JP2011225639A - Thermosetting resin composition, and resin varnish, prepreg and metal-clad laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition for a printed wiring board, the composition used as the inner layer adhesive of a multilayer printed wiring board for usage in a high-frequency range, and satisfying a low coefficient of thermal expansion, a low dielectric constant, low dielectric loss, low moisture absorption and good hyper-multilayer formability, and to provide a resin varnish, a prepreg and a metal-clad laminate using the composition.SOLUTION: The thermosetting resin composition contains an uncured semi-IPN composite material and (D) a radical reaction initiator. The uncured semi-IPN composite material comprises (A) a polyphenylene ether compatibilized with a prepolymer formed of (B) a chemically unmodified butadiene polymer containing 1,2-butadiene units having 1,2-vinyl groups in side chains by 40% or more in the molecule and (C) a crosslinking agent. The component (D) comprises a dialkyl peroxide-based radical reaction initiator and a hydroperoxide-based radical reaction initiator. There are provided the resin varnish, the prepreg and the metal-clad laminate using the thermosetting resin composition.

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, particularly two or more types of specific radical reaction initiators. It relates to the composition containing this. More specifically, a novel semi-IPN composite thermosetting resin composition used for electronic devices whose operating frequency exceeds 1 GHz, and a resin varnish for printed wiring boards, a prepreg, and a metal-clad laminate using the same It is about a board. The semi-IPN type composite is a composite having a mutual network intrusion structure when a cross-linked polymer and a linear polymer are entangled with each other.

  Mobile communication devices such as mobile phones, their base station devices, network-related electronic devices such as servers and routers, and large computers are required to transmit and process large amounts of information with low loss and high speed. Has been. When transmitting and processing large amounts of information, electrical signals with higher frequency can be transmitted and processed faster. However, an electrical signal basically has a property of being easily attenuated as it becomes a high frequency, 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-mentioned requirements for low loss and high speed, it is necessary to further reduce the transmission loss, particularly the transmission loss in the high frequency band, in the characteristics of the printed wiring board itself that performs transmission and processing mounted on the device. There is.

  In order to obtain a printed wiring board with low transmission loss, conventionally, a substrate material using a fluorine-based resin having a low relative dielectric constant and a low dielectric loss tangent has been used. However, since the fluorine-based resin generally has a high melting temperature and melt viscosity and relatively low fluidity, there is a problem that it is necessary to set high-temperature and high-pressure conditions during press molding. In addition, the processability, dimensional stability, and adhesion to metal plating are insufficient for use as a high-layer printed wiring board used in the above-mentioned communication equipment, network-related electronic equipment, large computers, and the like. There is a problem.

  Therefore, research is being conducted on resin materials for printed wiring boards that can be used for high-frequency applications instead of fluororesins. Of these, the use of polyphenylene ether, which is known as one of the resins having the most excellent dielectric properties among heat resistant polymers, has attracted attention. However, polyphenylene ether is a thermoplastic resin having a high melting temperature and high melt viscosity like the above fluororesin. 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 above the melting temperature (230 to 250 ° C.) of polyphenylene ether. For the purpose of imparting, it has been used as a resin composition in which polyphenylene ether and a thermosetting resin are used in combination.

  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 Resin composition using copolymer or polystyrene and triallyl cyanurate or triallyl isocyanurate in combination (see Patent Documents 4 to 5), resin composition using polybutadiene in combination (see Patent Document 6 and Patent Document 7), hydroxyl group , A resin composition obtained by pre-reacting a modified polybutadiene having a functional group such as an epoxy group, a carboxyl group, a (meth) acryl group, and bismaleimide and / or a cyanate ester (see Patent Document 8), an unsaturated double bond group The above-mentioned triallyl cyanurate on polyphenylene ether provided or grafted with a compound having A resin composition using triallyl isocyanurate, the above polybutadiene, or the like (see Patent Document 9 and Patent Document 10), or a reaction product of polyphenylene ether and an unsaturated carboxylic acid or unsaturated acid anhydride with the above bismaleimide, etc. A combined resin composition (see Patent Document 11) has been proposed. According to these documents, it is disclosed that it is preferable that the cured resin does not have many polar groups in order to improve the above-described thermoplastic defects while maintaining the low transmission loss of polyphenylene ether. Yes.

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 2009-35710 A

The present inventors have detailed the applicability to the use for laminated boards for printed wiring boards such as those described in Patent Documents 1 to 11, including resin compositions using polyphenylene ether and thermosetting resin in combination. It was examined.
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, which is not suitable for high frequency applications. there were.
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, in addition to the slightly higher relative dielectric constant, the dielectric properties associated with moisture absorption 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 modified polybutadiene is used in combination to improve adhesion to metals and glass substrates. However, there is a problem that the dielectric characteristics are greatly deteriorated compared with the case of using unmodified polybutadiene, particularly in a high frequency region of 1 GHz or more.
Furthermore, in the composition using the reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride shown in Patent Document 11, the influence of highly polar unsaturated carboxylic acid or unsaturated acid anhydride. As a result, the dielectric properties are worse than when ordinary polyphenylene ether is used.
Therefore, there is a demand for a thermosetting resin composition containing polyphenylene ether which has improved the above-mentioned thermoplastic defects and has excellent dielectric properties.
On the other hand, the resin composition containing only one kind of radical reaction initiator shown in Patent Document 12 has a large melt viscosity and a low curing start temperature, and therefore, particularly when a high multilayer printed wiring board having a large number of stages is produced. Therefore, it is required to improve the multilayer formability by further improving the resin flow property.

  In addition, the present inventors conducted research by paying attention to the point of reducing dielectric loss, particularly transmission loss. As a result, only by using a resin having a low dielectric constant and a low dielectric loss tangent, it is possible to further increase the electrical signal in recent years. It was found that it was insufficient as a response to higher frequencies. Transmission loss of electrical signals is classified into loss due to insulation layer (dielectric loss) and loss due to conductor layer (conductor loss), so when using a resin with low dielectric constant and low dielectric loss tangent, dielectric Only the loss is reduced. In order to further reduce the transmission loss, it is necessary to reduce the conductor loss.

As a method for reducing the conductor loss, a metal foil having a small surface unevenness on the roughened surface (hereinafter referred to as “M surface”) side, which is an adhesive surface between the conductor layer and the insulating layer, specifically, M For example, a method using a metal-clad laminate using a metal foil (hereinafter referred to as “low profile foil”) having a surface roughness (ten-point average roughness; Rz) of 5 μm or less can be used.
Therefore, the present inventors examined using a thermosetting resin having a low dielectric constant and a low dielectric loss tangent as a printed wiring board material for high frequency applications, and using a low profile foil as the metal foil.

  However, as a result of the studies by the present inventors, when the resin composition described in Patent Documents 1 to 11 is used to form a laminated plate with a low profile foil, the insulating (resin) layer and the conductor (metal foil) layer are used. It was found that the adhesive strength (bonding strength) was weakened and it was not possible to ensure the required peeling strength with the metal foil. This is presumably because the polarity of the resin is low and the anchor effect due to the unevenness of the M surface of the metal foil is reduced. Moreover, in the heat resistance test after moisture absorption in these laminated boards, the malfunction that peeling arises between resin and metal foil generate | occur | produced. This is considered because the adhesive force between the resin and the metal foil is low. From these results, the present inventors have found that the resin compositions described in Patent Documents 1 to 11 are metal foils having a small surface roughness such as a low profile foil, in addition to the problems described above. I found the problem that it was difficult to apply.

  In particular, in the system of polyphenylene ether and butadiene homopolymer, the following was remarkable. These resins are inherently incompatible with each other, and it is difficult to obtain a uniform resin. Therefore, when resin compositions containing these are used as they are, there is a problem of tack (adhesiveness), which is a drawback of the butadiene homopolymer system, in an uncured state, so the appearance is uniform and handling properties are good It is very difficult to obtain a simple prepreg. In addition, when this prepreg and metal foil are used to form a metal-clad laminate, the resin is cured in a non-uniform state (macro phase separation state). The heat resistance at the time is lowered, and further, the disadvantages of the butadiene homopolymer system are emphasized, and various problems such as low fracture strength and large thermal expansion coefficient are caused. Therefore, a polyphenylene ether and butadiene homopolymer resin composition that satisfies the level required for printed wiring board use has not been found.

  Further, in the resin composition of polyphenylene ether and butadiene homopolymer, the peel strength between the metal foil was low and there was not enough strength to apply the low profile foil. This is thought to be due to the fact that the lower cohesive failure strength of the resin near the metal foil at the time of peeling has a greater influence than the low interfacial adhesion between the butadiene homopolymer and the metal foil. It is done.

  Also, improvement in impact resistance of polyphenylene ether and compatibility issues with polyphenylene ether and thermosetting resins having unsaturated double bond groups such as butadiene polymer, triallyl cyanurate and triallyl isocyanurate as described above As an improvement measure against this, an unsaturated crosslinkable polymer that also functions as a compatibilizing agent such as a styrene-butadiene copolymer as shown in Patent Documents 4 to 6 may be used in combination. In the resin composition, since the thermosetting resin and the styrene-butadiene copolymer are compatible, the resin composition is formed by a co-curing reaction between the styrene-butadiene copolymer having a low glass transition temperature (Tg) and the thermosetting resin. A decrease in Tg is inevitable.

  In order to solve the above problems, the present invention has a good dielectric characteristic particularly in a high frequency band, can significantly reduce transmission loss, and has excellent moisture absorption heat resistance and thermal expansion characteristics. It aims at providing the thermosetting resin composition which can manufacture the printed wiring board with the favorable moldability at the time of a multilayer, and the resin varnish, prepreg, and metal-clad laminate using the same.

  As a result of intensive studies on the resin composition containing polyphenylene ether to solve the above-mentioned problems, the present inventors have found that a specific saturated thermoplastic elastomer is added to a compatibilized uncured semi-IPN composite. , A non-cured semi-IPN type composite having a novel composition in which a prepolymer of a polyphenylene ether, a butadiene polymer not chemically modified and a cross-linking agent is compatible, And a thermosetting resin composition containing a saturated thermoplastic elastomer. Furthermore, it is a thermosetting resin composition of a semi-IPN type composite containing a compatibilized uncured polyphenylene ether-modified butadiene polymer produced by a new unique compatibility method and a saturated thermoplastic elastomer. . Furthermore, by containing two or more types of radical reaction initiators having different one-hour half-life temperatures, it is possible to control the resin flow properties by reducing the melt viscosity during press molding and controlling the curing start temperature. The present inventors have found that the formability at the time of high multilayering can be achieved at a sufficiently high level.

That is, the present invention relates to the following.
(1) A thermosetting resin composition containing an uncured semi-IPN type complex and (D) a radical reaction initiator, wherein the uncured semi-IPN type complex comprises (A) polyphenylene ether (B) a prepolymer formed from a butadiene polymer containing 1,2-butadiene units having a 1,2-vinyl group in the side chain of 40% or more in the molecule and not chemically modified, and (C) a crosslinking agent. A thermosetting characterized in that a polymer and an uncured semi-IPN type composite, wherein (D) component contains a dialkyl peroxide radical initiator and a hydroperoxide radical initiator Resin composition.
(2) The 1-minute half-life temperature of the dialkyl peroxide radical initiator of component (D) is 175.4 ° C. or higher, and the 1-minute half-life temperature of the hydroperoxide radical initiator is 232.5 The thermosetting resin composition described above, wherein the thermosetting resin composition is equal to or higher than C.
(3) The thermosetting resin composition described above, wherein the dialkyl peroxide radical initiator in component (D) is α, α'-bis (t-butylperoxy) diisopropylbenzene.
(4) The hydroperoxide radical initiator in component (D) is one or more radical initiators selected from p-mentahydroperoxide, diisopropylbenzene hydroperoxide, and t-hexyl hydroperoxide. The thermosetting resin composition as described above, wherein
(5) (A) In the presence of polyphenylene ether, (B) a chemically modified butadiene polymer containing 40% or more of 1,2-butadiene units having 1,2-vinyl groups in the side chain in the molecule; (C) a thermosetting resin obtained by pre-reacting a crosslinking agent and containing an uncured semi-IPN type composite containing a polyphenylene ether-modified butadiene prepolymer, and (D) a radical reaction initiator A thermosetting resin composition, wherein the component (D) contains a dialkyl peroxide radical reaction initiator and a hydroperoxide radical reaction initiator.
(6) 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 component, and the mixture ratio (total amount of a dialkyl peroxide type radical reaction initiator and a hydroperoxide type radical reaction initiator) of (D) component is. , (A) component, (B) component, and (C) component in a range of 0.05 to 10 parts by mass with respect to 100 parts by mass, and (a) dialkyl peroxide and (b) hydro The said thermosetting resin composition characterized by the compounding ratio of a peroxide being (a) :( b) = 20: 80-50: 50, respectively.
(7) The said thermosetting resin composition obtained by pre-reacting a polyphenylene ether modified butadiene prepolymer so that the conversion rate of (C) component may be 5 to 100% of range.
(8) The said thermosetting resin composition containing the at least 1 or more types of maleimide compound represented by General formula (1) as (C) component.

（式中、Ｒ_１は、ｍ価の脂肪族性又は芳香族性の有機基であり、Ｘａ及びＸｂは、水素原子、ハロゲン原子及び脂肪族性の有機基から選ばれた同一又は異なっていてもよい一価の原子又は有機基であり、そしてｍは、１以上の整数を示す。）

Wherein R ₁ is an m-valent aliphatic or aromatic organic group, and Xa and Xb are the same or different selected from a hydrogen atom, a halogen atom and an aliphatic organic group. A monovalent atom or an organic group, and m represents an integer of 1 or more.)

(9) Component (C) is N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2 , 6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide, and N-cyclohexylmaleimide. The thermosetting resin composition as described above.
(10) The thermosetting resin composition described above, wherein the component (C) is at least one or more maleimide compounds containing 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane.
(11) The thermosetting resin composition described above, wherein the component (C) is at least one maleimide compound containing bis (3-ethyl-5-methyl-4-maleimidophenyl) methane.
(12) The thermosetting resin composition as described above, wherein the component (C) is at least one vinyl compound containing divinylbiphenyl.
(13) The thermosetting resin composition further comprising (E) a saturated thermoplastic elastomer.
(14) The thermosetting resin composition described above, wherein the component (E) is at least one kind of saturated thermoplastic elastomer containing a styrene-ethylene-butylene copolymer.
(15) The component (E) is at least one kind of saturated thermoplastic elastomer 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 above, wherein
(16) The thermosetting resin composition described above, wherein the component (E) is at least one kind of saturated thermoplastic elastomer containing a chemically modified saturated thermoplastic elastomer.
(17) The component (E) is at least one kind of saturated thermoplastic elastomer containing a saturated thermoplastic elastomer containing a styrene block in the molecule and a styrene block content ratio of 20 to 70%. The thermosetting resin composition described above.
(18) Further comprising (F) a crosslinkable monomer or a crosslinkable polymer containing one or more ethylenically unsaturated double bond groups in the molecule, which does not constitute an uncured semi-IPN type complex. Thermosetting resin composition.
(19) The component (F) is a crosslinkable monomer or a crosslinkable polymer containing at least one ethylenically unsaturated double bond group selected from the group consisting of a butadiene polymer and a maleimide compound not chemically modified, Thermosetting resin composition.
(20) The thermosetting resin composition further comprising (G) at least one of a brominated flame retardant and a phosphorus flame retardant.
(21) The thermosetting resin composition further comprising (H) an inorganic filler.
(22) A resin varnish for a printed wiring board obtained by dissolving or dispersing the thermosetting resin composition in a solvent.
(23) A prepreg obtained by impregnating a base material with the resin varnish for a printed wiring board and drying it.
(24) A metal-clad laminate obtained by stacking one or more of the prepregs, placing a metal foil on one or both sides, and heating and pressing.

  According to the present invention, when a printed wiring board is formed using the resin composition or the like of the present invention, excellent high frequency characteristics, good heat resistance (particularly moisture absorption heat resistance) and low thermal expansion characteristics can be achieved, and a high multilayer is achieved. It is possible to provide a resin composition, a resin varnish, a prepreg, and a metal-clad laminate that can achieve moldability at a sufficiently high level. Accordingly, the present invention provides a printed wiring board for use in mobile communication devices that handle high-frequency signals of 1 GHz or higher, base station devices, network-related electronic devices such as servers and routers, and various electric and electronic devices such as large computers. It is useful for members and parts.

It is a schematic diagram which shows the thermosetting resin composition of an uncured semi-IPN type composite.

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, 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 best 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) or in the presence of a saturated thermoplastic elastomer as component (A) and component (E), 1, 2 is added to the side chain of component (B). -A chemically modified butadiene polymer containing 40% or more of 1,2-butadiene units having a vinyl group in the molecule and a crosslinking agent of (C) component, and (C) component with an appropriate conversion rate (reaction) The linear polymer component (here, the component (A), or the component (A) and the component (E), solid line portion) is once cured in an uncured state before being completely cured. And a polyphenylene ether-modified butadiene prepolymer in which a so-called “semi-IPN” is formed between the other crosslinkable component (here, components (B) and (C), dotted line portion). Resin composition Obtained and (thermosetting resin composition of an uncured semi-IPN composite; see Fig. 1). 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 with an apparently uniform appearance. A polyphenylene ether-modified butadiene prepolymer as conventionally known does not form a semi-IPN, and since the constituent components are not compatible, it is in a state of phase separation. Therefore, unlike the composition of the present invention, the conventional polyphenylene ether-modified butadiene prepolymer 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 also cures while molecular chains are partially and physically entangled with each other. Compared to the case where the product is cured, the crosslink density is increased in a pseudo manner, so that 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, by improving the breaking strength of the resin, a high metal foil peeling strength up to a level where a low profile foil can be applied can be exhibited. Furthermore, as a component (C), by selecting a specific cross-linking agent that enhances the resin strength and toughness when cured, or restricts the 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.

  The thermosetting resin composition of the novel semi-IPN type composite of the present invention has 1,2-vinyl groups in the side chain of the component (B) in the presence of the polyphenylene ether of the component (A). -A polyphenylene ether-modified butadiene prepolymer obtained by pre-reacting a butadiene homopolymer containing 40% or more of butadiene units in the molecule and a crosslinking agent of component (C), and (E) a saturated thermoplastic elastomer. Hereinafter, the suitable manufacturing method of each component of a resin composition and a polyphenylene ether modified butadiene prepolymer is demonstrated.

  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, poly (2,3,6-trimethyl-1,4-phenylene) ether and 2,6-dimethylphenol obtained by homopolymerization of trimethylphenol Examples thereof include a copolymer with 2,3,6-trimethylphenol. In addition, so-called modified polyphenylene ether such as an alloyed polymer of these with polystyrene or styrene-butadiene copolymer can also be used. 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. More preferred.

  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 in the production of the polyphenylene ether-modified butadiene prepolymer is chemically modified so that it contains 40% or more of 1,2-butadiene units having 1,2-vinyl groups in the side chain. The butadiene polymer is not particularly limited as long as it is not a butadiene polymer. ) Unmodified butadiene polymer, not chemically modified modified polybutadiene such as acrylation and urethanization. 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. Moreover, it is preferable that the number average molecular weight of (B) component is the range of 500-10000. If it exceeds 10,000, the fluidity of the resin is inferior when made into a prepreg, which is not preferable. If it is less than 500, the curability of the resin composition and the dielectric properties of the cured product are inferior. In consideration of 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, it is more preferably in the range of 700 to 8000, more preferably in the range of 1000 to 5000. More preferably. 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 B-1000, B-2000, B-3000 (trade name, manufactured by Nippon Soda Co., Ltd.), B-1000, B-2000, B-3000. (Commercial name, manufactured by Shin Nippon Petrochemical Co., Ltd.), Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154 (manufactured by SARTOMER Co., Ltd., trade name) and the like are commercially available.

  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 at least one or more maleimide compounds or at least one vinyl compound, and is excellent in co-crosslinking property with the component (B). Good curability and storage stability, formability when 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 not particularly limited as long as it is a compound containing one or more maleimide groups in the molecule represented by the following general formula (1). A monomaleimide compound or a polymaleimide compound represented by the following general formula (2) can be preferably used.

（式中、Ｒ_１はｍ価の脂肪族性、脂環式、芳香族性、複素環式のいずれかである一価又は多価の有機基であり、Ｘａ及びＸｂは水素原子、ハロゲン原子及び脂肪族性の有機基から選ばれた同一又は異なっていてもよい一価の原子又は有機基であり、ｍは１以上の整数を示す。）

(In the formula, R ₁ is a monovalent or polyvalent organic group which is _one of m-valent aliphatic, alicyclic, aromatic and heterocyclic, and Xa and Xb are a hydrogen atom or a halogen atom. And a monovalent atom or an organic group which may be the same or different and selected from aliphatic organic groups, and m represents an integer of 1 or more.)

（式中、Ｒ_２は、−Ｃ（Ｘｃ）_２−、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、又は連結する結合であり、それぞれ同一又は異なっていてもよい、Ｘｃは炭素数１〜４のアルキル基、−ＣＦ_３、−ＯＣＨ_３、−ＮＨ_２、ハロゲン原子又は水素原子を示し、それぞれ同一又は異なっていてもよい、それぞれベンゼン環の置換位置は相互に独立であり、ｎ及びｐは、０〜１０の整数を示す。）

(Wherein R ₂ is —C (Xc) ₂ —, —CO—, —O—, —S—, —SO ₂ —, or a linking bond, which may be the same or different, Xc 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, and the substitution positions of the benzene rings are mutually independent. Yes, and n and p represent 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 (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-male Dophenyl) 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, aliphatic, alicyclic such as the following general formula (3) and the following general formula (4) Aromatic and heterocyclic poly maleimide (however, each including 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 a prepreg is formed, monomaleimide that causes a gradual curing reaction is preferable, and among them, 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 you may use these at least 1 type or more of maleimide compounds and the crosslinking agent shown above in combination of 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. However, it is more preferable to use the maleimide compound alone than to use it in combination with another crosslinking agent.

（式中、ｑは平均値で０〜１０である。）

(In the formula, q is an average value of 0 to 10.)

（式中、ｒは平均値で０〜１０である。）

(In the formula, r is an average value of 0 to 10.)

  Examples of the vinyl compound suitably used as the component (C) include styrene, divinylbenzene, vinyltoluene, and divinylbiphenyl. Divinylbiphenyl is preferred. As a specific example of the component (B) 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 thermosetting resin composition of the novel semi-IPN composite of the present invention is preferably a component (B) in the presence of the component (A) developed in a medium, C) It is manufactured by pre-reacting with component 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.

  The resin composition of the present invention contains (D) a radical reaction initiator for the purpose of initiating or promoting the curing reaction of the cured product of the resin composition when producing a metal-clad laminate or a multilayer printed wiring board. Specific examples of the component (D) include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-bis. (T-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne, dialkyl peroxide radical initiators such as di-t-butyl peroxide, p- Hydroperoxide radical initiators such as mentahydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide However, it is not limited to these. Moreover, in order to improve the moldability when it is used as a prepreg, it is preferable to combine radical reaction initiators having different half-life temperatures. Among them, α, α ′ are preferred from the viewpoint of dielectric properties, moisture absorption resistance, thermal expansion coefficient, etc. -Dialkyl peroxide radical initiators such as bis (t-butylperoxy) diisopropylbenzene and p-mentahydroperoxide, diisopropylbenzene hydroperoxide or t-hexylhydro having a higher reaction initiation temperature It is more preferable to use one or more radical reaction initiators selected from hydroperoxide-based radical reaction initiators such as peroxide.

  The resin composition of the present invention contains a radical reaction initiator for the purpose of initiating or accelerating the preliminary reaction between the component (B) and the component (C) during the production of the polyphenylene ether-modified butadiene prepolymer. It is preferable. In that case, the same kind as the component (D) may be used, or a different kind may be used, and t-butylcumyl peroxide, benzoyl peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-hexylperper Oxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di (t-butylperoxy) cyclohexyl) propane, 2,5-dimethylhexane-2,5 -Dihydroperoxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, t-butylperoxyacetate, 2,2 Bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, bis (t-butylperoxy) Peroxides such as isophthalate, isobutyryl peroxide, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4- Examples include, but are not limited to, isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzoin methyl ether, methyl-o-benzoylbenzoate, and the like. Moreover, these radical reaction initiators may be used individually by 1 type, and may mix and use 2 or more types.

  The blending ratio of the component (D) 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 the component (D) is blended within this numerical range, good curability can be obtained in the curing reaction when producing a metal-clad laminate or a multilayer printed wiring board.

  The component (E) used in the thermosetting resin composition of the present invention is not particularly limited as long as it is a saturated thermoplastic elastomer, but is styrene-based saturated with good compatibility with the component (A). Mold thermoplastic elastomers are desirable. Specific examples of the component (E) preferably used in the present invention include a styrene-ethylene-butylene copolymer, and a method of hydrogenating an unsaturated double bond portion of a butadiene block of the 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 (E), a chemically modified saturated thermoplastic elastomer having a functional group such as an epoxy group, a hydroxyl group, a carboxyl group, an amino group, or an acid anhydride in the molecule can be used. In addition, the component (E) 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.

  Although the compounding ratio of (E) component in the resin composition of this invention is not specifically limited, 1-100 mass parts with respect to 100 mass parts of total amounts of (A) component, (B) component, and (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. When the blending ratio of the component (E) is less than 1 part by mass, the effect of improving the dielectric characteristics tends to be insufficient, and when it exceeds 100 parts by mass, the thermal expansion characteristics of the cured product tend to deteriorate.

  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) at least one of bromine-based flame retardant and phosphorus-based flame retardant, (H) inorganic filler, various thermosetting resins, various thermoplastic resins, and various additives were used as printed wiring boards. At a blending amount within a range not deteriorating properties such as dielectric properties, heat resistance, adhesiveness (metal foil peeling strength, adhesion to a substrate such as glass), moisture resistance, Tg, 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 not particularly limited. Specifically, it is selected from the group consisting of a butadiene polymer that is not chemically modified and a maleimide compound. The compounds mentioned as the component (B) and the component (C) can be used as long as they do not constitute an uncured semi-IPN type composite. 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 compounds as those exemplified as the components (B) and (C) are blended as the component (F), an uncured semi-IPN composite thermosetting resin composition (polyphenylene ether-modified butadiene) In this case, the blending amount of the component (F) is distinguished from the blending amounts of the component (B) and the component (C), and preferable blending amounts are separately described below. 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.

  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.

  The blending ratio of the component (G) 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 the components (A), (B), (C) and (E), It is preferable to set it as 5-200 mass parts, It is more preferable to set it as 5-150 mass parts, It is still more preferable to set it as 5-100 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 inorganic filler of the component (H) is not particularly limited, and specifically, alumina, titanium oxide, mica, silica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, carbonic acid Aluminum, 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, etc. Is used. These inorganic fillers may be used alone or in combination of two or more. Moreover, there is no restriction | limiting in particular also about the shape and particle size of an inorganic filler, Usually, the particle size of 0.01-50 micrometers, Preferably 0.1-15 micrometers is used suitably.

  The blending ratio of the component (H) 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 the components (A), (B), (C) and (E), 1-1000 mass parts is preferable and 5-500 mass parts is more preferable.

  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. In addition, these may be used alone or in combination of two or more, aromatic hydrocarbons such as toluene, xylene and mesitylene, aromatic hydrocarbons and acetone, methyl ethyl ketone, methyl A mixed solvent with ketones such as isobutyl ketone and cyclohexanone is more preferable. 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 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 may 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. These various thermosetting resins, various thermoplastic resins and various additives may be used alone or in combination of two or more.

  The resin composition of the present invention is a polyphenylene ether-modified butadiene prepolymer obtained from the above-mentioned components (A), (B) and (C), (D) component, (E) component, and blended as necessary. (F) a crosslinkable monomer or crosslinkable polymer containing one or more ethylenically unsaturated double bond groups in the molecule, which does not constitute an uncured semi-IPN type composite, (G) a flame retardant, H) An inorganic filler and various thermosetting resins, various thermoplastic resins, and various additives can be produced by blending, stirring and mixing by a known method. In the case where the polyphenylene ether-modified butadiene prepolymer used in combination with the saturated thermoplastic elastomer obtained in advance with the components (A), (B), (C) and (E) is blended and stirred in the same manner. -It can be manufactured by mixing.

  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 used as a resin varnish. In the polyphenylene ether-modified butadiene prepolymer solution, the (D) component, the (E) component, and the (F) component, the (G) component, the (H) component, and the above-mentioned other compounding agents as necessary. If necessary, an additional solvent may be further blended to form a resin varnish. In the case where a polyphenylene ether-modified butadiene prepolymer combined with a saturated thermoplastic elastomer is used in advance, it can be varnished by the same method.

  The solvent used when varnishing the above resin composition is not particularly limited, but specific examples and preferred solvents include the above polyphenylene ether-modified butadiene prepolymer or saturated thermoplastic elastomer combined polyphenylene ether. What was described about the solvent used in manufacture of a modified butadiene prepolymer can be used, These may be used individually by 1 type and may be used in combination of 2 or more types, toluene, xylene, mesitylene And a mixed solvent of an aromatic hydrocarbon and a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone is 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. Etc., by adjusting the amount of solvent, the solid content (non-volatile content) concentration and varnish viscosity are optimal for coating work (for example, to achieve a good appearance and proper resin adhesion). be able to.

  Using the resin composition and resin varnish of the present invention described above, 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 or organic fiber with the thermosetting resin composition and the 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, one or a plurality of the prepregs are stacked, a metal foil is disposed on one side or both sides thereof, 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 manufactured 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 embodiment, and can be arbitrarily changed and modified within a range not departing from the object of the 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, 350 parts by mass of toluene and polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals Corporation, Mn: 16000) 50 parts by mass were charged, and the temperature in the flask was set at 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) 30 parts by mass of bis (4-maleimidophenyl) methane (BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and methyl isobutyl as a solvent so that the solid content (nonvolatile content) concentration in the solution is 30% by mass Ketone (MIBK) was added and stirring was continued to confirm that these were dissolved or uniformly dispersed. Thereafter, the liquid temperature was raised to 110 ° C., and 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, Nippon Oil & Fats was used as a reaction initiator while maintaining the temperature. Co., Ltd.) 0.5 parts by mass, pre-reacted with stirring for about 1 hour, (A) polyphenylene ether, (B) butadiene polymer not chemically modified, and (C) crosslinking agent A compatibilized polyphenylene ether-modified butadiene prepolymer solution was obtained. When the conversion rate of bis (4-maleimidophenyl) methane in this polyphenylene ether-modified butadiene prepolymer solution was measured by gel permeation chromatography, the conversion rate was 33%. The conversion rate is a value obtained by subtracting the unconverted portion (measured value) of bis (4-maleimidophenyl) methane from 100.

  Subsequently, after setting the liquid temperature in a flask to 80 degreeC, it concentrated so that solid content concentration of a solution might be 45 mass%, stirring. Next, after cooling the solution to room temperature, 20 parts by mass of a hydrogenated product of styrene-butadiene copolymer (Tuftec H1053, styrene content ratio: 29%, manufactured by Asahi Kasei Chemicals Co., Ltd.) as component (E), After confirming the dissolution, 3.5 parts by mass of α, α'-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and p-menta hydroperoxide (Permenta H) as component (D) After adding 1.5 parts by mass of NOF Corporation, methyl ethyl ketone (MEK) was blended to prepare the resin varnish of Preparation Example 1 (solid content concentration: about 41% by mass).

Preparation Example 2
Preparation Example 1 except that 30 parts by mass of polyphenylmethanemaleimide (BMI-2000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was used instead of bis (4-maleimidophenyl) methane as component (C). In the same manner as in Example 1, a polyphenylene ether-modified butadiene prepolymer was obtained. The conversion ratio of BMI-2000 in this polyphenylene ether-modified butadiene prepolymer solution was measured by gel permeation chromatography and found to be 35%. Subsequently, using this solution, instead of Tuftec H1053 as the component (E), a hydrogenated styrene-butadiene copolymer (Tuftec H1051, styrene content ratio: 42%, manufactured by Asahi Kasei Chemicals Corporation) 20 mass After mixing and confirming dissolution, 3.5 parts by mass of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and p-menthane hydro as component (D) Resin varnish of preparation example 2 (solid content concentration of about approx. 2.5 parts by weight of each) instead of 1.5 parts by weight of peroxide (Permenta H, manufactured by NOF Corporation) 41% by mass) was prepared.

Preparation Example 3
In Preparation Example 1, instead of bis (4-maleimidophenyl) methane as component (C), bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-5100, manufactured by Daiwa Kasei Kogyo Co., Ltd.) ) A polyphenylene ether-modified butadiene prepolymer was obtained in the same manner as in Preparation Example 1 except that 35 parts by mass was used. The conversion of BMI-5100 in this polyphenylene ether-modified butadiene prepolymer solution was measured by gel permeation chromatography and found to be 25%. Subsequently, using this solution, instead of Tuftec H1053 as component (E), a hydrogenated styrene-butadiene copolymer (Tuftec H1043, styrene content ratio: 67%, manufactured by Asahi Kasei Chemicals Corporation) 20 mass After mixing and confirming dissolution, 3.5 parts by mass of α, α'-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and p-mentahydro as component (D) The resin varnish of Preparation Example 3 was prepared in the same manner as Preparation Example 1 except that 1.5 parts by weight and 3.5 parts by weight of peroxide (Permenta H, manufactured by NOF Corporation) were added. A solid concentration of about 41% by mass was prepared.

Preparation Example 4
In Preparation Example 1, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (BMI-4000, Daiwa Kasei Kogyo Co., Ltd.) instead of bis (4-maleimidophenyl) methane as component (C) (Manufactured) A polyphenylene ether-modified butadiene prepolymer was obtained in the same manner as in Preparation Example 1 except that 40 parts by mass were used. The conversion ratio of BMI-4000 in this polyphenylene ether-modified butadiene prepolymer solution was measured by gel permeation chromatography and found to be 30%. Subsequently, using this solution, instead of Tuftec H1053 as the component (E), a hydrogenated styrene-butadiene copolymer (Tuftec H1081, styrene content ratio: 60%, manufactured by Asahi Kasei Chemicals Corporation) 20 mass After mixing and confirming dissolution, 3.5 parts by mass of α, α'-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and p-mentahydro as component (D) Instead of 1.5 parts by mass of peroxide (Permenta H, manufactured by NOF CORPORATION), 2.5 mass of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) Parts and diisopropylbenzene hydroperoxide (Park Mill P, manufactured by NOF Corporation) in the same manner as in Preparation Example 1 except that 1.5 parts by mass was added. Resin varnish of Preparation Example 4 (solid content concentration of about 41 wt%) was prepared.

Preparation Example 5
(A) In Preparation Example 1, instead of bis (4-maleimidophenyl) methane as component (C), 15 parts by mass of N-phenylmaleimide (Imirex-P, manufactured by Nippon Shokubai Co., Ltd.) was used. In the same manner as in Preparation Example 1, a polyphenylene ether-modified butadiene prepolymer was obtained. The conversion of imilex-P in this polyphenylene ether-modified butadiene prepolymer solution was measured by gel permeation chromatography and found to be 26%.

(B) Subsequently, this solution was concentrated in the same manner as in Preparation Example 1, and then 2,2-bis (4- (4-maleimidophenoxy) as the component (F) was maintained while maintaining the liquid temperature at 80 ° C. 25 parts by mass of phenyl) propane (BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was blended. Next, after cooling to room temperature with stirring, 10 parts by mass of two kinds of hydrogenated products of styrene-butadiene copolymer (Tuftec H1043 and H1081) as component (E) were blended, and dissolution was confirmed. D) α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and p-menta hydroperoxide (Permenter H, manufactured by NOF Corporation) Instead of 1.5 parts by mass, 2.5 parts by mass of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and diisopropylbenzene hydroperoxide (Park Mill P, NOF) Co., Ltd.) 2.5 parts by mass, methyl ethyl ketone (MEK) was blended, and the resin varnish of Preparation Example 5 (solid content concentration of about 41) The amount%) was prepared.

Preparation Example 6
In Preparation Example 5 (a), instead of N-phenylmaleimide as component (C), 15 parts by mass of bis (4-maleimidophenyl) methane (BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was used. Obtained a polyphenylene ether-modified butadiene prepolymer in the same manner as in Preparation Example 5. The conversion ratio of BMI-1000 in this polyphenylene ether-modified butadiene prepolymer solution was measured by gel permeation chromatography and found to be 32%. Subsequently, using this solution, 10 parts by mass of Tuftec H1051 was blended instead of Tuftec H1081 as the component (E), and after confirming dissolution, α, α'-bis (t-butyl) was used as the component (D). Instead of 3.5 parts by mass of peroxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and 1.5 parts by mass of p-menta hydroperoxide (Permenta H, manufactured by NOF Corporation), α, α ′ -Except for adding 2.5 parts by mass of bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and 3.5 parts by mass of diisopropylbenzene hydroperoxide (Park Mill P, manufactured by NOF Corporation). Prepared a resin varnish (solid content concentration of about 41% by mass) of Preparation Example 6 in the same manner as Preparation Example 5 (b).

Preparation Example 7
(A) In Preparation Example 5 (a), instead of N-phenylmaleimide as component (C), 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (BMI-4000, Daiwa Chemical Industries) A polyphenylene ether-modified butadiene prepolymer was obtained in the same manner as in Preparation Example 5 except that 25 parts by mass was used. The conversion ratio of BMI-4000 in this polyphenylene ether-modified butadiene prepolymer solution was measured by gel permeation chromatography and found to be 31%.

(B) Subsequently, using this solution, instead of 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane as component (F) in Preparation Example 5 (b), bis (3-ethyl Hydrogen of styrene-butadiene copolymer instead of 15 parts by mass of -5-methyl-4-maleimidophenyl) methane (BMI-5100, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and Tuftec H1043 and H1081 as component (E) 20 parts by weight of an acid anhydride-modified elastomer (Tuftec M1913, styrene content ratio: 30%, manufactured by Asahi Kasei Chemicals Corporation) as an additive, and ethylenebis (pentabromophenyl) (SAYTEX8010, manufactured by Albemarle Co.) as a flame retardant 70 After blending parts by mass and confirming dissolution, α, α'-bis (t-butyl peroxide) is used as component (D). ) Α, α'-bis instead of 3.5 parts by mass of diisopropylbenzene (perbutyl P, manufactured by NOF Corporation) and 1.5 parts by mass of p-menta hydroperoxide (permenta H, manufactured by NOF Corporation) Except for adding 2.5 parts by mass of (t-butylperoxy) diisopropylbenzene (perbutyl P, manufactured by NOF Corporation) and 1.5 parts by mass of t-hexyl hydroperoxide (PARK Mill H, manufactured by NOF Corporation). In the same manner as in Preparation Example 5, the resin varnish of Preparation Example 7 (solid content concentration of about 41% by mass) was prepared.

Preparation Example 8
In Preparation Example 1, in the same manner as Preparation Example 1 except that 20 parts by mass of divinylbiphenyl (manufactured by Nippon Steel Chemical Co., Ltd.) was used instead of bis (4-maleimidophenyl) methane as the component (C). Thus, a polyphenylene ether-modified butadiene prepolymer was obtained. The conversion rate of divinylbiphenyl in the polyphenylene ether-modified butadiene prepolymer solution was measured by gel permeation chromatography and found to be 28%.
Subsequently, using this solution, 70 parts by mass of brominated polystyrene (PBS64HW, manufactured by Great Lakes Co., Ltd.) as a flame retardant was blended, and after confirming dissolution, α, α′-bis (t-butyl) was used as component (D). Instead of 3.5 parts by mass of peroxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and 1.5 parts by mass of p-menta hydroperoxide (Permenta H, manufactured by NOF Corporation), α, α ′ -2.5 parts by mass of bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) and 3.5 parts by mass of t-hexyl hydroperoxide (PARK Mill H, manufactured by NOF Corporation) were added. The resin varnish (solid content concentration of about 41% by mass) of Preparation Example 8 was prepared in the same manner as Preparation Example 1 except for the above.

Comparative Preparation Example 1
To a 1 liter separable flask equipped with a thermometer, a reflux condenser, and a stirrer, 200 parts by mass of toluene and 50 parts by mass of polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) were charged. The temperature was set at 90 ° C. and dissolved by stirring. Next, 100 parts by mass of triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Co., Ltd.) was added, and after confirming that it was dissolved or uniformly dispersed, it was cooled to room temperature. Subsequently, after cooling to room temperature with stirring, 5 parts by mass of α, α'-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) was added as a reaction initiator, and then methyl ethyl ketone (MEK) was added. The resin varnish of Comparative Preparation Example 1 (solid content concentration of about 40% by mass) was prepared.

Comparative Preparation Example 2
In Comparative Preparation Example 1, except for using 100 parts by mass of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-5100, manufactured by Daiwa Kasei Kogyo Co., Ltd.) instead of triallyl isocyanurate Prepared the resin varnish (solid content concentration of about 40% by mass) of Comparative Preparation Example 2 in the same manner as Comparative Preparation Example 1.

Comparative Preparation Example 3
In Comparative Preparation Example 1, instead of triallyl isocyanurate, 100 parts by mass of a chemically modified butadiene polymer (B-3000, manufactured by Nippon Soda Co., Ltd., Mn: 3000, 1,2-vinyl structure: 90%) A resin varnish (solid content concentration of about 40% by mass) of Comparative Preparation Example 3 was prepared in the same manner as Comparative Preparation Example 1 except that it was used.

Comparative Preparation Example 4
In Comparative Preparation Example 3, the resin varnish of Comparative Preparation Example 4 (solid content concentration: about 50% by weight) was added in the same manner as Comparative Preparation Example 3 except that 50 parts by mass of triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Chemical Co., Ltd.) was added. 40% by mass) was prepared.

Comparative Preparation Example 5
In Comparative Preparation Example 4, the same as Comparative Preparation Example 4 except that 30 parts by mass of bis (4-maleimidophenyl) methane (BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was added instead of triallyl isocyanurate. Thus, a resin varnish (solid content concentration of about 40% by mass) of Comparative Preparation Example 5 was prepared.

Comparative Preparation Example 6
350 parts by mass of toluene and 50 parts by mass of polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) are put into a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator and stirrer. The temperature in the flask was set to 90 ° C. and dissolved with stirring. Subsequently, glycol modified 1,2-polybutadiene having a hydroxyl group at the terminal (G-3000, manufactured by Nippon Soda Co., Ltd., Mn: 3000, 1,2-vinyl structure: 90%) 100 parts by mass, bis (4-maleimidophenyl) Methyl (BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 30 parts by mass and methyl isobutyl ketone (MIBK) was added so that the solid content (non-volatile content) concentration in the solution was 30% by mass, and dissolved or uniformly dispersed. 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation) 0 while maintaining the liquid temperature at 110 ° C. after confirming this .5 parts by mass was mixed and pre-reacted with stirring for about 10 minutes. The conversion rate of BMI-1000 in this preliminary reaction product was measured by gel permeation chromatography and found to be 4%. Subsequently, after setting the liquid temperature in a flask to 80 degreeC, it concentrated so that the solid content (nonvolatile content) density | concentration of a solution might be set to 45 mass%, stirring. Next, after cooling the solution to room temperature, 5 parts by mass of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) was added as a reaction initiator, and then methyl ethyl ketone ( MEK) was blended to prepare a resin varnish of Comparative Preparation Example 6 (solid content concentration of about 40% by mass).

Comparative Preparation Example 7
In Comparative Preparation Example 6, instead of glycol-modified 1,2-polybutadiene, a carboxylic acid-modified 1,2-polybutadiene having a carboxyl group at the terminal (C-1000, manufactured by Nippon Soda Co., Ltd., Mn: 1400, 1,2- A preliminary reaction product was obtained in the same manner as in Comparative Preparation Example 6 except that 100 parts by mass of vinyl structure (89%) was used. The conversion rate of BMI-1000 of this preliminary reaction product was measured by gel permeation chromatography and found to be 19%. Subsequently, a resin varnish (solid content concentration of about 40% by mass) of Comparative Preparation Example 7 was prepared using this solution in the same manner as Comparative Preparation Example 6.

Comparative Preparation Example 8
In Comparative Preparation Example 3, the same procedure as in Comparative Preparation Example 3 was conducted except that 20 parts by mass of a styrene-butadiene copolymer (Tufprene 125, manufactured by Asahi Kasei Chemicals Corporation), which is an unsaturated (crosslinkable) elastomer, was further added. A resin varnish of Comparative Preparation Example 8 (solid content concentration of about 41% by mass) was prepared.

Comparative Preparation Example 9
Resin of Comparative Preparation Example 9 in the same manner as Preparation Example 1 except that in Preparation Example 1, the hydrogenated styrene-butadiene copolymer (Tuftec H1053, styrene content ratio: 29%, manufactured by Asahi Kasei Chemicals Corporation) was removed. A varnish (solid content concentration of about 40% by mass) was prepared.

Preparation of Prepreg After impregnating the resin varnish obtained in Preparation Examples 1 to 8 and Comparative Preparation Examples 1 to 9 into a glass cloth (E glass, manufactured by Nitto Boseki Co., Ltd.), 5 The prepregs of Production Examples 1 to 8 and Comparative Production Examples 1 to 9 having a resin content of 50% by mass were produced by heating and drying for 5 minutes. In addition, the case where the resin varnishes of Preparation Examples 1 to 8 correspond to Preparation Examples 1 to 8, respectively, and the case where the resin varnishes of Comparative Preparation Examples 1 to 9 are used correspond to Comparative Preparation Examples 1 to 9, respectively. .

Evaluation of Prepreg The appearance and tackiness of the prepregs of Production Examples 1 to 8 and Comparative Production Examples 1 to 9 described above were evaluated. The evaluation results are shown in Table 1. The appearance was evaluated by visual observation. The surface of the prepreg had some unevenness and streaks, and the surface lacking surface smoothness was evaluated as x. The tackiness of the prepreg was evaluated as x when the surface of the prepreg was somewhat sticky (tack) at 25 ° C, and ◯ when it was not.

Preparation of double-sided copper-clad laminate A component obtained by stacking the four prepregs prepared in Preparation Examples 1 to 8 and Comparative Preparation Examples 1 to 9 is provided, and a low profile copper foil (F3) having a thickness of 18 μm is provided on both upper and lower surfaces. -WS, M surface Rz: 3 μm, Furukawa Electric Co., Ltd.) M surface is in contact with each other, each copper foil is placed, heat press molding under press conditions of 200 ° C., 2.9 MPa, 70 minutes Thus, a double-sided copper-clad laminate (thickness: 0.5 mm) was produced. Moreover, about the prepreg of the manufacture example 1 and the comparative manufacture example 1, using a general copper foil (GTS, M surface Rz: 8 micrometers, Furukawa Electric Co., Ltd.) of thickness 18 micrometers as a copper foil, a double-sided copper clad laminated board is used. Each was produced separately under the same pressing conditions as when a low profile copper foil was used. In addition, it shows in Table 1 about the combination of the prepreg of the manufacture examples 1-8 in the copper clad laminated board of Examples 1-9 and Comparative Examples 1-10, and Comparative Preparation Examples 1-9, and the copper foil to be used.

Characteristic evaluation of double-sided copper-clad laminate For the copper-clad laminates of Examples 1-9 and Comparative Examples 1-10 described above, transmission loss, dielectric properties, copper foil peel strength, solder heat resistance, thermal expansion coefficient, Tg Evaluated. The evaluation results are shown in Table 1. The characteristic evaluation method of the copper clad laminate is as follows.

Measurement of transmission loss and dielectric properties The transmission loss of the copper clad laminate was measured by a triplate line resonator method using a vector network analyzer. The measurement conditions were: line width: 0.6 mm, insulating layer distance between upper and lower ground conductors: about 1.0 mm, line length: 200 mm, characteristic impedance: about 50Ω, frequency: 3 GHz, measurement temperature: 25 ° C. In addition, a dielectric characteristic (relative dielectric constant, dielectric loss tangent) of 3 GHz was calculated from the obtained transmission loss.

Measurement of peel strength of copper foil The peel strength of the copper clad laminate was measured in accordance with the standard JIS-C-6481 of the test method for copper clad laminate for printed wiring boards. Sample was used).

Evaluation of solder heat resistance of copper clad laminate The copper foil on both sides and one side of the copper clad laminate cut into 50 mm square is etched, and its normal state and pressure cooker test (PCT) apparatus (conditions: 121 ° C., 2 .2 atm) is immersed in molten solder at 288 ° C. for 20 seconds, and the appearance of the obtained copper-clad laminate (3 sheets) is visually observed. Examined. The numbers in the table are the number of the copper-clad laminates that have been dipped in the solder, and the number of swells and mess rings that were not observed in the base material (in the insulating layer) and between the base material and the copper foil. Means.

Measurement of Thermal Expansion Coefficient and Tg of Copper Clad Laminate Thermal expansion coefficient (plate thickness direction, 30 to 130 ° C.) and Tg in the above copper clad laminate obtained by etching copper foils on both sides and cutting to 5 mm square are TMA It was measured by.

  When resin varnish and prepreg derived from the same resin composition are used, as can be seen from Examples 1 and 2 or Comparative Examples 1 and 2, the low profile foil is superior in transmission loss compared to the low profile foil and the general foil. On the contrary, the low profile foil is inferior in the peeling strength (peeling strength) between the metal foil. In particular, in Comparative Example 1 in which a low profile foil was used for a conventional resin composition, the transmission loss was slightly improved from 5.72 dB / m to 5.02 dB / m from the general foil, but the peel strength was high. Is inferior to the general foil 0.92 at a low profile foil of 0.58 kN / m, which is insufficient for practical use. As described in the above-mentioned problem, the low profile foil is superior to the general foil in reducing the transmission loss, but the peel strength between the metal foil and the foil is opposite. This confirms that it was difficult to achieve both the reduction in transmission loss and the required peeling strength between the metal foils.

  As is apparent from Table 1, Examples 1 to 9 using the resin composition of the present invention were uniform with no unevenness or streaks in the appearance of any prepreg, and tack (stickiness on the surface). Therefore, it has excellent properties as a prepreg. In terms of characteristics as a laminated board, the relative dielectric constant is 3.25 or less and the dielectric loss tangent is 0.0029 or less, and the solder heat resistance is good because no blistering or measling is observed in all three measurement samples. The coefficient of thermal expansion is not more than 66 ppm / ° C. and has a good thermal expansion characteristic, and also has a high Tg of 172 ° C. or more, so that it has excellent characteristics as a laminate.

  As is apparent from Table 1, Examples 1 to 9 using the resin composition of the present invention are based on a resin composition in which different types and blending amounts of radical reaction initiators are added in combination, and are comparative examples. Compared with 1-10, the reaction start temperature of the prepreg is increased, and the minimum melt viscosity is decreased. In addition, it has excellent dielectric properties, copper foil peel strength, solder heat resistance, thermal expansion characteristics and good moldability at the time of high multi-layer, so it has excellent characteristics especially for high multi-layer copper-clad laminates. Yes.

  And regarding transmission loss and peeling strength, Example 2 using the resin composition of this invention and general foil similarly compared with Comparative Example 2 using general foil, and transmission loss 4.12. It is remarkably excellent and the peel strength is also excellent at 1.16 kN / m.

  The copper-clad laminates of Examples 1 and 3 to 9 using the resin composition of the present invention and the low profile foil are particularly excellent with a transmission loss of 3.49 or less, and although the low profile foil is used, pulling is not possible. It is apparent that the resin composition is excellent in peeling strength of 0.80 or more and extremely effective in achieving both reduction in transmission loss and peeling strength.

  Comparative Examples 1 and 2 are systems of polyphenylene ether and triallyl isocyanurate, and Comparative Example 1 corresponds to Patent Documents 4 and 5 in which a low profile foil is used instead of a general foil. Comparative Example 2 was equivalent to Patent Documents 4 and 5. This system has good prepreg characteristics and thermal expansion coefficient, but is inferior in relative dielectric constant, dielectric loss tangent, and transmission loss. Moreover, when a low profile foil is used, the peel strength is inferior, the solder heat resistance is inferior, and the overall performance is insufficient.

  Comparative Example 3 is a system of polyphenylene ether and bismaleimide compound, and corresponds to Patent Document 2 in which a low profile foil is used instead of a general foil. This system has good prepreg characteristics and coefficient of thermal expansion, but is inferior in relative dielectric constant, dielectric loss tangent, transmission loss, inferior in peeling strength, and has poor overall performance.

  Comparative Example 4 is a conventional system of polyphenylene ether and butadiene homopolymer that is not compatible, and corresponds to Patent Documents 6 and 7 in which a low profile foil is used instead of a general foil. This system has relatively good relative permittivity, dielectric loss tangent, and transmission loss, but is inferior in prepreg characteristics, peel strength, solder heat resistance, and thermal expansion coefficient, and has poor overall performance. Since it can be visually confirmed that this system is macroscopically phase-separated, it can be easily discriminated visually from a sample using the compatibilized composition of the present invention.

  Comparative Example 5 is a conventional system of polyphenylene ether, butadiene homopolymer, and triallyl isocyanurate that is not compatibilized. This system has insufficient relative permittivity, dielectric loss tangent, and transmission loss, is inferior in prepreg characteristics, peel strength, solder heat resistance, and thermal expansion coefficient, and is generally inferior in performance. Since this system is macroscopically phase-separated, it can be easily discriminated visually from a sample using the compatibilized composition of the present invention.

  Comparative Example 6 is a system of polyphenylene ether, butadiene homopolymer, and maleimide compound, and corresponds to an uncompatibilized resin composition of the same components as in the present invention. This system has a slightly insufficient relative dielectric constant, dielectric loss tangent, and transmission loss, is inferior in prepreg characteristics, peel strength, solder heat resistance, and thermal expansion coefficient, and is generally inferior in performance. Since this system is macroscopically phase-separated, it can be easily discriminated visually from a sample using the compatibilized composition of the present invention.

  Comparative Example 7 is a system of a conventional polyphenylene ether, glycol-modified polybutadiene, and maleimide compound that are not compatible, and corresponds to Patent Document 8 in which a low profile foil is used instead of a general foil. This system is inferior in relative dielectric constant, dielectric loss tangent, and transmission loss, inferior in prepreg characteristics, peel strength, solder heat resistance, and thermal expansion coefficient, and generally inferior in performance. Since this system is macroscopically phase-separated, it can be easily discriminated visually from a sample using the compatibilized composition of the present invention.

  Comparative Example 8 is a system of polyphenylene ether, carboxylic acid-modified polybutadiene, and a maleimide compound, and corresponds to Patent Document 8 in which a low profile foil is used instead of a general foil. This system has good prepreg characteristics and peel strength, but is inferior in relative dielectric constant, dielectric loss tangent and transmission loss, inferior in solder heat resistance and thermal expansion coefficient, and has poor overall performance.

  Comparative Example 9 is a system in which an unsaturated (crosslinkable) elastomer is added to a resin system (Comparative Example 4) of a conventional polyphenylene ether and butadiene homopolymer which are not compatible, and a low profile foil instead of a general foil. This corresponds to Patent Document 6 in which This system has relatively good dielectric constant, dielectric loss tangent, and transmission loss, but has poor prepreg characteristics, peel strength, solder heat resistance, thermal expansion coefficient, and Tg decreases, resulting in poor overall performance. It is enough. Since this system is macroscopically phase-separated, it can be easily discriminated visually from a sample using the compatibilized composition of the present invention.

  The resin composition of the present invention achieves further improvement in dielectric properties by a novel configuration of a thermosetting resin composition in which a saturated thermoplastic elastomer is combined with a compatibilized uncured semi-IPN composite. It is a thing. The printed wiring board using the resin composition of the present invention has high heat resistance (especially moisture absorption) in addition to excellent electrical characteristics such as good dielectric characteristics in the high frequency band and characteristics that reduce transmission loss while suppressing a decrease in Tg. Heat resistance), low thermal expansion characteristics, and excellent properties of sufficiently high peel strength between metal foils, particularly low profile foils.

  Resin varnish, prepreg and metal-clad laminate can be formed using the resin composition of the present invention, and the resin composition of the present invention and resin varnish, prepreg and metal-clad laminate using the same are resin compositions We approached the improvement of electrical characteristics from both the aspect of reducing the dielectric loss due to the improvement of the dielectric characteristics of the object itself and the aspect of reducing the conductor loss by making it applicable to a metal foil with a small surface roughness. Therefore, the transmission loss in the high frequency band has been reduced to a level that meets the extremely high demand level of the printed wiring board industry, and can be suitably used in the manufacture of printed wiring boards used in the high frequency field. it can.

  Since the resin composition of the present invention and the resin varnish, prepreg, and metal-clad laminate using the same achieve the above-described characteristics, mobile communication devices that handle high-frequency signals in a high-frequency band, for example, 1 GHz or more, and base station devices thereof It is useful as a member / part for printed wiring boards used in network-related electronic devices such as servers and routers and various electric and electronic devices such as large computers.

  And since the resin varnish using the resin composition of the present invention has a low melt viscosity and a high curing start temperature, the prepreg using the resin varnish can realize a good moldability at the time of multi-layering, and is good It has particularly good dielectric properties, copper foil peel strength, solder heat resistance, and thermal expansion properties, so that it is particularly useful for printed wiring boards for high multilayers.

Claims (24)

  A thermosetting resin composition containing an uncured semi-IPN type complex and (D) a radical reaction initiator, wherein the uncured semi-IPN type complex comprises (A) polyphenylene ether, (B ) A prepolymer formed from a butadiene polymer containing 1,2-butadiene units having 1,2-vinyl groups in the side chain in an amount of 40% or more and not chemically modified, and (C) a crosslinking agent; Is a non-cured semi-IPN type composite that is compatibilized, and (D) component contains a dialkyl peroxide radical initiator and a hydroperoxide radical initiator. object.   The (D) component dialkyl peroxide radical initiator has a one-minute half-life temperature of 175.4 ° C. or higher, and the hydroperoxide radical initiator has a one-minute half-life temperature of 232.5 ° C. or higher. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is present.   The thermosetting resin composition according to claim 1 or 2, wherein the dialkyl peroxide radical initiator in component (D) is α, α'-bis (t-butylperoxy) diisopropylbenzene. .   The hydroperoxide radical initiator in component (D) is one or more radical initiators selected from p-mentahydroperoxide, diisopropylbenzene hydroperoxide, and t-hexyl hydroperoxide. The thermosetting resin composition according to any one of claims 1 to 3.   (A) in the presence of polyphenylene ether, (B) an unmodified butadiene polymer containing 40% or more of 1,2-butadiene units in the molecule having 1,2-vinyl groups in the side chain; A thermosetting resin composition containing an uncured semi-IPN composite containing a polyphenylene ether-modified butadiene prepolymer and (D) a radical reaction initiator, A thermosetting resin composition, wherein the component (D) includes a dialkyl peroxide radical reaction initiator and a hydroperoxide radical reaction initiator.   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 in the range of 2 to 200 parts by mass with respect to 100 parts by mass of the component, and the blending ratio of component (D) (total amount of dialkyl peroxide-based radical reaction initiator and hydroperoxide-based radical reaction initiator) is (A ) Component, (B) component, and (C) component in a range of 0.05 to 10 parts by mass with respect to 100 parts by mass, and (a) dialkyl peroxide and (b) hydroperoxide The thermosetting resin composition according to any one of claims 1 to 5, wherein the blending ratio is (a) :( b) = 20: 80 to 50:50, respectively.   The thermosetting resin composition according to claim 6, wherein the polyphenylene ether-modified butadiene prepolymer is pre-reacted so that the conversion rate of the component (C) is in the range of 5 to 100%. (C) The thermosetting resin composition in any one of Claims 1-7 which contains at least 1 or more types of maleimide compound represented by General formula (1) as a component.

Wherein R ₁ is an m-valent aliphatic or aromatic organic group, and Xa and Xb are the same or different selected from a hydrogen atom, a halogen atom and an aliphatic organic group. A monovalent atom or an organic group, and m represents an integer of 1 or more.)   Component (C) is N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6- It is at least one maleimide compound selected from the group consisting of (diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-dodecylmaleimide, N-isopropylmaleimide and N-cyclohexylmaleimide. Item 8. The thermosetting resin composition according to any one of Items 1 to 7.   The thermosetting resin according to claim 1, wherein the component (C) is at least one maleimide compound containing 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane. Composition.   The thermosetting resin composition according to any one of claims 1 to 7, wherein the component (C) is at least one maleimide compound containing bis (3-ethyl-5-methyl-4-maleimidophenyl) methane. object.   The thermosetting resin composition according to any one of claims 1 to 7, wherein the component (C) is at least one or more vinyl compounds containing divinylbiphenyl.   The thermosetting resin composition according to any one of claims 1 to 12, further comprising (E) a saturated thermoplastic elastomer.   The thermosetting resin composition according to claim 13, wherein the component (E) is at least one kind of saturated thermoplastic elastomer containing a styrene-ethylene-butylene copolymer.   The component (E) is at least one type of saturated thermoplastic elastomer including a saturated thermoplastic elastomer obtained by hydrogenating an unsaturated double bond group of the butadiene portion of the styrene-butadiene copolymer. The thermosetting resin composition according to claim 13.   The thermosetting resin composition according to any one of claims 13 to 15, wherein the component (E) is at least one kind of saturated thermoplastic elastomer containing a chemically modified saturated thermoplastic elastomer. object.   The component (E) is at least one kind of saturated thermoplastic elastomer containing a saturated thermoplastic elastomer containing a styrene block in the molecule and a content ratio of the styrene block of 20 to 70%. The thermosetting resin composition according to claim 13.   Furthermore, (F) a crosslinkable monomer or a crosslinkable polymer containing one or more ethylenically unsaturated double bond groups in the molecule, which does not constitute an uncured semi-IPN type complex, is contained. The thermosetting resin composition according to any one of the above.   The component (F) is at least one ethylenically unsaturated double bond group-containing crosslinkable monomer or crosslinkable polymer selected from the group consisting of a butadiene polymer that is not chemically modified and a maleimide compound. Thermosetting resin composition.   Furthermore, (G) The thermosetting resin composition in any one of Claims 1-19 containing at least any one of a brominated flame retardant and a phosphorus flame retardant.   Furthermore, the thermosetting resin composition in any one of Claims 1-20 containing (H) inorganic filler.   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 21 in a solvent.   A prepreg obtained by impregnating a resin varnish for a printed wiring board according to claim 22 into a substrate and then drying the substrate.   A metal-clad laminate obtained by stacking one or more prepregs according to claim 23, placing a metal foil on one or both sides thereof, and heating and pressing.

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