JP5261943B2 - Semi-IPN type thermosetting resin composition and varnish, prepreg and metal-clad laminate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which can be used for production of a print circuit board showing good dielectric properties at high frequency region, capable of significantly reducing a propagation loss, excellent in moisture-absorbability/heat resistance and thermal expansion properties, and providing a satisfactory level of a peeling strength between the print circuit board and a metal foil. <P>SOLUTION: The thermocurable resin composition of a semi-IPN-type compound material which comprises: a polyphenylene ether (A); and a prepolymer comprising a butadiene polymer (B) and a cross-linking agent (C), wherein the butadiene polymer (B) contains a 1,2-butadiene unit having a 1,2-vinyl group in a side chain in an amount of 40% or larger in the molecule and is chemically unmodified, and wherein the polyphenylene ether (A) and the prepolymer are dissolved in each other and are in an uncured form. Further disclosed are a resin varnish, a prepreg and a metal-clad laminate sheet using the resin composition. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a novel semi-IPN composite thermosetting resin composition, and a resin varnish for printed wiring boards, a prepreg, and a metal-clad laminate using the same. 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 Regarding the board.

  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 a large amount of information, the higher the frequency of the electrical signal, the faster the transmission and processing. 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-described requirements for low loss and high speed, it is necessary to further reduce the transmission loss, particularly in the high frequency band, in the characteristics of the printed wiring board itself that performs transmission and processing mounted on the device. is there.

  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 similar to 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 A resin composition using a copolymer or polystyrene and triallyl cyanurate or triallyl isocyanurate in combination (see Patent Documents 4 to 5), a resin composition using polybutadiene in combination (see Patent Documents 6 and 7), Resin composition obtained by pre-reaction of modified polybutadiene having a functional group such as hydroxyl group, epoxy group, carboxyl group, (meth) acryl group, and bismaleimide and / or cyanate ester (see Patent Document 8), unsaturated double bond The above-mentioned triallyl cyanu is added to a polyphenylene ether provided or grafted with a group-containing compound. A resin composition (see Patent Document 9 and Patent Document 10), or a reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride with the above bis A resin composition using maleimide or the like (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

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 the 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, it is accompanied by moisture absorption in the dielectric properties. There was a tendency for large drift.
In the resin composition combined with polybutadiene shown in Patent Documents 4 to 7 and Patent Document 10, although the dielectric properties are excellent, there is a problem that the strength of the resin itself is low and the coefficient of thermal expansion is high. It was inappropriate for printed wiring board use.
Patent Document 8 is a resin composition in which a modified polybutadiene is used in combination in order to improve adhesion to metals and glass substrates. However, there is a problem that the dielectric characteristics are greatly deteriorated particularly in a high frequency region of 1 GHz or more as compared with the case where unmodified polybutadiene is used.
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, it is considered that there is a demand for a thermosetting resin composition containing PPE which has improved the above-described thermoplastic defects and has excellent dielectric properties.

  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 study 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, an insulating (resin) layer and a conductor (metal foil) layer It was found that the adhesive strength (bonding force) between the two was weak, and the required peel strength could not be ensured. 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 these Patent Documents 1 to 11 are metal foils having a low surface roughness such as low profile foils in addition to the problems described above. I found a problem that is 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 the resin composition containing these is used as it is, there is a problem of tack which is a drawback of the butadiene homopolymer system in an uncured state, so that a prepreg having a uniform appearance and good handleability is obtained. It is not possible. 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.
In addition, the peel strength between the metal foil is low enough that the low profile foil can be applied, but this is less than the low interfacial adhesion between the butadiene homopolymer and the metal foil. The lower the cohesive fracture strength of the resin in the vicinity of the metal foil at the time of peeling, is considered to have an influence as a larger factor.

Therefore, in order to solve the above problems, the present invention has good dielectric properties particularly in a high frequency band, can significantly reduce transmission loss, and is excellent in moisture absorption heat resistance and thermal expansion properties, Moreover, it is an object to provide a thermosetting resin composition capable of producing a printed wiring board satisfying the peel strength between the metal foil, and a resin varnish, a prepreg and a metal-clad laminate using the same. .
The embodiments of the present invention are not limited to the invention that solves all the problems of the prior art.

The present inventors and applicants' Japanese applications 2006-4067, 2006-1116405 and 2006-246722 are incorporated herein in their entirety and for all purposes.
As a result of intensive research on the resin composition containing polyphenylene ether to solve the above-mentioned problems, the present inventors have made uncured polyphenylene ether and a prepolymer from a specific butadiene polymer compatible. Is a thermosetting resin composition of a semi-IPN type composite and containing a compatibilized uncured polyphenylene ether-modified butadiene polymer produced by a novel and unique compatibility method The composition was a semi-IPN composite thermosetting resin composition. It is clear that by using this resin composition for printed wiring board applications, it has excellent dielectric properties in the high frequency band, excellent transmission loss reduction characteristics, and good hygroscopic heat resistance and low thermal expansion characteristics. It was. Since this resin composition has a high peel strength between the metal foil, it has been found that a metal foil having a small surface roughness such as a low profile foil can be applied, and the present invention has been completed. .

  That is, the present invention is a semi-IPN composite thermosetting resin composition comprising (A) polyphenylene ether and (B) 1,2-butadiene units having a 1,2-vinyl group in the side chain. The present invention relates to a resin composition comprising a butadiene polymer which is contained in a molecule of 40% or more and which is not chemically modified and (C) a prepolymer from a cross-linking agent, which is compatibilized and uncured.

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

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

  Furthermore, the present invention includes (A) polyphenylene ether in the presence of (B) 1,2-butadiene unit having 1,2-vinyl group in the side chain in the molecule of 40% or more, and is chemically modified. A polyphenylene ether-modified butadiene prepolymer obtained by prereacting a butadiene polymer having no conversion with (C) a crosslinking agent so that the conversion of component (C) is 5 to 100%, preferably 5 to 80%. It is related with the resin composition to contain.

  In the present invention, as the component (C), the general formula (1):

Where
R ₁ is an m-valent aliphatic or aromatic organic group,
Xa and Xb are the same or different monovalent atoms or organic groups selected from a hydrogen atom, a halogen atom and an aliphatic organic group, and m represents an integer of 1 or more.
It relates to a resin composition containing at least one or more maleimide compounds represented by the formula:

  In the present invention, the component (C) contains 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 It is related with the resin composition which is.

  The present invention relates to a resin composition in which the component (C) is at least one maleimide compound containing 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane.

  The present invention relates to a resin composition in which the component (C) is at least one maleimide compound containing bis (3-ethyl-5-methyl-4-maleimidophenyl) methane.

  The present invention relates to a resin composition in which the component (C) is at least one vinyl compound containing divinylbiphenyl.

  In the present invention, 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 related with the resin composition which is the range of 2-200 weight part with respect to 100 weight part of component.

  The present invention further relates to a resin composition containing (D) a radical reaction initiator.

  The present invention further includes (E) a resin containing 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. Relates to the composition.

  In the present invention, the component (E) contains at least one ethylenically unsaturated double bond group-containing crosslinkable material selected from the group consisting of a butadiene polymer that is not chemically modified, a maleimide compound, and a styrene-butadiene copolymer. The present invention relates to a resin composition that is a monomer or a crosslinkable polymer.

  The present invention further relates to a resin composition containing (F) at least one of a brominated flame retardant and a phosphorous flame retardant.

  The present invention further relates to a resin composition containing (G) an inorganic filler.

  The present invention relates to a resin varnish for a printed wiring board obtained by dissolving or dispersing the above resin composition in a solvent.

  The present invention relates to a prepreg obtained by impregnating a substrate with the resin varnish for a printed wiring board and drying it.

  The present invention relates to a metal-clad laminate obtained by stacking one or more prepregs for a printed wiring board as described above, placing a metal foil on one or both sides thereof, and heating and pressing.

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

Hereinafter, preferred embodiments of the present invention will be described in detail.
The reason why the novel semi-IPN composite thermosetting resin composition of the present invention can achieve the above-mentioned object is not clear 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 most excellent dielectric properties after curing are essential. By containing as a component, it aims at improving a dielectric characteristic markedly. As described above, the polyphenylene ether and the butadiene polymer that has not been chemically modified are inherently incompatible with each other, and it has been difficult to obtain a uniform resin. However, a resin having a novel structure uniformly compatible can be obtained by the method using the preliminary reaction of the present invention.

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

  In the present invention, in the presence of polyphenylene ether as component (A), the component (B) contains 1,2-butadiene units having a 1,2-vinyl group in the side chain of 40% or more in the molecule, A butadiene polymer not chemically modified and a crosslinking agent of component (C) are pre-reacted with component (C) at an appropriate conversion rate (reaction rate), in an uncured state before being completely cured, Once, between one linear polymer component (here, component (A), solid line portion) and the other crosslinkable component (here, components (B) and (C), dotted line portion), a so-called “ A uniform resin composition is obtained by using a polyphenylene ether-modified butadiene prepolymer formed with semi-IPN ″ (a thermosetting resin composition of an uncured semi-IPN composite; see the figure below). In this case, the homogenization (compatibility) does not mean that (A) component and other components (partially crosslinked product of (B) component and (C) component) form a chemical bond, It is considered that the molecular chains of the component A) and the other components are oligomerized while being partially and physically entangled with each other, so that a microphase separation structure is formed and apparently uniform (compatibilized). .

The resin composition containing this polyphenylene ether-modified butadiene prepolymer (thermosetting resin composition of an uncured semi-IPN composite) can provide a resin film having an apparently uniform appearance. The polyphenylene ether-modified butadiene prepolymer itself as known in the art does not form a semi-IPN, and the components are not compatible, so 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 heat 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). 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 or poly (2,3,6-trimethyl-1,4-phenylene) ether or 2,6-dimethylphenol obtained by homopolymerization of, -trimethylphenol And a copolymer of 2,3,6, -trimethylphenol and the like. In addition, so-called modified polyphenylene ether such as an alloyed polymer of these with polystyrene or styrene-butadiene copolymer can also be used. In this case, poly (2,6-dimethyl-1,4-phenylene) ether component, It is a polymer containing 50% or more of a (2,3,6-trimethyl-1,4-phenylene) ether component and a copolymer component of 2,6-dimethylphenol and 2,3,6, -trimethylphenol. Is more preferable.

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

  In the present invention, the component (B) used for the production of the polyphenylene ether-modified butadiene prepolymer contains 40% or more of 1,2-butadiene units having 1,2-vinyl groups in the side chain in the molecule, and is chemically modified. The butadiene polymer is not particularly limited as long as it is not made. The side chain 1,2-vinyl group in the molecule and / or one of the terminals is not chemically modified polybutadiene such as epoxidation, glycolation, phenolization, maleation, (meth) acrylation and urethanization, It is essential to be an unmodified butadiene polymer. 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 is 10,000 or more, the fluidity of the resin is inferior when a prepreg is formed, 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 ( New Nippon Petrochemical Co., Ltd., trade name), Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154 (SARTOMER, trade name) 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, unsaturated polyesters, and styrene-butadiene copolymers. 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 In addition, it is desirable from the viewpoint of excellent total balance such as flame resistance.

  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.

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

In the formula, R ₂ is —C (Xc) ₂ —, —CO—, —O—, —S—, —SO ₂ —, or a linking bond, and each may be the same or different. C 1 -C 4 alkyl group, —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. , N and p each 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 (-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-maleimi Phenyl) 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, aromatic such as the following general formula (3) and the following general formula (4) Fine heterocyclic polymaleimide like (although 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 weight or more, more preferably 80% by weight or more. However, it is more preferable to use the maleimide compound alone than to use it in combination with another crosslinking agent.

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

  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 weight. 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 weight part with respect to 100 weight part of total amounts of a component and (C) component, It is more preferable to set it as 10-100 weight part, It is referred to as 15-50 weight part. 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 weight of the total amount of the component (B) and the component (C). Moreover, it is preferable that the mixture ratio of (C) component shall be the range of 2-200 weight part with respect to 100 weight part of (B) component, It is more preferable to set it as 5-100 weight part, 10-75 weight 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 thermal expansion coefficient, Tg, metal foil peel strength, 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 weight, 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 weight, 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 includes a purpose of initiating or promoting a preliminary reaction between the component (B) and the component (C) in the production of a polyphenylene ether-modified butadiene prepolymer, a metal-clad laminate, and a multilayer printed wiring board. For the purpose of initiating or accelerating the curing reaction of the resin composition when producing, it is preferable to contain (D) a radical reaction initiator.

  Specific examples of the component (D) include dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, cumene hydroperoxide, 1,1-bis (t-hexylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2 , 2-bis (4,4-di (t-butylperoxy) cyclohexyl) propane, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis (t -Butylperoxy) hexyne-3, di-t-butyl peroxide, 1,1'-bis (t-butylperoxy) diisop Pyrbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, t-butylperoxyacetate, 2,2- Bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, bis (t-butylperoxy) Peroxides such as isophthalate, isobutyryl peroxide, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4- Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzoin methyl Ether, methyl -o- benzoyl benzoate, but not limited thereto.

  The component (D) is used for the purpose of starting or accelerating a preliminary reaction at the time of producing the polyphenylene ether-modified butadiene prepolymer, and the component (D) is used for the purpose of starting or accelerating the curing reaction after the production of the polyphenylene ether-modified butadiene prepolymer. Are preferably added separately before and after the production of the polyphenylene ether-modified butadiene prepolymer. In that case, (D) component mix | blended for each purpose may use the same kind, may use a different kind, may each be used individually, and mixes two or more types. It may be used.

  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 weight part with respect to 100 weight part. When the radical reaction initiator of component (D) is blended within this numerical range, an appropriate reaction rate can be obtained in a preliminary reaction when producing a polyphenylene ether-modified butadiene prepolymer, and a metal-clad laminate or a multilayer printed wiring board can be obtained. In the curing reaction during production, good curability is obtained.

  In addition, the resin composition of the present invention contains (E) an uncured semi-IPN type composite as necessary, and contains at least one ethylenically unsaturated double bond group in the molecule. Monomers or crosslinkable polymers; (F) flame retardants; (G) inorganic fillers; and various thermosetting resins; various thermoplastic resins; various additives may be further blended, and the resin composition is printed circuit board. The blending amount does not deteriorate the characteristics such as dielectric properties, heat resistance, adhesiveness (stripping strength of metal foil, adhesion to a substrate such as glass), moisture resistance, Tg, and thermal expansion characteristics. It is preferable that

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 (E) is not particularly limited. Specifically, it is selected from the group consisting of a butadiene polymer that is not chemically modified, a maleimide compound, and a styrene-butadiene copolymer. 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 (B) component and the (C) component are blended as the (E) component, a thermosetting resin composition of an uncured semi-IPN type composite (polyphenylene ether-modified butadiene) The amount of the (E) component in this case is distinguished from the amount of the (B) component and the (C) component, and a preferable amount is separately described below. When the same compound as exemplified as the component (B) and the component (C) is blended as the component (E), use the same type as that used when producing the polyphenylene ether-modified butadiene prepolymer. Alternatively, different types may be used.

  When a styrene-butadiene copolymer is blended as the component (E), it can be used in a rubber type or an elastomer type, its molecular weight, the copolymerization ratio of styrene and butadiene, 1,2-vinyl in the butadiene unit. There are no particular restrictions on the bond ratio and the 1,4-bond ratio. Moreover, when blending a butadiene polymer which is not chemically modified with a number average molecular weight exceeding 10,000 as the component (E), it can be used in either a liquid type or a solid type, and a 1,2-vinyl bond ratio and 1,4 -The binding ratio is not particularly limited.

  The blending ratio of the component (E) in the resin composition of the present invention is not particularly limited, but is 2 to 100 weights with respect to 100 parts by weight of the total amount of the components (A), (B) and (C). 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 (F) component, Flame retardants, such as a bromine type, a phosphorus type, and a metal hydroxide, are used suitably. More specifically, brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl). , Ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated Brominated flame retardants such as polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromide Bisphenol A dimethacrylate, brominated reactive flame retardant unsaturated double bond-containing, such as pentabromobenzyl acrylate and brominated styrene.

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

  Although the compounding ratio of the component (F) in the resin composition of the present invention is not particularly limited, it is 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the components (A), (B) and (C). Preferably, the amount is 5 to 150 parts by weight, more preferably 5 to 100 parts by weight. If the blending ratio of the flame retardant is less than 5 parts by weight, the flame resistance tends to be insufficient, and if it exceeds 200 parts by weight, 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 (G) 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 (G) in the resin composition of the present invention is not particularly limited, but is 1 to 1000 parts by weight with respect to 100 parts by weight of the total amount of the components (A), (B) and (C). Is preferable, and 5-500 weight part 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 using aromatic hydrocarbons and ketones as a mixed solvent is preferably 5 to 100 parts by weight of ketones with respect to 100 parts by weight of aromatic hydrocarbons. 10 to 80 parts by weight, more preferably 15 to 60 parts by weight.

  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, complete or partial hydrogenation of styrene-butadiene copolymers, complete or partial hydrogenation of polybutadiene, polyethersulfone, polyetherketone, polyetherimid , Polyphenylene sulfide, polyamideimide, polyamide, thermoplastic polyimide, and liquid crystal polymers such as aromatic polyesters. 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.

  As one production method of the resin composition of the present invention, the polyphenylene ether-modified butadiene prepolymer obtained by the above-mentioned components (A), (B) and (C); (D) a radical reaction initiator; necessary (E) 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) Inorganic filler; and various thermosetting resins; various thermoplastic resins; various additives can be produced by blending, stirring and mixing by known methods.

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

  The solvent used when varnishing the resin composition described above is not particularly limited, but specific examples and preferred solvents include those used in the production of the polyphenylene ether-modified butadiene prepolymer. Those described can be used, these may be used alone or in combination of two or more, aromatic hydrocarbons such as toluene, xylene, mesitylene, and aromatic hydrocarbons More preferred is a mixed solvent of alcohols and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. 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 (non-volatile content) concentration in the varnish is 5 to 80% by weight, 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 modes and embodiments, and can be arbitrarily changed and modified within the scope not departing from the object of the present invention.

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

Preparation of resin varnish (resin composition)

Preparation Example 1
In a 1 liter separable flask equipped with a thermometer, a reflux condenser, a vacuum concentrator and a stirrer, 350 parts by weight of toluene and polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals, Mn: 16000) as component (A) 50 parts by weight were charged, and the temperature in the flask was set to 90 ° C. and dissolved by stirring. Next, butadiene polymer (B-3000, manufactured by Nippon Soda Co., Ltd., Mn: 3000, 1,2-vinyl structure: 90%) 100 parts by weight as component (B) and component (C) 30 parts by weight of bis (4-maleimidophenyl) methane (BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and methyl isobutyl ketone (as a solvent) so that the solid content (nonvolatile content) concentration in the solution is 30% by weight. MIBK) was added and stirring was continued. It was confirmed that these were dissolved or uniformly dispersed. Thereafter, the liquid temperature was raised to 110 ° C. While maintaining the temperature of 110 ° C., 0.5 parts by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation) was used as a reaction initiator. Blended. The blended product is pre-reacted with stirring for about 1 hour, so that (A) polyphenylene ether, (B) butadiene polymer not chemically modified, and (C) cross-linking agent are compatibilized with polyphenylene ether-modified butadiene. A prepolymer solution was obtained. The conversion rate of bis (4-maleimidophenyl) methane in this polyphenylene ether-modified butadiene prepolymer solution was measured using gel permeation chromatography (GPC). The conversion rate was 33%. The conversion rate is a value obtained by subtracting the unconverted portion (measured value) of bis (4-maleimidophenyl) methane from 100.
Subsequently, the liquid temperature in a flask was set to 80 degreeC. Thereafter, the solution was concentrated with stirring so that the solid concentration of the solution became 45% by weight. The solution was then cooled to room temperature. Next, 5 parts by weight of 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) as component (D) was added. Thereafter, methyl ethyl ketone (MEK) was blended to prepare the resin varnish of Preparation Example 1 (solid content concentration: about 40% by weight).

Preparation Example 2
In Preparation Example 1, Preparation Example except that 30 parts by weight of polyphenylmethane maleimide (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 of BMI-2000 in this polyphenylene ether-modified butadiene prepolymer solution was measured using GPC. The conversion rate was 35%.
Subsequently, a resin varnish (solid content concentration of about 40% by weight) of Preparation Example 2 was prepared using this solution in the same manner as Preparation Example 1.

Preparation Example 3
In Preparation Example 1, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-5100, manufactured by Daiwa Kasei Kogyo Co., Ltd.) instead of bis (4-maleimidophenyl) methane as component (C) A polyphenylene ether-modified butadiene prepolymer was obtained in the same manner as in Preparation Example 1, except that 35 parts by weight was used. The conversion of BMI-5100 in this polyphenylene ether-modified butadiene prepolymer solution was measured using GPC. The conversion rate was 25%. Subsequently, a resin varnish (solid content concentration of about 40% by weight) of Preparation Example 3 was prepared using this solution in the same manner as Preparation Example 1.

Preparation Example 4
In Preparation Example 1, instead of bis (4-maleimidophenyl) methane as component (C), 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (BMI-4000, 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 40 parts by weight were used. The conversion of BMI-4000 in this polyphenylene ether-modified butadiene prepolymer solution was measured using GPC. The conversion rate was 30%. Subsequently, the resin varnish (solid content concentration of about 40% by weight) of Preparation Example 4 was prepared using this solution in the same manner as Preparation Example 1.

Preparation Example 5
(a) In Preparation Example 1, instead of bis (4-maleimidophenyl) methane as component (C), 15 parts by weight 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 Imirex-P in this polyphenylene ether-modified butadiene prepolymer solution was measured using GPC. The conversion rate was 26%.
(b) Subsequently, the solution was concentrated in the same manner as in Preparation Example 1, and then 2,2-bis (4- (4-maleimidophenoxy) as the component (E) was maintained while maintaining the liquid temperature at 80 ° C. 25 parts by weight of phenyl) propane (BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was blended. Subsequently, after cooling to room temperature with stirring, 5 parts by weight of 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) was added as component (D). Thereafter, methyl ethyl ketone (MEK) was blended to prepare the resin varnish of Preparation Example 5 (solid content concentration: about 40% by weight).

Preparation Example 6
In Preparation Example 5 (a), 15 parts by weight of bis (4-maleimidophenyl) methane (BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was used instead of N-phenylmaleimide as component (C). In the same manner as in Preparation Example 5, a polyphenylene ether-modified butadiene prepolymer was obtained. The conversion of BMI-1000 in this polyphenylene ether-modified butadiene prepolymer solution was measured using GPC. The conversion rate was 32%.
Subsequently, using this solution, a resin varnish (solid content concentration of about 40% by weight) of Preparation Example 6 was prepared 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 weight were used. The conversion of BMI-4000 in this polyphenylene ether-modified butadiene prepolymer solution was measured using GPC. The conversion rate was 31%.
(b) Subsequently, using this solution, instead of 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane as component (E) in Preparation Example 5 (b), bis (3-ethyl 15 parts by weight of -5-methyl-4-maleimidophenyl) methane (BMI-5100, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and 70 parts by weight of ethylene bis (pentabromophenyl) (SAYTEX 8010, manufactured by Albemarle) as component (F) A resin varnish (solid content concentration of about 40% by weight) of Preparation Example 7 was prepared in the same manner as Preparation Example 5 except that the parts were blended.

Preparation Example 8
In Preparation Example 7 (a), the amount of 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) as component (C) was 40 parts by weight. Except that, a polyphenylene ether-modified butadiene prepolymer was obtained in the same manner as in Preparation Example 7. The conversion of BMI-4000 in this polyphenylene ether-modified butadiene prepolymer solution was measured using GPC. The conversion rate was 30%.
Subsequently, using this solution, instead of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane as component (E) in Preparation Example 7 (b), a styrene-butadiene copolymer (tuffprene) 125, manufactured by Asahi Kasei Chemicals Co., Ltd. 10 parts by weight, and preparation examples except that 70 parts by weight of ethylene bistetrabromophthalimide (BT-93W, manufactured by Albemarle) was blended instead of ethylene bis (pentabromophenyl) In the same manner as in Example 7, the resin varnish of Preparation Example 8 (solid content concentration of about 40% by weight) was prepared.

Preparation Example 9
(a) In Preparation Example 1, instead of bis (4-maleimidophenyl) methane as component (C), 20 parts by weight of divinylbiphenyl (manufactured by Nippon Steel Chemical Co., Ltd.) was used. Similarly, a polyphenylene ether-modified butadiene prepolymer was obtained. The conversion rate of divinylbiphenyl in the polyphenylene ether-modified butadiene prepolymer solution was measured using GPC. The conversion rate was 28%.
(b) Subsequently, after concentrating the solution in the same manner as in Preparation Example 1, 70 parts by weight of brominated polystyrene (PBS64HW, manufactured by Great Lakes) was added as a component (F) while keeping the liquid temperature at 80 ° C. Blended. Next, after cooling to room temperature with stirring, 5 parts by weight of 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) was added as component (D), and then methyl ethyl ketone (MEK) was added. The resin varnish of Preparation Example 9 (solid content concentration of about 40% by weight) was prepared.

Preparation Example 10
Resin varnish produced in the same manner as in Preparation Example 3 (conversion rate of BMI-5100 in the polyphenylene ether-modified butadiene prepolymer solution is 24%), spherical silica (SO-25R, After blending 35 parts by weight of an average particle size of 0.5 μm (manufactured by Admatex), methyl ethyl ketone (MEK) was blended to prepare the resin varnish of Preparation Example 10 (solid content concentration: about 45% by weight).

Preparation Example 11
In Preparation Example 3, Ricon 142 (manufactured by SARTOMER, Mn: 3900, 1,2-vinyl structure: 55%) was used in place of B-3000 as the butadiene polymer that was not chemically modified as component (B). Obtained a polyphenylene ether-modified butadiene prepolymer in the same manner as in Preparation Example 3. The conversion of BMI-5100 in this polyphenylene ether-modified butadiene prepolymer solution was measured using GPC. The conversion rate was 27%. Subsequently, a resin varnish (solid content concentration of about 40% by weight) of Preparation Example 11 was prepared using this solution in the same manner as Preparation Example 3.

Comparative Preparation Example 1
200 parts by weight of toluene and 50 parts by weight of polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) were charged into a 1 liter separable flask equipped with a thermometer, a reflux condenser, and a stirring device, and the temperature in the flask Was set at 90 ° C. and dissolved by stirring. Next, 100 parts by weight of triallyl isocyanurate (TAIC, Nippon Kasei Co., Ltd.) was added, and after confirming that it was dissolved or uniformly dispersed, it was cooled to room temperature. Next, after cooling to room temperature with stirring, 5 parts by weight of 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) was added as a reaction initiator, and then methyl ethyl ketone (MEK). The resin varnish of Comparative Preparation Example 1 (solid content concentration of about 40% by weight) was prepared.

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

Comparative Preparation Example 3
In Comparative Preparation Example 1, instead of triallyl isocyanurate, 100 parts by weight of a butadiene polymer (B-3000, manufactured by Nippon Soda Co., Ltd., Mn: 3000, 1,2-vinyl structure: 90%) not chemically modified is used. A resin varnish (solid content concentration of about 40% by weight) of Comparative Preparation Example 3 was prepared in the same manner as in Comparative Preparation Example 1 except that it was not.

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

Comparative Preparation Example 5
In Comparative Preparation Example 4, the same procedure as in Comparative Preparation Example 4 was performed except that 30 parts by weight 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 weight) of Comparative Preparation Example 5 was prepared.

Comparative Preparation Example 6
350 parts by weight of toluene and 50 parts by weight of polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., Mn: 16000) were charged into a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator and stirrer. The temperature in the flask was set to 90 ° C. and dissolved by 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 weight, bis (4-maleimidophenyl) methane (BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 30 parts by weight and methyl isobutyl ketone (MIBK) was added so that the solid content (nonvolatile content) concentration in the solution was 30% by weight, and dissolved or uniformly dispersed. 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation) 0.5 weight as a reaction initiator while keeping the liquid temperature at 110 ° C. after confirmation The parts were mixed and pre-reacted with stirring for about 10 minutes. The conversion rate of BMI-1000 in the preliminary reaction product was measured using GPC. The conversion was 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 45 weight%, stirring. The solution was then cooled to room temperature. Then, after adding 5 parts by weight of 1,1′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation) as a reaction initiator, methyl ethyl ketone (MEK) was blended, and Comparative Preparation Example No. 6 resin varnish (solid content concentration of about 40% by weight) was prepared.

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-vinyl) A preliminary reaction product was obtained in the same manner as in Comparative Preparation Example 6 except that 100 parts by weight of 89% of the structure was used. The BMI-1000 conversion of this pre-reacted product was measured using GPC. The conversion rate was 19%. Subsequently, a resin varnish (solid content concentration of about 40% by weight) of Comparative Preparation Example 7 was prepared using this solution in the same manner as Comparative Preparation Example 6.

Comparative Preparation Example 8
In Preparation Example 1, polyphenylene was used in the same manner as Preparation Example 1 except that Ricon 130 (manufactured by SARTOMER, Mn: 2500, 1,2-vinyl structure: 28%) was used as the butadiene homopolymer instead of B-3000. A polybutadiene pre-reactant was obtained in the presence of ether. The conversion rate of BMI-1000 in this preliminary reaction solution was measured using GPC. The conversion rate was 24%. Subsequently, a resin varnish (solid content concentration of about 40% by weight) of Comparative Preparation Example 8 was prepared using this solution in the same manner as Preparation Example 1.

  Table 1 shows the amount of each raw material used for the preparation of the resin varnishes (curable resin compositions) of Preparation Examples 1 to 11 and Comparative Preparation Examples 1 to 8.

In the table, abbreviations have the following meanings.
BMI: bismaleimide compound imiflex-P: N-phenylmaleimide TAIC: triallyl isocyanurate perhexa TMH: 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane-butyl P: 1,1′-bis (t-butylperoxy) diisopropylbenzene SAYTEX8010: ethylenebis (pentabromophenyl)
BT-93W: Ethylene bistetrabromophthalimide PBS64HW: Brominated polystyrene SO-25R: Spherical silica

Preparation of Prepreg After impregnating the resin varnish obtained in Preparation Examples 1 to 11 and Comparative Preparation Examples 1 to 8 into a glass cloth having a thickness of 0.1 mm (E glass, manufactured by Nitto Boseki Co., Ltd.), at 100 ° C. for 5 minutes. Heat drying was performed to prepare prepregs of Preparation Examples 1 to 11 and Comparative Preparation Examples 1 to 8 having a resin content of 50% by weight. In addition, the case where the resin varnishes of Preparation Examples 1 to 11 correspond to Preparation Examples 1 to 11, respectively, and the case where the resin varnishes of Comparative Preparation Examples 1 to 8 are used correspond to Comparative Preparation Examples 1 to 8, respectively. .

Evaluation of Prepreg The appearance and tackiness of the prepregs of Preparation Examples 1 to 11 and Comparative Preparation Examples 1 to 8 were evaluated. The evaluation results are shown in Table 2. 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.

Production of double-sided copper-clad laminate A component (unpressed) in which the four prepregs of Production Examples 1 to 11 and Comparative Production Examples 1 to 8 described above are stacked is provided, and a low profile copper foil having a thickness of 18 μm (up and down) F3-WS, M-plane Rz: 3 μm, manufactured by Furukawa Electric Co., Ltd.) is placed so that the M-plane is in contact, and heat-press molding is performed at 200 ° C., 2.9 MPa, 70 minutes, and double-sided copper-clad laminate A plate (thickness: 0.5 mm) was produced. For the prepregs of Production Example 1 and Comparative Production Example 1, a double-sided copper-clad laminate using a general copper foil (GTS, M-plane Rz: 8 μm, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 18 μm is used as the copper foil. Each was produced under the same pressing conditions as when the profile copper foil was used. In addition, it shows in Table 2 about the combination of the preparation examples 1-11 in the copper clad laminated board of Examples 1-12 and Comparative Examples 1-9, and the prepreg of Comparative Preparation Examples 1-8, and use copper foil.

Characteristic evaluation of double-sided copper-clad laminates Evaluation of transmission loss, dielectric properties, copper foil peel strength, solder heat resistance, and thermal expansion coefficient for the copper-clad laminates of Examples 1 to 12 and Comparative Examples 1 to 9 described above did. The evaluation results are shown in Table 2. 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. Measurement conditions were as follows: line width: 0.6 mm, upper and lower ground conductor insulating layer distance: about 1.0 mm, line length: 200 mm, characteristic impedance: about 50Ω, frequency: 3 GHz, measurement temperature: 25 ° C. Further, the dielectric characteristics (relative dielectric constant, dielectric loss tangent) of 3 GHz were calculated from the obtained transmission loss.

Measurement of copper foil peeling strength The copper foil peeling strength of the copper clad laminate was measured according to the copper clad laminate test standard JIS-C-6481 (measurement under normal conditions).
For the measurement, after producing a copper clad laminate, the copper foil was etched to produce a measurement test line (width 10 mm ± 0.1 mm). Subsequently, the peeling strength was measured at a peeling speed of about 50 mm / min.

Evaluation of solder heat resistance of copper-clad laminate Etching copper foil on both sides and one side of the above-mentioned copper-clad laminate cut to 50 mm square, its normal state and pressure cooker test (PCT) equipment (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.

Evaluation of Thermal Expansion Coefficient of Copper Clad Laminate The thermal expansion coefficient (plate thickness direction, 30 to 130 ° C.) of the copper clad laminate obtained by etching the copper foils on both sides and cutting into 5 mm squares was measured by TMA.

When the resin varnish and prepreg derived from the same resin composition were used, as can be seen from Examples 1 and 2 or Comparative Examples 1 and 2, low profile foil and general foil were compared. In this case, the low profile foil is excellent in transmission loss, and conversely, the peel strength between the metal foil (peel strength) is inferior to the low profile foil. In particular, in Comparative Example 1 in which a low profile foil was used for the 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 strong. The general foil 0.92 is inferior to the low profile foil 0.58 kN / m, which is insufficient for practical use.
As described in the above problem, this is because the low profile foil is superior to the general foil in reducing transmission loss. The peel strength between the metal foil is the opposite. Therefore, it is proved that it is difficult to achieve both reduction in transmission loss and required peeling strength between the metal foil.

As is apparent from Table 2, Examples 1 to 12 using the resin composition of the present invention are uniform with no appearance, unevenness, streaks, etc. in any prepreg. Furthermore, since there is no tack (stickiness of the surface), it has excellent prepreg characteristics. In addition, the characteristics as a laminated board are excellent, such as a relative dielectric constant of 3.30 or less and a dielectric loss tangent of 0.0034 or less, and the solder heat resistance is good without any occurrence of blistering or measling in all three measurement samples. Also, the coefficient of thermal expansion is 65 ppm / ° C. or less, which also has good thermal expansion characteristics.
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 4.29. It is extremely excellent and the peel strength is also excellent at 1.12 kN / m.
The copper-clad laminates of Examples 1 and 3 to 12 using the resin composition of the present invention and the low profile foil are particularly excellent with a transmission loss of 3.72 or less, and despite using the low profile foil, the pulling It is clear that the resin composition is excellent at a peel strength of 0.77 or more, and is extremely effective for achieving both a reduction in transmission loss and a peel 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 thermal expansion coefficient, but is inferior in relative dielectric constant, dielectric loss tangent and transmission loss, inferior in peeling strength, or inferior in heat resistance, 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 good relative dielectric constant, dielectric loss tangent, and transmission loss, but is inferior in prepreg characteristics, peel strength, solder heat resistance, and thermal expansion coefficient, and its overall performance is insufficient. 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 5 is a conventional system of polyphenylene ether, butadiene homopolymer, and triallyl isocyanurate that is not compatibilized. This system is insufficient in relative permittivity, 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 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 is insufficient in relative permittivity, 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 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 produced in the same manner as in Example 1 using a butadiene polymer that is not chemically modified and has a 1,2-vinyl structure of less than 40%, which is not applied to the present invention. This system is inferior to that of Example 1 in terms of dielectric loss tangent and thermal expansion coefficient because the curability decreases as the crosslinking density decreases as compared with the present invention.

The resin composition of the present invention has a novel configuration of a compatibilized uncured semi-IPN type composite thermosetting resin composition, and for this purpose, a printed wiring board using the resin composition of the present invention is used. In this case, excellent dielectric properties in the high frequency band and excellent electrical properties to reduce transmission loss, good moisture absorption heat resistance and low thermal expansion properties, and pulling between metal foil (especially rope file foil) It has an excellent property that the peel strength is sufficiently high.
Moreover, a resin varnish, a prepreg, and a metal-clad laminate can be formed using the resin composition of the present invention, and a resin varnish, a prepreg, and a metal-clad laminate using the resin composition of the present invention, Since the dielectric loss was reduced by improving the dielectric characteristics of the resin material itself, the electrical characteristics could be improved. Furthermore, the resin composition of the present invention has an excellent characteristic that it can be applied to a metal foil having a small surface roughness in addition to a metal foil having a normal surface roughness. Therefore, in the combination of the resin composition of the present invention and the metal foil having a small surface roughness, the electrical characteristics can be improved in order to further reduce the conductor loss. Therefore, the transmission loss in the high frequency band has been reduced to a level that meets the required level of the printed wiring board industry, and can be suitably used for manufacturing printed wiring boards used in the high frequency field.
And since the resin composition, resin varnish, prepreg and metal-clad laminate of the present invention achieve the above-mentioned characteristics, mobile communication devices that handle high-frequency signals in a high-frequency band, for example, 1 GHz or more, their base station devices, servers, It is useful as a component / part of printed wiring boards used in network-related electronic devices such as routers and various electric and electronic devices such as large computers.

Claims (18)

  A thermosetting resin composition of a semi-IPN type composite, wherein (A) polyphenylene ether and (B) 1,2-butadiene units having a 1,2-vinyl group in the side chain are 40% or more in the molecule A resin composition comprising a butadiene polymer which is contained and not chemically modified, and (C) a prepolymer from a cross-linking agent, which is compatibilized and uncured. A semi-IPN type composite comprising (A) polyphenylene ether, (B) a radical polymerizable polymer obtained by radical polymerization of a butadiene polymer and (C) a crosslinking agent,
A chemically modified butadiene polymer in which (B) is composed of — [CH ₂ —CH═CH—CH ₂ ] —unit (j) and — [CH ₂ —CH (CH═CH ₂ )] — unit (k) And the ratio of j: k is 60-5: 40-95;
(C) is a compound having one or more ethylenically unsaturated double bonds in the molecule,
An uncured semi-IPN composite thermosetting resin composition.   (A) in the presence of polyphenylene ether, (B) 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; C) A thermosetting resin composition of an uncured semi-IPN composite containing a polyphenylene ether-modified butadiene prepolymer obtained by pre-reacting with a crosslinking agent.   The resin composition according to claim 3, wherein the polyphenylene ether-modified butadiene prepolymer is pre-reacted so that the conversion ratio of the component (C) is in the range of 5 to 100%. As the component (C), the general formula (1):

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. 5 is a monovalent atom or an organic group, and m represents an integer of 1 or more. 5) contains at least one maleimide compound represented by the formula (1): Resin composition.   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 5. The resin composition according to any one of Items 1 to 4.   The resin composition according to any one of claims 1 to 4, wherein the component (C) is at least one or more maleimide compounds containing 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane. .   The resin composition according to claim 1, wherein the component (C) is at least one maleimide compound containing bis (3-ethyl-5-methyl-4-maleimidophenyl) methane.   The resin composition according to any one of claims 1 to 4, wherein the component (C) is at least one vinyl compound containing divinylbiphenyl.   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). The resin composition of any one of Claims 1-9 which is the range of 2-200 weight part with respect to 100 weight part of components.   The resin composition according to any one of claims 1 to 10, further comprising (D) a radical reaction initiator.   Furthermore, (E) 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 complex, 11. The resin composition according to any one of 11 above.   The component (E) is a crosslinkable monomer or crosslinkable containing at least one ethylenically unsaturated double bond group selected from the group consisting of a butadiene polymer that is not chemically modified, a maleimide compound, and a styrene-butadiene copolymer. The resin composition according to claim 12, which is a polymer.   The resin composition according to any one of claims 1 to 13, further comprising (F) at least one of a brominated flame retardant and a phosphorous flame retardant.   The resin composition according to claim 1, further comprising (G) an inorganic filler.   A resin varnish for a printed wiring board obtained by dissolving or dispersing the resin composition according to any one of claims 1 to 15 in a solvent.   A prepreg obtained by impregnating a substrate with the resin varnish for printed wiring board according to claim 16 and then drying the substrate.   A metal-clad laminate obtained by stacking one or more prepregs for printed wiring boards according to claim 17, placing a metal foil on one side or both sides, and heating and pressing.