treatment agent (a silane surface treatment agent or a silicone surface treatment agent). The agent is not particularly limited, and specifically, aluminum oxide, titanium oxide, mica, silicon oxide, beryllium oxide, 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, etc. are used. These inorganic fillers may be used alone or in combination of two or more. The shape and particle size of the inorganic filler are not particularly limited, but those having a particle size of 0.01 to 30 μm, preferably 0.1 to 15 μm are suitably used.

  In the thermosetting resin composition of the present invention, the specific surface treatment agent used for the component (D) is a silane surface treatment agent or a silicone surface treatment agent having a low polarity. Specific examples include alkyltrialkoxysilanes having 6 or more carbon atoms such as hexyltrimethoxysilane and decyltrimethoxysilane, aromatic trialkoxysilanes such as phenyltrimethoxysilane, alkyldialkoxysilanes such as cyclohexylmethyldimethoxysilane, and tris. Silicone oils such as tris (trialkylsiloxy) silanes such as (trimethylsiloxy) silane, silicone oligomers such as alkoxysilicone oligomers, long-chain alkyl-modified non-reactive silicone oils or long-chain alkyl-aralkyl-modified non-reactive silicone oils, silicones A coating agent is mentioned. For example, Formula (D-1):

Wherein R ¹ and R ² are H, CH ₃ , C ₆ H ₅ , C _a H _{2a + 1} , C ₂ H ₄ CF ₃ , or

A is an integer of 1 or more, and n is an integer of 1 or more)
A silicone oligomer represented by formula (D-2):

Wherein R ¹ , R ² , a and n are as defined above,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are H, CH ₃ , C ₆ H ₅ , C _a H _{2a + 1} , C ₂ H ₄ CF ₃ , or

One of
And a silicone oil represented by formula (D-3):

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , a and n are as defined above,
R ⁸ and R ⁹ are H, CH ₃ , C ₆ H ₅ , C _a H _{2a + 1} , C ₂ H ₄ CF ₃ , or

And b is an integer of 1 or more, c is an integer of 1 or more, and d is an integer of 1 or more)
It is the silicone coating agent represented by these.

  Of these, hexyltrimethoxysilane, decyltrimethoxysilane, cyclohexylmethyldimethoxysilane, tris (trimethylsiloxy) silane, silicone oligomer, long-chain alkyl-modified non-reactive silicone oil, and silicone coating agent are particularly preferable.

  These specific surface treatment agents (silane-based surface treatment agents or silicone-based surface treatment agents) may be used alone or in combination of two or more. Examples of the surface treatment agent include hexyltrimethoxysilane (KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.), decyltrimethoxysilane (KBM-3103, manufactured by Shin-Etsu Chemical Co., Ltd.), methyltrimethoxysilane (KBM-13, Shin-Etsu). Chemical Industry Co., Ltd.), phenyltrimethoxysilane (KBM-103, Shin-Etsu Chemical Co., Ltd.), cyclohexylmethyldimethoxysilane (CHMS-112, Shin-Etsu Chemical Co., Ltd.), tris (trimethylsiloxy) silane (S-1003TS, Shin-Etsu) Chemical Industries), silicone oligomer (KR-2000, Shin-Etsu Chemical Co., Ltd.), alkoxy silicone oligomer (X-40-9225, Shin-Etsu Chemical Co., Ltd.), long chain alkyl-modified non-reactive silicone oil (KF-4917) , Manufactured by Shin-Etsu Chemical Co., Ltd.), long chain alkyl aralkyl modification Non-reactive silicone oil (X-22-1877, manufactured by Shin-Etsu Chemical Co., Ltd.), a silicone coating agent (KPN-3504, manufactured by Shin-Etsu Chemical Co., Ltd.).

  The amount of the surface treatment agent attached to the inorganic filler is not particularly limited, but considering the dispersibility of the inorganic filler in the resin material and the heat resistance when cured, the amount of the inorganic filler 0.01-20 mass% is suitable, Preferably it is 0.05-10 mass%, More preferably, it is 0.1-7 mass%.

  The blending ratio of component (D) in the resin composition of the present invention is not particularly limited, but with respect to 100 parts by mass of the total amount of component (A), component (B), component (C) and component (D), 1-1000 mass parts is preferable, 5-500 mass parts is more preferable, 10-350 mass parts is still more preferable, and the compounding quantity which considered desired relative dielectric constant control, heat resistance improvement, and the moldability of a prepreg can be determined suitably. .

  In addition, the component (D) may be pretreated by a wet or dry process with a surface treatment agent, or a polyphenylene ether-modified butadiene prepolymer is mixed and mixed with a surface treatment agent and an inorganic filler. Then, the surface treatment may be used.

  In the case of a wet method, it can be used as a surface-treated slurry in which a surface treatment agent and an inorganic filler are dispersed in an organic solvent or the like (dispersion medium). And can be used as a slurry. In addition, processing conditions such as time and temperature during the surface treatment are not particularly limited.

  The resin composition of the present invention includes a purpose of initiating or promoting a preliminary reaction between the component (B) and the component (C) in the production of a polyphenylene ether-modified butadiene prepolymer, a metal-clad laminate, and a multilayer printed wiring board. For the purpose of initiating or accelerating the curing reaction of the resin composition when producing, it is preferable to contain (E) a radical reaction initiator.

  Specific examples of the component (E) 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) Hexin-3, di-t-butyl peroxide, α, α'-bis (t-butylperoxy) diisopropyl Pyrbenzene, 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) isophthalate, isobutyryl peroxide , Peroxides such as di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy -2-Methylpropan-1-one, benzoin methyl Ether, although methyl -o- benzoyl benzoate, and the like, without limitation.

  Component (E) is used for the purpose of initiating or accelerating a pre-reaction during the production of the polyphenylene ether-modified butadiene prepolymer, and for the purpose of initiating or accelerating the curing reaction after the production of the polyphenylene ether-modified butadiene prepolymer. Are preferably blended separately before and after the production of the polyphenylene ether-modified butadiene prepolymer. In that case, (E) component mix | blended for each objective may use the same kind, may use a different kind, each may be used individually, and two or more types may be mixed. It may be used.

  The blending ratio of the component (E) in the resin composition of the present invention can be determined according to the blending ratio of the component (B) and the component (C), and the total amount of the component (B) and the component (C). It is preferable to set it as 0.05-10 mass parts with respect to 100 mass parts. When the radical reaction initiator of component (E) is blended within this numerical range, an appropriate reaction rate can be obtained in a preliminary reaction when producing a polyphenylene ether-modified butadiene prepolymer, and metal-clad laminates and multilayer printed wiring boards can be obtained. In the curing reaction during production, good curability is obtained.

  In addition, the resin composition of the present invention contains (F) an uncured semi-IPN type composite, and if necessary, contains at least one ethylenically unsaturated double bond group in the molecule. Monomer or crosslinkable polymer, (G) brominated flame retardant and / or phosphorus flame retardant, (H) saturated thermoplastic elastomer and various thermosetting resins, various thermoplastic resins, various additives, When blended in a range that does not deteriorate properties such as dielectric properties, heat resistance, adhesiveness (stripping strength of metal foil, adhesion to a substrate such as glass), moisture resistance, Tg, and thermal expansion properties Furthermore, you may mix | blend.

  The crosslinkable monomer or crosslinkable polymer containing one or more ethylenically unsaturated double bond groups in the molecule that does not constitute the uncured semi-IPN type complex of the component (F) is polyphenylene ether-modified butadiene. It is blended after the production of the prepolymer and is not particularly limited.

  Component (F) is specifically selected from the group consisting of butadiene polymers and maleimide compounds that are not chemically modified.

  As the component (F), compounds exemplified as the component (B) and the component (C) can be used. Moreover, as a butadiene polymer not chemically modified, a butadiene polymer having a number average molecular weight exceeding 10,000 is not chemically modified. These compounds may be used alone or in a combination of two or more.

  When the same compound as exemplified as the component (B) and the component (C) is blended as the component (F), use the same type as that used when producing the polyphenylene ether-modified butadiene prepolymer. Alternatively, different types may be used. In this case, since it is blended after the production of the uncured semi-IPN composite thermosetting resin composition (polyphenylene ether-modified butadiene prepolymer), the blending amount of the component (F) in that case is the component (B) In addition, it is distinguished from the blending amount of the component (C), and preferable blending amounts are separately described below.

  As the component (F), when a butadiene polymer having a number average molecular weight exceeding 10,000 is not chemically modified, it can be used in a liquid type or a solid type, and a 1,2-vinyl bond ratio and a 1,4-bond can be used. The ratio is not particularly limited.

  Although the compounding ratio of the said (F) component in the resin composition of this invention is not specifically limited, 2-100 mass with respect to 100 mass parts of total amounts of (A) component, (B) component, and (C) component. Part, preferably 2 to 80 parts by weight, more preferably 2 to 60 parts by weight.

  Although it does not specifically limit as a flame retardant of the said (G) component, 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, brominated reactive flame retardant unsaturated double bond-containing, such as pentabromobenzyl acrylate 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.

  Although the compounding ratio of the (G) component in the resin composition of the present invention is not particularly limited, it is 5 to 200 parts by mass with respect to 100 parts by mass of the total amount of the (A) component, the (B) component, and the (C) component. It is preferable to set it as 5 to 150 mass parts, and it is still more preferable to set it as 5 to 100 mass parts.

  If the blending ratio of the flame retardant is less than 5 parts by mass, the flame resistance tends to be insufficient, and if it exceeds 200 parts by mass, the heat resistance and the metal foil peeling strength tend to be reduced when a printed wiring board is used. .

  The component (H) is not particularly limited as long as it is a saturated thermoplastic elastomer, but a styrene saturated thermoplastic elastomer having good compatibility with the component (A) is desirable. Specific examples of the component (H) preferably used in the present invention include styrene-ethylene-butylene copolymers, and a method of hydrogenating an unsaturated double bond portion of a butadiene block of a styrene-butadiene copolymer. Etc. can be obtained.

  Further, when using a styrene-based saturated thermoplastic elastomer, the content ratio of the styrene block is 20 to 20 from the balance between the compatibility with the polyphenylene ether-modified butadiene prepolymer and the thermal expansion characteristics when the resin composition is cured. 70% is preferable.

  Furthermore, as the component (H), a chemically modified saturated thermoplastic elastomer having a functional group such as an epoxy group, a hydroxyl group, a carboxy group, an amino group, or an acid anhydride in the molecule can be used. In addition, the component (H) may be used alone or in combination of two or more kinds, and when a styrene saturated thermoplastic elastomer is used, two or more kinds having different styrene contents may be used in combination.

  Further, the saturated thermoplastic elastomer of component (H) may be blended after the production of the polyphenylene ether-modified butadiene prepolymer, for example, component (A) and component (H) developed in a medium such as a solvent. May be used as a polyphenylene ether-modified butadiene prepolymer combined with a saturated thermoplastic elastomer produced by pre-reacting the component (B) and the component (C) in the presence of

  When producing a saturated thermoplastic elastomer combined polyphenylene ether-modified butadiene prepolymer, the preferred specific examples and blending amounts in each component and the production method such as the conversion rate (reaction rate) of the component (C) are described above. The description in the production of modified butadiene prepolymers applies.

  Although the compounding ratio of the (H) component in the resin composition of the present invention is not particularly limited, it is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the (A) component, the (B) component, and the (C) component. It is preferable to set it as 2-50 mass parts, and it is still more preferable to set it as 5-30 mass parts. If the blending ratio of the component (H) is less than 1 part by mass, the effect of improving the dielectric characteristics tends to be insufficient, and if it exceeds 100 parts by mass, the thermal expansion characteristics of the cured product tend to deteriorate.

  The solvent in the present invention is not particularly limited, but specific examples include alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol and butyl carbitol. , Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, mesitylene, esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, N, N -Solvents such as nitrogen-containing compounds such as dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone.

  Moreover, these solvents may be used alone or in combination of two or more. More preferred are aromatic hydrocarbons such as toluene, xylene and mesitylene, and mixed solvents of aromatic hydrocarbons and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.

  Among these solvents, the blending ratio when aromatic hydrocarbons and ketones are used as a mixed solvent is preferably 5 to 100 parts by mass of ketones with respect to 100 parts by mass of aromatic hydrocarbons. 10 to 80 parts by mass, more preferably 15 to 60 parts by mass.

  In addition, also when using the inorganic filler slurry surface-treated in the organic solvent as (D) component, the solvent etc. which were shown above can be used. These solvents may be used alone or in combination of two or more. Even if they are the same as the solvent used in the production of the polyphenylene ether-modified butadiene prepolymer, different types of solvents may be used. It may be used.

  In the resin composition of the present invention, various thermosetting resins to be blended as necessary are not particularly limited, but specific examples include epoxy resins, cyanate ester resins, phenol resins, urethane resins, and melamine resins. Benzoxazine resin, benzocyclobutene resin, dicyclopentadiene resin and the like, and these curing agents and curing accelerators can be used.

  Further, various thermoplastic resins to be blended as necessary are not particularly limited, but specific examples include polyolefins such as polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, and poly (4-methyl-pentene). And derivatives thereof, polyesters and derivatives thereof, polycarbonate, polyacetal, polysulfone, (meth) acrylic acid ester copolymers, polystyrene, acrylonitrile styrene copolymers, acrylonitrile styrene butadiene copolymers, polyvinyl acetal, polyvinyl Butyrals, polyvinyl alcohols, polybutadiene complete hydrogenates, polyethersulfone, polyetherketone, polyetherimide, polyphenylene sulfite, polyamideimide, polyamide, heat Plastic polyimide, and a liquid crystal polymer such as aromatic polyester.

  Various additives are not particularly limited, but specific examples include silane coupling agents, titanate coupling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and the like. Can be mentioned.

  Moreover, these thermosetting resins, thermoplastic resins and additives may be used alone or in combination of two or more.

  As one method for producing the resin composition of the present invention, the polyphenylene ether-modified butadiene prepolymer obtained from the above-mentioned component (A), component (B) and component (C), component (D), radical (E) Initiator, crosslinkable monomer or crosslinkable containing one or more ethylenically unsaturated double bond groups in the molecule, which does not constitute (F) an uncured semi-IPN type composite compounded as necessary A polymer, (G) a flame retardant, (H) a saturated thermoplastic elastomer and various thermosetting resins, various thermoplastic resins, and various additives can be produced by blending, stirring and mixing by known methods. .

  The resin varnish of the present invention can be obtained by dissolving or dispersing the above-described resin composition of the present invention in a solvent. In addition, when a polyphenylene ether-modified butadiene prepolymer is produced in a solution, the solvent is once removed, and the solvent-free polyphenylene ether-modified butadiene prepolymer and the above-described other compounding agents are dissolved or dispersed in the solvent. It may be a resin varnish. A slurry in which (D) component or (D) component is dispersed in a solvent in a polyphenylene ether-modified butadiene prepolymer solution, (E) component, and (F) component, (G) component as required The (H) component, the above-mentioned other compounding agents, and an additional solvent may be further blended as necessary to obtain a resin varnish.

  The solvent used for varnishing the above resin composition is not particularly limited, but specific examples of preferred solvents include the above polyphenylene ether-modified butadiene prepolymer or saturated thermoplastic elastomer combined polyphenylene ether-modified butadiene. What was described about the solvent used in the case of manufacture of a prepolymer can be used, These may be used individually by 1 type and may be used in combination of 2 or more types. Of these, aromatic hydrocarbons such as toluene, xylene, and mesitylene, and mixed solvents of aromatic hydrocarbons and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are more preferable.

  The solvent used for varnishing may be the same type as the solvent used in the production of the polyphenylene ether-modified butadiene prepolymer or a different type of solvent. In addition, when the varnish is formed, 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 prepreg is prepared using the resin varnish of the present invention. When manufacturing, etc., by adjusting the amount of solvent, it is adjusted to a solid content (non-volatile content) concentration and varnish viscosity that is optimal for coating work (for example, to achieve a good appearance and an appropriate resin adhesion amount). be able to.

  Using the above-described resin composition and resin varnish of the present invention, the prepreg and metal-clad laminate of the present invention can be produced by a known method. For example, after impregnating the reinforcing fiber base material such as glass fiber and organic fiber with the thermosetting resin composition and resin varnish of the present invention, it is usually 60 to 200 ° C., preferably 80 to 170 ° C. in a drying furnace or the like. The prepreg is obtained by drying at a temperature of 2 to 30 minutes, preferably 3 to 15 minutes.

  Next, a metal foil is placed on one or both sides of the prepreg or a plurality of the prepregs, and heated and / or pressurized under predetermined conditions to obtain a double-sided or single-sided metal-clad laminate.

  The heating in this case can be carried out preferably in a temperature range of 100 ° C. to 250 ° C., and the pressurization can be carried out preferably in a pressure range of 0.5 to 10.0 MPa. Heating and pressing are preferably performed simultaneously using a vacuum press or the like. In this case, it is preferable to perform these treatments for 30 minutes to 10 hours.

In addition, using the prepreg and metal-clad laminate produced as described above, drilling, metal plating, circuit formation by etching metal foil, and multilayer bonding are performed by known methods. Thus, a single-sided, double-sided or multilayer printed wiring board can be obtained.
The present invention is not limited to the above-described modes and embodiments, and can be arbitrarily changed and modified within the scope not departing from the object of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Preparation example 1 of resin varnish (resin composition)
In a 1 liter separable flask equipped with a thermometer, a reflux condenser, a vacuum concentrator and a stirrer, 333 parts by mass of toluene and polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals, Mn: 16000) as component (A) ) 13 parts by mass were charged, and the temperature in the flask was set to 90 ° C and dissolved by stirring. Next, butadiene polymer (B-3000, manufactured by Nippon Soda Co., Ltd., Mn: 3000, 1,2-vinyl structure: 90%) 100 parts by mass as component (B) and component (C) 16 parts by mass of N-phenylmaleimide (Imirex-P, manufactured by Nippon Shokubai Co., Ltd.) was added and stirring was continued. It was confirmed that these were dissolved or uniformly dispersed. Thereafter, the liquid temperature was raised to 110 ° C. While maintaining the temperature at 110 ° C., 0.5 parts by mass of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation) was blended as a reaction initiator. .
The blended product is pre-reacted for about 1 hour with stirring, so that (A) polyphenylene ether, (B) butadiene polymer not chemically modified, and (C) cross-linking agent are compatibilized. A prepolymer solution was obtained. When the conversion rate of bis (4-maleimidophenyl) methane in this polyphenylene ether-modified butadiene prepolymer solution was measured using gel permeation chromatography (GPC), the conversion rate was 30%. Here, the conversion rate is a value obtained by subtracting the unconverted portion (measured value) of N-phenylmaleimide from 100. Subsequently, the liquid temperature in a flask was set to 80 degreeC. Then, it concentrated under reduced pressure so that the solid content concentration of a solution might be 60 mass%, stirring. The solution was then cooled to room temperature.

  Next, as component (D), spherical silicon oxide (spherical silica: SO-25R, average particle) obtained by surface-treating hexyltrimethoxysilane (KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.) in a solvent in a treatment amount of 2% by mass in advance. A slurry (solid content: 70% by mass, solvent: MIBK) of 315 parts by mass (solid content: 220 parts by mass) was blended. Next, 155 parts by mass (solid content) of 24.5% toluene solution of 2 types of hydrogenated styrene-butadiene copolymer (Tuftec H1043 and Tuftech H1051, manufactured by Asahi Kasei Chemicals) as a saturated thermoplastic elastomer of component (H) Min: 19 parts by mass). Next, 4 parts by mass of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-5100, manufactured by Daiwa Kasei Kogyo Co., Ltd.) as the component (F) was blended. Next, 50 parts by mass of ethylenebis (pentabromophenyl) (SAYTEX8010, manufactured by Albemarle) as a component (G) was blended. Next, 3 parts by mass of α, α'-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) was added as component (E). Subsequently, methyl isobutyl ketone (MIBK) was mix | blended and the resin varnish (solid content concentration of about 50 mass%) of the preparation example 1 was prepared.

Preparation Example 2
A resin varnish of Preparation Example 2 was prepared in the same manner as in Preparation Example 1, except that decyltrimethoxysilane (KBM-3103, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

Preparation Example 3
A resin varnish of Preparation Example 3 was prepared in the same manner as in Preparation Example 1, except that methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

Preparation Example 4
A resin varnish of Preparation Example 4 was prepared in the same manner as in Preparation Example 1, except that phenyltrimethoxysilane (KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

Preparation Example 5
A resin varnish of Preparation Example 5 was prepared in the same manner as in Preparation Example 1, except that cyclohexylmethyldimethoxysilane (CHMS-112, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

Preparation Example 6
A resin varnish of Preparation Example 6 was prepared in the same manner as in Preparation Example 1, except that tris (trimethylsiloxy) silane (S-1003TS, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

Preparation Example 7
A resin varnish of Preparation Example 7 was prepared in the same manner as in Preparation Example 1, except that a silicone oligomer (KR-2000, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

Preparation Example 8
A resin varnish of Preparation Example 8 was prepared in the same manner as in Preparation Example 1, except that an alkoxysilicone oligomer (X-40-9225, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

Preparation Example 9
The resin varnish of Preparation Example 9 was prepared in the same manner as in Preparation Example 1 except that long-chain alkyl-modified non-reactive silicone oil (KF-4917, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane. did.

Preparation Example 10
In Preparation Example 1, the same procedure as in Preparation Example 10 was performed except that long-chain alkyl / aralkyl-modified non-reactive silicone oil (X-22-1877, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane. A resin varnish was prepared.

Preparation Example 11
A resin varnish of Preparation Example 11 was prepared in the same manner as in Preparation Example 1, except that a silicone coating agent (KPN-3504, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

Preparation Example 12
Preparation Example 12 was carried out in the same manner as in Preparation Example 1, except that 1000 parts by mass of strontium titanate (SL250, average particle size: 0.85 μm, manufactured by Fuji Titanium Industry Co., Ltd.) was used instead of spherical silica (SO-25R). A resin varnish was prepared.

Preparation Example 13
In Preparation Example 1, 1000 parts by mass of calcium titanate (average particle size 2 μm, trade name CT-D50, manufacturer: manufactured by Fuji Titanium Industry Co., Ltd.) was used instead of spherical silica (SO-25R). In the same manner, a resin varnish of Preparation Example 13 was prepared.

Comparative Preparation Example 1
A resin varnish of Comparative Preparation Example 1 was prepared in the same manner as in Preparation Example 1, except that vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

Comparative Preparation Example 2
A resin varnish of Comparative Preparation Example 2 was prepared in the same manner as in Preparation Example 1, except that styryltrimethoxysilane (KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hexyltrimethoxysilane.

  The usage-amounts of each raw material used for preparation of the resin varnish (curable resin composition) of Preparation Examples 1-13 and Comparative Preparation Examples 1-2 are collectively shown in Table 1-1 and Table 1-2.

Production of Resin Plate The resin varnishes obtained in Preparation Examples 1 to 13 and Comparative Preparation Examples 1 and 2 were coated on a glass plate with a gap of 0.3 mm. Subsequently, it heat-dried at 110 degreeC for 10 minute (s), and B stage resin was obtained. A predetermined amount of this is put in a Teflon (R) formwork, and a low profile copper foil (F3-WS, M surface Rz: 3 μm, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 18 μm is arranged on both sides so that the glossy surface is in contact. The resin plate (thickness: 0.1 mm) was produced by heating and pressing under the press conditions of 185 ° C., 2 MPa, and 90 minutes.

Preparation of Prepreg The resin varnish obtained in Preparation Examples 1 to 13 and Comparative Preparation Examples 1 and 2 was impregnated into a glass cloth (E glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm. Subsequently, it heat-dried at 100 degreeC for 6 minute (s), and produced the prepreg with a resin content rate of 56-57 mass%.

Production of double-sided copper-clad laminate On both sides of the base material formed by stacking the above six prepregs, a low profile copper foil (F3-WS, M-plane Rz: 3 μm, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 18 μm is provided on the M-plane. Were placed in contact with each other and vacuum-heated and pressure-molded under press conditions of 185 ° C., 4 MPa, and 80 minutes to produce a double-sided copper-clad laminate (thickness: 0.7 mm). For the copper-clad laminate, copper was entirely etched with an aqueous ammonium persulfate solution for evaluation.

  The above-described resin plate and etched copper-clad laminate were evaluated for dielectric properties, water absorption, and moisture absorption heat resistance at 10 GHz. Moreover, the thermal expansion characteristic and peeling strength were evaluated about the copper clad laminated board.

The characteristic evaluation method is as follows.
Measurement of dielectric properties:
Dielectric properties were measured by the cavity resonator method. Furthermore, the dielectric properties (relative dielectric constant, dielectric loss tangent) are measured for those after being held in a constant temperature and humidity chamber (conditions: 85 ° C., 85% RH) for 500 hours (abbreviation: C-500 / 85/85). did. The difference in dielectric constant between normal and moisture absorption was ΔDk, and the difference in dielectric loss tangent was ΔDf. The measurement conditions were the same as in the normal case.

Measurement of water absorption:
The water absorption was determined from the change in mass before and after moisture absorption. The moisture absorption treatment was performed under the above conditions of C-500 / 85/85. The mass of the resin plate before moisture absorption and the etched copper clad laminate (MCL) was Wd, the mass after moisture absorption was Ww, and the value (%) of ((Ww / Wd) -1) * 100 was the water absorption rate.

Measurement of moisture absorption heat resistance:
The whole-surface etched MCL was subjected to pressure cooker treatment (121 ° C.-2 atm) to absorb moisture and submerged in a solder bath heated to 288 ° C. for 20 seconds.
After submerging in the solder bath, those that did not cause blistering or measling by visual inspection were regarded as acceptable.

Measurement of thermal expansion characteristics:
About the MCL which etched the whole surface, the thermal expansion coefficient (alpha) and glass transition temperature Tg were measured using the thermomechanical analyzer (TMA Q-400, TA instruments).
The measurement conditions were as follows: 1st run was 250 ° C., 2nd run was 10 ° C./min up to 260 ° C., and the load was 0.05N. The inflection point of the 2nd run linear expansion curve was defined as Tg.

Measurement of peel strength:
It measured based on JIS-C-6481.

Characterization results:
Regarding the dielectric characteristics and water absorption, Table 2 shows the results of the resin plate and Table 3 shows the results of the etched MCL.
The moisture absorption heat resistance (after PCT-5h treatment) was good.
The thermal expansion characteristics are shown in Table 4.
The peel strength was good.

  From the results shown in Tables 2 and 3, when ΔDk is small, it is possible to suppress a decrease in signal level during moisture absorption. Further, when ΔDf is small, the Q value representing the sharpness of the resonance signal peak can be maintained, and a decrease in the electric signal level during moisture absorption can be suppressed as in the case of ΔDk. Furthermore, since Df does not become large, the attenuation amount of the electric signal on the circuit board can be suppressed.

  When the dielectric constant change ΔDk when the resin plate is placed at 85 ° C. and 85% RH for 500 hours in Table 2, the average value is 0.037 in the vinyl group-containing silane coupling agents of Comparative Examples 1 and 2. On the other hand, in the examples, the average value is as small as about 0.031, indicating a reduction of about 15%. According to Patent Document 15, the resin system using the vinyl group-containing silane coupling agent of the comparative example is excellent in dielectric properties and the dielectric constant change after moisture absorption is small, but when the surface treatment agent group of the present invention is used, It can also be seen that the change in dielectric constant is small and even better. The dielectric loss tangent variation ΔDf is smaller than the average value of about 0.00195 in the comparative example, about 0.00125 in the example, indicating a decrease of about 35%. This is also the case of the surface treatment agent of the present invention. You can see that it is better. Similarly, the water absorption rate (C-500 / 85/85) is about 40% less than the average value of the comparative example of about 0.195%, and the average value of the example is about 0.12%. Are better.

    Next, when ΔDk of the copper-clad laminate etched in Table 3 is seen, the average value in the example is as small as about 0.032 compared to the average value of about 0.0375 in the comparative example. It can be seen that the property is about 15% smaller. As for ΔDf, the average value of the comparative example is about 0.00115 in comparison with the average value of about 0.05765, indicating a decrease of about 55%. The water absorption rate is about 0.24% in the comparative example, while the average value in the example is as small as about 0.17%, showing a decrease of about 30%, and having a moisture absorption resistance equivalent to or higher. I understand.

    From the above, the surface treatment agent within the scope of the present invention has low moisture absorption dependency in dielectric properties (low moisture absorption dependency), and is excellent in low moisture absorption dependency properties as compared with the vinyl group-containing silane coupling agent of Patent Document 15. It can be said that. And in the Example of this invention, it was excellent also in moisture absorption heat resistance, a thermal expansion characteristic, and peeling strength.

  The resin composition of the present invention has a novel configuration of a thermosetting resin composition in which an inorganic filler surface-treated with a specific surface treatment agent is combined with a compatibilized uncured semi-IPN type composite, The printed wiring board using the resin composition of the present invention has a sufficient dielectric strength at a high frequency, a characteristic to reduce transmission loss, and a low thermal expansion characteristic, but has a sufficient peeling strength with a metal foil. Can be raised to a certain level. Further, in addition to the improvement in heat resistance, desired dielectric constant control and further reduction in thermal expansion obtained when an inorganic filler is used in combination, in the present invention, the rate of change in dielectric properties due to moisture absorption can be kept small. Furthermore, resin varnishes, prepregs, and metal-clad laminates that use the resin composition of the present invention are approached from both aspects of reducing dielectric loss by improving dielectric properties and reducing conductor loss by applying metal foil with low surface roughness. In addition, the transmission loss in the high frequency band can be reduced to a sufficient level, and can be suitably used for the manufacture of printed wiring boards used in the high frequency field. Therefore, the present invention is used in mobile communication devices that handle high-frequency signals in a high-frequency band, for example, 1 GHz or more, and network-related electronic devices such as base station devices, servers, and routers, and various electric and electronic devices such as large computers. It is useful as a printed wiring board member / part application.

Claims (19)

A thermosetting resin composition comprising an uncured semi-IPN type composite and a surface-treated inorganic filler,
The uncured semi-IPN type composite contains (A) polyphenylene ether and (B) 1,2-butadiene unit having 1,2-vinyl group in the side chain in the molecule of 40% or more, and is chemically modified. Uncured butadiene polymer and (C) a prepolymer formed from a crosslinker are uncured semi-IPN type composites that are compatibilized,
Surface treatment agent for treating a surface treated inorganic filler, alkyltrialkoxysilane, alkyl dialkoxy silanes, cycloalkyl trialkoxysilane, cycloalkyl dialkoxysilane, phenyltrialkoxysilane and tris (trialkylsiloxy) Sila down at least one is a surface treatment agent, the thermosetting resin composition is selected from or Ranaru group. The uncured semi-IPN type composite consists of (A) polyphenylene ether, (B) a radical polymerizable polymer obtained by radical polymerization of a butadiene polymer and (C) a crosslinking agent,
A chemically modified butadiene polymer in which (B) is composed of — [CH ₂ —CH═CH—CH ₂ ] —unit (j) and — [CH ₂ —CH (CH═CH ₂ )] — unit (k) And the ratio of j: k is 60-5: 40-95,
The thermosetting resin composition according to claim 1, wherein (C) is a compound having one or more ethylenically unsaturated double bonds in the molecule.   The uncured semi-IPN type composite contains (A) polyphenylene ether in the presence of (B) 1,2-butadiene unit having a 1,2-vinyl group in the side chain in a molecule of 40% or more, The thermosetting resin composition according to claim 1, which is a polyphenylene ether-modified butadiene prepolymer obtained by pre-reacting a butadiene polymer not chemically modified and (C) a crosslinking agent.   The thermosetting resin composition according to claim 3, which is obtained by pre-reacting an uncured semi-IPN composite so that the conversion rate of the component (C) is in the range of 5 to 100%. (D) The inorganic filler used for the surface-treated inorganic filler is aluminum oxide, titanium oxide, mica, silicon oxide, beryllium oxide, 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, talc, aluminum borate, carbonization silicon, and from mixtures thereof The thermosetting resin composition according to any one of claims 1 to 4, which is at least one inorganic filler selected.   The thermosetting resin composition according to any one of claims 1 to 5, wherein the inorganic filler is spherical silicon oxide having an average particle diameter of 0.01 to 30 µm. (D) a surface treatment agent used in the component, C ₁ -C ₃₀ alkyl trialkoxysilane, C ₁ -C ₃₀ alkyl dialkoxy silanes, cycloalkyl trialkoxysilane, cycloalkyl dialkoxysilane, phenyltrialkoxysilane and tris it is at least one selected from (trialkylsiloxy) Sila down or Ranaru group, a thermosetting resin composition of any one of claims 1-6. (D) a surface treatment agent used in component selection, hexyl trimethoxysilane, decyl trimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, from cyclohexyl methyl dimethoxy silane and tris (trimethylsiloxy) Sila down or Ranaru group The thermosetting resin composition as described in any one of Claims 1-6 containing the at least 1 type | mold made.   The thermosetting resin composition as described in any one of Claims 1-8 which uses the surface treating agent used for (D) component by 0.01-20 mass% of an inorganic filler mass. As the component (C), the general formula (C-1):

(Wherein R ¹⁰ is an m-valent aliphatic or aromatic organic group, and X ^a and X ^b are the same or different selected from a hydrogen atom, a halogen atom and an aliphatic organic group. It is a monovalent atom or an organic group that may be present, and m represents one or more maleimide compounds represented by the formula (1). Thermosetting resin composition.   Component (C) is N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6- One or more maleimide compounds (I) selected from the group consisting of diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide, and N-cyclohexylmaleimide One or more maleimide compounds (II) containing 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, one containing bis (3-ethyl-5-methyl-4-maleimidophenyl) methane One or more maleimide compounds (III) or one or more containing divinylbiphenyl Vinyl compounds, the thermosetting resin composition of any one of claims 1 to 10.   The blending ratio of component (A) is in the range of 2 to 200 parts by weight with respect to 100 parts by weight of the total amount of component (B) and component (C), and the blending ratio of component (C) is (B). It is the range of 2-200 mass parts with respect to 100 mass parts of components, and the mixture ratio of (D) component is with respect to 100 mass parts of total amounts of (A) component, (B) component, and (C) component. The thermosetting resin composition according to any one of claims 1 to 11, which is in a range of 1 to 1000 parts by mass.   Furthermore, (E) a radical reaction initiator, (F) a crosslinkable monomer or crosslinkable polymer that does not constitute an uncured semi-IPN type complex and contains one or more ethylenically unsaturated double bond groups in the molecule, The thermosetting resin according to any one of claims 1 to 12, comprising (G) one or more selected from a brominated flame retardant and a phosphorus flame retardant, and / or (H) a saturated thermoplastic elastomer. Composition.   The component (F) is a crosslinkable monomer or crosslinkable polymer containing one or more ethylenically unsaturated double bond groups selected from the group consisting of a butadiene polymer that is not chemically modified and a maleimide compound. Thermosetting resin composition.   The saturated thermoplastic elastomer (H) is one or more types including a saturated thermoplastic elastomer obtained by hydrogenating an unsaturated double bond group of a butadiene portion of a styrene-butadiene copolymer. The thermosetting resin composition as described.   A resin varnish for a printed wiring board obtained by dissolving or dispersing the thermosetting resin composition according to any one of claims 1 to 15 in a solvent.   A prepreg obtained by impregnating a substrate with the resin varnish for a printed wiring board according to claim 16 and drying at 60 to 200 ° C.   The content ratio of the component (D), or, when the substrate is an inorganic substrate, the content ratio of the component (D) and the inorganic component combined with the substrate is less than 50% by volume of the prepreg volume. Prepreg.   A metal-clad laminate obtained by stacking one or more prepregs according to claim 17 or 18, placing a metal foil on one side or both sides, and heating and pressing.