JP2010111758A - Resin composition, prepreg, laminate and printed board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material for a high frequency-capable wiring board that satisfies all of adhesion, low thermal expansion, low dielectric loss, low conductor loss and processability, to provide a multilayer printed board using the material and to provide an electronic component. <P>SOLUTION: A resin composition including 70-90 pts.wt. crosslinking component, 10-30 pts.wt. high molecular weight component having an elongation at break of 700% or more and 150-400 pts.wt. inorganic filler is used in an insulating layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition, a prepreg, a laminated board, and a printed board.

  In recent years, electronic devices have been reduced in size and weight, and printed circuit boards used therefor are required high-density wiring by multilayering and fine wiring. In order to realize high-density wiring, the printed circuit board is required to have high adhesiveness and low thermal expansion for improving the reliability of the interphase connection wiring for the purpose of improving the reliability of the fine wiring on the substrate.

  On the other hand, the signal band of information communication devices such as PHS and mobile phones, and the CPU clock time of computers have reached the GHz band, and higher frequencies are advancing. The transmission loss of an electric signal is represented by the sum of dielectric loss, conductor loss, and radiation loss, and the dielectric loss, conductor loss, and radiation loss increase as the frequency of the electric signal increases.

  Since transmission loss attenuates an electrical signal and impairs the reliability of the electrical signal, a circuit board that handles high-frequency signals must be devised to suppress increases in dielectric loss, conductor loss, and radiation loss.

  Dielectric loss is proportional to the product of the square root of the relative permittivity of the insulator forming the circuit, the dielectric loss tangent and the frequency of the signal used. Therefore, an increase in dielectric loss can be suppressed by selecting an insulating material having a small relative dielectric constant and dielectric loss tangent as the insulator.

  The conductor loss is generally reduced by reducing the surface roughness of the conductor layer. However, when the surface roughness of the conductor layer is reduced, there arises a new problem that the adhesiveness with the insulating layer is lowered. Development of a resin composition and a substrate material that satisfy all of high adhesiveness, low dielectric loss, and low thermal expansion is demanded.

  Conventional resin materials having a low dielectric constant and low dielectric loss tangent are shown below. A fluororesin typified by polytetrafluoroethylene (PTFE) has a low relative dielectric constant and dielectric loss tangent, and has long been used as a substrate material for handling high-frequency signals.

  On the other hand, various non-fluorine insulating materials having a low dielectric constant and a low dielectric loss tangent, which can be easily varnished with an organic solvent, have a low molding temperature and curing temperature, and are easy to handle, have been studied.

  For example, there is an example in which a glass cloth is impregnated with a diene polymer such as polybutadiene described in Patent Document 1 and cured with a peroxide.

  In addition, as described in Patent Document 2, there is an example in which cyanate ester, diene polymer, and epoxy resin are heated to form a B stage.

  Examples of resin compositions composed of allylated polyphenylene ether and triallyl isocyanate described in Patent Document 3, and examples of using all-hydrocarbon polyfunctional styrene compounds described in Patent Document 4 and Patent Document 5 as crosslinking components Is mentioned. However, no system that satisfies all of high adhesion, low dielectric loss and low thermal expansion has been found.

  On the other hand, the insulating layer of the wiring board often contains glass cloth as a base material, and various studies have been made on the low dielectric constant and low dielectric loss tangent of the base material. Examples include NE glass cloth that defines the compounding ratio of silicon oxide, aluminum oxide, boron oxide, and the like described in Patent Document 6, glass cloth that is a composite of quartz glass fiber and non-quartz glass fiber described in Patent Document 7, Examples thereof include a fine-line quartz glass fiber having a diameter of 7 μm or less described in Document 8, a method for producing a cloth using the same. By combining a low dielectric constant and low dielectric loss tangent cloth or non-woven fabric with a resin composition that satisfies all of high adhesion, low dielectric loss and low thermal expansion, excellent high frequency signal transmission characteristics and fine wiring It is possible to obtain a wiring board material such as a high-frequency printed circuit board, a multilayer printed circuit board, a laminated board used therein, and a prepreg having excellent reliability while being compatible with processing.

  Further, Patent Document 9 aims to provide a low dielectric loss resin composition that is soluble in a low-boiling general-purpose solvent and excellent in processability of a wiring board while maintaining the excellent characteristics of polyphenylene ether. For example, a low dielectric loss resin for multilayer wiring boards, which is a copolymer composed of repeating units represented by a specific structural formula, is disclosed.

  Patent Document 10 also discloses a resin composition having excellent varnish storage stability, low dielectric constant and dielectric loss tangent and high heat resistance, and a curable film using the composition. A curable resin composition in which a specific polymerization inhibitor or antioxidant is combined with a styrenic thermoplastic elastomer having a double bond with a compound obtained by styrenating a functional phenylene ether oligomer is disclosed.

  Further, Patent Document 11 discloses a thermoplastic resin having a small coefficient of linear expansion, sufficient strength, heat resistance and chemical resistance, and good dielectric properties, and an automobile outer plate obtained from the thermoplastic resin. For the purpose of providing a molded article, a polyphenylene ether resin (A), a polystyrene resin (B), an inorganic filler (C) having a relative dielectric constant of 50 or more, and a plate shape and / or needle shape having an aspect ratio of 5 or more. Inorganic filler (D), the weight ratio of the content of (A) and (B) is 70/30 to 10/90, and (C) per 100 parts by weight in total of (A) and (B) ) Is 10 to 250 parts by weight, (A) and (B) are 100 parts by weight in total (D) content is 1 to 100 parts by weight, and (A) is a continuous phase. A thermoplastic resin composition to be molded is disclosed. There.

  Patent Document 12 discloses a specific polyetherimide, a specific polyphenylene oxide, and a silane for the purpose of providing a composite material having excellent heat resistance, electrical insulation, dielectric properties, and thermal conductivity and good compatibility. A composite material comprising a coupling agent, a filler, and a styrene copolymer or a divinyl compound is disclosed.

Japanese Patent Laid-Open No. 08-208856 Japanese Patent Laid-Open No. 11-124491 JP 09-246429 A Japanese Patent Laid-Open No. 2002-249531 JP 2005-89691 A JP-A-9-74255 JP 2005-336695 A JP 2006-282401 A JP 2006-93690 A JP 2007-191681 A JP-A-2005-97477 Japanese Patent Laid-Open No. 6-1911

  Patent Document 5 discloses wiring board materials such as a prepreg, a laminated board, a wiring board, and a multilayer wiring board in which a quartz glass cloth is impregnated with a resin composition containing a polyfunctional styrene compound having a very low dielectric loss tangent as a crosslinking component. Therefore, the dielectric loss tangent of the insulating layer is 0.0009 at 10 GHz and exhibits extremely excellent characteristics. However, the laminated board, wiring board, and multilayer wiring board described in Patent Document 5 lack consideration for drilling workability (drilling workability). That is, the quartz glass cloth is very hard, and the drilling workability by a drill or the like is inferior to the case of using a general glass cloth. Moreover, the quartz glass fiber used for the production of the quartz glass cloth has low productivity, and there are problems in terms of stable supply and cost.

  As a technology to improve processability while maintaining the low dielectric loss tangent property of quartz glass cloth, we use technology that uses a composite cloth in which quartz fiber and olefin fiber such as polypropylene, polyethylene, and polymethylpentene are combined. We have found a technique to apply a thin quartz cloth having a thin and dense structure, and have been studying it.

  As a result, as a common problem for the practical application of the composite cloth and the thin quartz cloth, it was found that the thermal expansion coefficient in the Z direction (hereinafter abbreviated as the thermal expansion coefficient) when the laminated board and the printed board were used.

  This is because in the case of composite cloth, the coefficient of thermal expansion tends to increase due to the influence of olefin fibers contained in the cloth, and in the case of thin quartz cloth, the resin composition is easily applied excessively during the production of the prepreg. The content of glass fiber or the like, which is a low thermal expansion component, decreased, and the thermal expansion coefficient of the laminate and the printed board increased. This problem is considered to be solved by highly filling the resin composition with a low thermal expansion inorganic filler such as quartz.

  However, in general, a resin composition highly filled with an inorganic filler is hard and forms a brittle cured product, which causes a new problem that the adhesive strength with a conductor layer is reduced.

  An object of this invention is to provide the low thermal expansion resin composition which raised the packing density of the inorganic filler and improved the adhesive force.

  Furthermore, the present invention applies this technology to a wiring board material that is a composite material of a low dielectric loss resin composition and a low dielectric loss cloth excellent in processability, and has low dielectric loss, low thermal expansion, and high adhesion. It aims at providing the resin composition which satisfy | fills all the characteristics and the outstanding drill workability, and the prepreg, laminated board, printed circuit board, and multilayer printed circuit board which use this resin composition.

  The resin composition of the present invention is a resin composition containing 70 to 90 parts by weight of a crosslinking component, 10 to 30 parts by weight of a high molecular weight component, and 150 to 400 parts by weight of an inorganic filler, The elongation at break is 700% or more.

  The prepreg of the present invention is characterized in that a cloth or a nonwoven fabric is impregnated with the resin composition.

  The laminated board of this invention has a conductor layer in the single side | surface or both surfaces of the hardened | cured material of the said prepreg, It is characterized by the above-mentioned.

  The printed circuit board of the present invention is characterized by having a conductor wiring on one side or both sides of the cured product of the prepreg.

  According to the present invention, it is possible to obtain a resin composition that achieves both high adhesion to the conductor layer and low thermal expansion, and wiring board materials such as prepregs and laminates, printed boards, and multilayer printed boards using the resin composition. .

  Furthermore, according to the present invention, a thermosetting polyphenylene ether which is a low dielectric loss material, a styrene-based elastomer, a resin composition in which a silicon oxide filler is combined, and a composite cloth or thin quartz cloth in which quartz fibers and olefin fibers are combined. Are combined, wiring board materials such as prepregs and laminates having low transmission loss and excellent drillability, as well as high-frequency printed boards and multilayer printed boards using the same can be obtained.

  The present invention relates to a multilayer printed circuit board that achieves both low thermal expansion and high adhesion, a printed circuit board, and a wiring board material such as a resin composition, a prepreg, and a laminate used for manufacturing the printed circuit board. The present invention also relates to a multilayer printed board having excellent low dielectric constant and low dielectric loss tangent, a printed board, and a wiring board material such as a resin composition, a prepreg, and a laminate used for producing the printed board.

  The present invention is characterized by the following configurations.

  (1) The resin composition of the present invention is a resin containing 70 to 90 parts by weight of the crosslinking component (A), 10 to 30 parts by weight of the high molecular weight component (B), and 150 to 400 parts by weight of the inorganic filler (C). It is a composition, Comprising: The breaking elongation rate of a high molecular weight component (B) is 700% or more.

  (2) In addition to the feature described in (1) above, the inorganic filler (C) is contained in an amount of 251 to 400 parts by weight.

  (3) In addition to the characteristics described in (1) or (2) above, the composition contains a curable polyphenylene ether compound as the crosslinking component (A) and a hydrogenated styrene elastomer as the high molecular weight component (B). And a spherical silicon oxide filler as an inorganic filler.

  (4) In addition to the characteristics described in (3) above, the curable polyphenylene ether is styrene in Gel Permeation Chromatography measurement (hereinafter referred to as GPC measurement) represented by the following general formula (1) or the following general formula (2). It is a compound having a converted number average molecular weight of 1000 to 15000.

（一般式（１）はフェノール誘導体のランダム共重合体を表し、ｌ、ｍは重合度であり、１以上の整数を表し、前記共重合体は分子量分布を持っていてもよい。Ｒ１、Ｒ２、Ｒ７は水素原子又は炭素数１〜９の炭化水素基を表し、Ｒ３〜Ｒ６は、同一又は異なって、水素原子あるいは炭素数１〜９の炭化水素基であるが少なくとも１つ以上が炭素数２〜９の不飽和炭化水素基を含む炭化水素基である。一般式（２）はフェノール誘導体の重合体を表し、ｎ、ｏは重合度であり、１以上の整数を表し、前記共重合体は分子量分布を持っていてもよい。Ｒ８は、炭素数１以上の有機基であり、Ｒ９〜Ｒ１６は、同一又は異なって、水素原子、炭素数１〜９の炭化水素基、Ｒ１７〜Ｒ１８は、水素原子又は炭素数１〜９の炭化水素基を表す。）
（５）上記（３）に記載の特徴に加え、水素添加されたスチレン系エラストマーが、全炭化水素骨格を有し、ＧＰＣ測定におけるスチレン換算数平均分子量が５００００〜１０００００であり、スチレン含有率が１０〜４０重量％である。

(General formula (1) represents a random copolymer of phenol derivatives, l and m are degrees of polymerization, and represent an integer of 1 or more, and the copolymer may have a molecular weight distribution. R1, R2 , R7 represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, and R3 to R6 are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, but at least one or more carbon atoms And a hydrocarbon group containing an unsaturated hydrocarbon group of 2 to 9. General formula (2) represents a polymer of a phenol derivative, n and o are degrees of polymerization, and represent an integer of 1 or more. The combination may have a molecular weight distribution, R8 is an organic group having 1 or more carbon atoms, and R9 to R16 are the same or different and are a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms, R17 to R18. Represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms.)
(5) In addition to the features described in (3) above, the hydrogenated styrene elastomer has a total hydrocarbon skeleton, the styrene-equivalent number average molecular weight in GPC measurement is 50,000 to 100,000, and the styrene content is 10 to 40% by weight.

  (6) In addition to the characteristics described in (3) above, the spherical silicon oxide filler has an average particle size of 0.2 to 3 μm, and vinyl, methacrylate, acrylate and styrene silane coupling agents are formed on the surface thereof. At least one is carried.

  (7) In addition to the feature described in the above (3), it further contains at least one flame retardant having a specific structure represented by the following general formula (3) or (4).

（８）上記（３）に記載の特徴に加え、更に、下記一般式（５）で表される多官能スチレン化合物、下記一般式（６）で表されるビスマレイミド化合物、下記一般式（７）で表される繰り返し単位を有する１、２−ポリブタジエン化合物の群から選ばれる少なくとも１つの架橋助剤を含有する。

(8) In addition to the characteristics described in (3) above, the polyfunctional styrene compound represented by the following general formula (5), the bismaleimide compound represented by the following general formula (6), the following general formula (7) And at least one crosslinking aid selected from the group of 1,2-polybutadiene compounds having a repeating unit represented by

（一般式（５）は、複数のスチレン基を有する多官能スチレン化合物を表し、ｐは２以上の整数を表し、Ｒ２１は炭化水素骨格を表し、ＧＰＣ測定におけるポリスチレン換算重量平均分子量は１０００以下である。一般式（６）において、Ｒ２２は、同一又は異なっている炭素数１〜４の炭化水素基を表し、ｑは１〜４の整数を表す。一般式（７）は１、２−ブタジエンの繰り返し単位を有する化合物を表し、ｒは重合度であり、１以上の整数を表し、前記化合物は分子量分布を持っていてもよい。ＧＰＣ測定におけるスチレン換算数平均分子量が１０００００〜２０００００である。）
（９）本発明のプリプレグは、上記（１）又は（２）に記載の樹脂組成物をクロス又は不織布に含浸している。

(General formula (5) represents a polyfunctional styrene compound having a plurality of styrene groups, p represents an integer of 2 or more, R21 represents a hydrocarbon skeleton, and the polystyrene-equivalent weight average molecular weight in GPC measurement is 1000 or less. In general formula (6), R22 represents the same or different hydrocarbon group having 1 to 4 carbon atoms, q represents an integer of 1 to 4. General formula (7) is 1,2-butadiene. Wherein r is the degree of polymerization and represents an integer of 1 or more, the compound may have a molecular weight distribution, and the number average molecular weight in terms of styrene in GPC measurement is 100,000 to 200,000. )
(9) The prepreg of the present invention is obtained by impregnating a cloth or a nonwoven fabric with the resin composition described in the above (1) or (2).

  (10) In addition to the characteristics described in (9) above, the cloth or the nonwoven fabric contains quartz fibers.

  (11) In addition to the features described in (9) or (10) above, the cloth or the nonwoven fabric contains polyolefin fibers.

  (12) The laminated board of this invention has a conductor layer in the single side | surface or both surfaces of the hardened | cured material of the prepreg as described in said (9).

  (13) The printed circuit board of the present invention has conductor wiring on one side or both sides of the cured product of the prepreg described in (9).

  (14) The multilayer printed circuit board of the present invention is manufactured by laminating and bonding a plurality of printed circuit boards described in (13) above through the prepreg described in (9), and then forming an interlayer wiring. .

  In printed boards, particularly multilayer printed boards, low thermal expansion in the Z direction is an important issue from the viewpoint of improving the reliability of interphase connection using through holes and blind via holes.

  In general, as a technique for reducing the thermal expansion of a resin, a technique for highly filling a filler is known.

  However, since the insulating layer highly filled with the filler is hard and brittle, the adhesion between the conductor layer and the insulating layer is lowered. In printed circuit boards and multilayer printed circuit boards, improvement in the adhesion between the conductor layer and the insulating layer is an important issue, and 0.7 kN / m or more is preferable in this industry.

  As a technique for improving the adhesion between the conductor layer and the insulating layer, a technique for applying a conductor layer having a large surface roughness and a technique for adding an elastomer component in a resin system are known.

  However, an increase in surface roughness is not preferable because it causes an increase in conductor loss. Usually, the surface roughness of a conductor (10-point average surface roughness Rz, hereinafter referred to as surface roughness) is about 7 μm, but in a high-frequency signal printed circuit board, the surface roughness of the conductor layer is preferably 3 μm or less. ing. On the other hand, an increase in the amount of the elastomer component has an effect on improving the adhesiveness, but increases the thermal expansion coefficient. In addition, an increase in the amount of the rubber component has a problem that it causes deterioration of moisture absorption heat resistance and solvent resistance. Conventionally, it has been difficult to achieve both low thermal expansion and high adhesion.

  We proceeded with research focusing on the physical properties and amount of the elastomer component added to the low thermal expansion resin composition highly filled with the filler, and the low thermal expansion property of the resin system was maintained in the region where the amount of the elastomer component was small. It has been found that even when the amount of the elastomer component added is small, when an elastomer component having a breaking elongation of 700% or more is added, specifically high adhesiveness is expressed. This is considered to be because the rubber component in the system effectively disperses the stress generated at the interface between the insulating layer and the conductor layer, which occurs when the conductor layer is peeled off, and the stress concentration on the peeled portion is alleviated. It is done.

  The basic composition of the resin composition that achieves both low thermal expansion and high adhesion is 70 to 90 parts by weight of the crosslinking component (A) and 10 to 30 of the high molecular weight component (B) having a breaking elongation of 700% or more. The ratio of 150 parts by weight and 150 parts by weight of the inorganic filler (C) is preferred. In the above ratio, the inorganic filler (C) is more preferably 251 to 400 parts by weight. By adopting this composition ratio, both low thermal expansion and high adhesiveness can be achieved.

  The combination of the crosslinking component and the high molecular weight component can be freely selected. It is preferable from the viewpoint of workability such as weissing or prepreg that both are soluble in the same single solvent or a mixed solvent having the same composition. Specifically, the cross-linking component is an epoxy resin having a plurality of epoxy groups, a phenol resin having a phenolic hydroxyl group, a cyanate resin having a plurality of cyanate groups, an acrylate resin having a plurality of acrylate groups or a methacrylate group, and an epoxy acrylate resin. In some cases, combinations of acrylonitrile butadiene rubber, epoxidized acrylonitrile butadiene rubber, natural rubber, polyamide elastomer, styrene-butadiene copolymer or styrene-butadiene-styrene copolymer having a styrene content of 50 wt% or more as a high molecular weight compound Is mentioned.

  The blending ratio of the crosslinking component (A) and the high molecular weight component (B) is preferably 50 to 90 parts by weight, more preferably 70 to 90 parts by weight, with the total amount of the resin components being 100 parts by weight. Part. When the addition amount of the crosslinking component is small, the thermal expansion coefficient may be increased, and the solvent resistance and heat resistance may be decreased.

  The compounding ratio of the inorganic filler can be arbitrarily adjusted according to the shape of the filler and a desired thermal expansion coefficient, but the thermal expansion coefficient of the cured product of the resin composition is 50 ppm / ° C. or less, more preferably 30 ppm / ° C. It is preferable to adjust so that it may become the following. By setting it as such a structure, it becomes possible to make low thermal expansion of a laminated board, a printed circuit board, and a multilayer printed circuit board irrespective of the kind of cloth or a nonwoven fabric.

Although the specific blending ratio of the inorganic filler is influenced by the thermal expansion coefficient of the resin itself, it is generally preferable to add 150 parts by weight or more with respect to 100 parts by weight of the resin component. More preferably, 251 parts by weight or more is added. More preferably, 300 parts by weight or more is added. The limit of the addition amount of the spherical silicon oxide filler is approximately 75 vol%. When the specific gravity of the resin component is 1 g / cm ³ and the specific gravity of the silicon oxide is 2.65 g / cm ³ , the resin component is 100 parts by weight. The amount is 796 parts by weight. In addition, when the moldability is taken into consideration, the addition amount of the silicon oxide filler is preferably about 400 parts by weight or less.

  When the low thermal expansion resin composition of the present invention is applied to an insulating material for a high frequency device, it is preferable to apply a thermosetting polyphenylene ether resin as a crosslinking component (A), and a particularly preferable example is varnishing. Examples thereof include thermosetting polyphenylene ethers represented by the general formulas (1) and (2), which have a high solubility in a solvent and excellent dielectric properties, and have a number average molecular weight in terms of styrene of 1000 to 15000.

  When a thermosetting polyphenylene ether is used as the crosslinking component (A), it is preferable to use a styrene elastomer excellent in compatibility with the polyphenylene ether as the high molecular weight component (B). It is preferable to use a styrene elastomer from the viewpoint of dielectric properties. As a preferable example of the hydrogenated styrene-based elastomer, among the hydrogenated styrene-butadiene copolymers having a styrene content of 10 to 40 wt% and a styrene-equivalent number average molecular weight of 50,000 to 100,000, the elongation at break A high molecular weight substance having a rate of 700% or more can be exemplified.

  Specific examples of such high molecular weight components include those manufactured by Asahi Kasei Chemicals Corporation, Tuftec (registered trademark) H1052, H1221, and H1272.

  As the inorganic filler, it is preferable to use a silicon oxide filler in order to improve the dielectric properties of the cured product of the resin composition, and it is preferable to use a spherical filler in order to make the filler highly filled. The particle size of the spherical silicon oxide filler is not particularly limited. However, when the low thermal expansion resin composition is varnished, no significant precipitation occurs in the varnish and the surface area is large. A small-diameter filler having a large contribution is preferably used. The particle diameter of the specific spherical silicon oxide filler is preferably 10 μm or less, and more preferably in the range of 0.2 to 3 μm. The spherical silicon oxide filler is preferably used after its surface is treated with a silane coupling agent from the viewpoint of improving dielectric properties, low moisture absorption, and solder heat resistance.

  The surface treatment of the spherical silicon oxide filler with a coupling agent may be performed by adding a filler that has been surface-treated in advance to the resin composition, or by adding a silane coupling agent to the resin composition and adjusting the resin composition You may carry it in. Examples of the silane coupling agent preferably used in the present invention include γ-methacryloxypropyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Examples thereof include vinyl tris (β-methoxyethoxy) silane and p-styryltrimethoxysilane.

  In printed circuit boards and multilayer printed circuit boards, flame retardancy is often required from the viewpoint of safety. In resin materials, flame retarding technology by adding a flame retardant is usually used.

  In the present invention, it is preferable to use a flame retardant that is solid at least at room temperature in order to achieve both low thermal expansion and adhesion of the insulating layer, and in order to maintain low dielectric loss, the general formula (3) and Application of a flame retardant having the structure (4) is preferred. The flame retardants represented by the general formulas (3) and (4) have a low dielectric loss tangent, and are suitable for flame retardant of electrical parts that handle high-frequency signals. Furthermore, although there is no restriction | limiting in particular in the average particle diameter of a flame retardant, precipitation of a flame retardant in a varnish can be suppressed by making an average particle diameter 0.2-3.0 micrometers, and the storage stability of a varnish. Can be improved. Although depending on the varnish viscosity, the occurrence of precipitation can be suppressed by using a flame retardant having a particle size in the range of 0.1 to 1.0 Pa · s (Pascal second) and a silicon oxide filler.

  The addition amount of the flame retardant is preferably 10 to 200 parts by weight, with the total amount of the resin component being 100 parts by weight, and is added in accordance with the desired flame retardant level, the cloth used, and the type of nonwoven fabric. It is desirable to determine. When the cloth or nonwoven fabric contains olefin fibers, it is desirable to add 100 parts by weight or more.

  In the present invention, a crosslinking aid represented by the general formulas (5), (6), and (7) can be added for the purpose of adjusting dielectric properties, varnish viscosity, and film formability. Since the polyfunctional styrene compound having an all-hydrocarbon skeleton represented by the general formula (5) does not contain a hetero atom in its structure, it has a function of further reducing the dielectric loss tangent of the cured product of the resin composition.

  Since the polyfunctional styrene compound of the general formula (5) has high reactivity, the resin system can be cured without adding a curing catalyst. Since the curing catalyst has a hetero atom in the structure, an effect of reducing the dielectric loss tangent by removing the curing catalyst is also expected.

  Although the details of the bismaleimide compound having a specific structure represented by the general formula (6) are unknown, it has an effect of reducing the varnish viscosity when added to the varnish, and its dielectric loss tangent is small as the maleimide compound.

  The 1,2-polybutadiene compound represented by the general formula (7) has an effect of increasing the varnish viscosity because it is a high molecular weight substance, and improves the film forming property of the prepreg and improves the flexibility of the prepreg. Contribute. Moreover, since it is a whole hydrocarbon skeleton and does not have an aromatic ring, it contributes to the reduction of dielectric constant.

  The blending ratio of each crosslinking aid may be 70 to 90 parts by weight of the thermosetting polyphenylene ether resin and 30 to 10 parts by weight of the crosslinking aid so as not to impair the low thermal expansibility, adhesiveness, and dielectric properties. preferable.

  Examples of the polyfunctional styrene compound represented by the general formula (5) include 1,2-bis (p-vinylphenyl) ethane, 1,2-bis (m-vinylphenyl) ethane, and 1- (p-vinyl). Phenyl) -2- (m-vinylphenyl) ethane, bis (p-vinylphenyl) methane, bis (m-vinylphenyl) methane, p-vinylphenyl-m-vinylphenylmethane, 1,4-bis (p- Vinylphenyl) benzene, 1,4-bis (m-vinylphenyl) benzene, 1- (p-vinylphenyl) -4- (m-vinylphenyl) benzene, 1,3-bis (p-vinylphenyl) benzene, 1,3-bis (m-vinylphenyl) benzene, 1- (p-vinylphenyl) -3- (m-vinylphenyl) benzene, 1,6-bis (p-vinylphenyl) hexane, Examples include 6-bis (m-vinylphenyl) hexane, 1- (p-vinylphenyl) -6- (m-vinylphenyl) hexane, and a divinylbenzene polymer (oligomer) having a vinyl group in the side chain. These can be used alone or as a mixture of two or more.

  Examples of the bismaleimide compound represented by the general formula (6) include bis (3-methyl-4-maleimidophenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, and bis (3-ethyl). -4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3-n-butyl-4-maleimidophenyl) methane, and the like.

  Examples of the 1,2-polybutadiene compound represented by the general formula (7) include RB810, RB820, and RB830 manufactured by JSR Corporation.

  In the present invention, a polymerization initiator may be added for the purpose of promoting the thermosetting reaction and lowering the temperature. The polymerization initiator is appropriately selected depending on the type of functional group of the crosslinking component. When the thermosetting polyphenylene ether represented by the general formula (1) or (2) is used as a crosslinking component, it is preferable to apply a radical polymerization initiator. The starting temperature of the curing reaction can be adjusted according to the type of radical polymerization initiator.

  Examples of radical polymerization initiators include isobutyl peroxide, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, 1, 1 3,3-tetramethylbutylperoxyneodecanoate, diisopropylperoxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2-ethoxyethylperoxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydidecanate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, t-butylperoxyneodecano Ate, t-hexylperoxypi Valate, t-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2, 5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, m-toluoyl peroxide, t-butylperoxyisobutyrate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumylper Xoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, t-butyltrimethylsilyl peroxide can be mentioned, and these initiators are complex Can be used. The addition amount is adjusted in the range of 0.0005 to 20 parts by weight, with the total amount of resin components being 100 parts by weight.

  Furthermore, a polymerization inhibitor may be added for the purpose of suppressing the curing reaction due to heating during the preparation of varnish and prepreg and suppressing the progress of the curing reaction during prepreg storage. The polymerization inhibitor is appropriately selected depending on the type of functional group of the crosslinking component. When the thermosetting polyphenylene ether represented by the general formula (1) or (2) is used as a crosslinking component, it is preferable to apply a radical polymerization inhibitor. Examples thereof include quinones such as hydroquinone, p-benzoquinone, chloranil, trimethylquinone, 4-t-butylpyrocatechol, and aromatic diols, and the preferred range of addition amount is 0.0005 to 5 parts by weight. is there.

  The varnishing solvent of the resin composition used in the present invention preferably has a boiling point of 140 ° C. or lower. As such a solvent, xylene can be exemplified as an example, and more preferably the boiling point is 110 ° C. or lower. Preferably, toluene, cyclohexane and the like are exemplified as such a solvent. These solvents may be used as a mixture, and may further contain a polar solvent such as methyl ethyl ketone and methanol used for the coupling treatment of the inorganic filler. The varnish concentration is preferably 40 to 65 wt%, and the varnish viscosity is 0.1 to 1.0 Pa · s (Pascal second) depending on the type and amount of the crosslinking component (A) and the high molecular weight body (B) constituting the resin composition. ) As appropriate.

  The prepreg can be produced by impregnating a varnish of the resin composition into a cloth or a nonwoven fabric and drying it. As for the drying conditions, the drying temperature is preferably 80 to 150 ° C. Further, the drying temperature is preferably 80 to 110 ° C. in order to sufficiently dry while suppressing unnecessary curing reaction during drying. . The drying time is preferably in the range of 10 to 90 minutes.

  There are no particular restrictions on the material of the cloth and non-woven fabric, but when applied to insulating materials for high-frequency equipment, a composite cloth in which quartz fibers and olefin fibers are combined, and a thin quartz cloth with a thin and dense structure are applied. It is preferable to do. The composite cloth is preferably produced using a yarn containing both olefin fiber and glass fiber and using this mixed yarn. Olefin fiber and glass fiber have different elongation at break, so when weaving alternately using olefin fiber yarn and glass fiber yarn, the cross will be wrinkled or twisted due to the difference in the degree of stretch of both fibers. This is because (twisting) may occur.

  The diameters of the glass fiber and olefin fiber are preferably in the range of 5 to 20 μm. If the fiber diameter is too large, the folds of the base material are rough and the unevenness of the surface becomes large, so that the appearance of the prepreg and the laminate is impaired, which is not preferable. Further, if the fiber system is too small, it is not preferable because the fiber is easily cut during weaving. The mixing ratio of the quartz fiber and the polyolefin fiber is preferably 40/60 weight ratio to 60/40 weight ratio in order to maintain the low thermal expansion of the laminated board, the printed board and the multilayer printed board.

A preferable configuration of the thin quartz glass cloth is a quartz glass cloth produced using quartz glass yarns containing 15 to 49 fused silica glass fibers having a filament diameter of 5 to 9 μm, and the weave density of warp and weft yarns Is a sparse quartz glass cloth having a weight per unit area of 10 to 18 g / m ² and a thickness of 15 to 30 μm.

  By adopting this configuration, the quartz fiber content per layer of the prepreg can be reduced, so that drilling workability can be improved. A prepreg to which a thin quartz cloth is applied can have a film thickness of 10 to 50 μm per layer, which can contribute to a reduction in thickness of an electronic device.

  The resin content of the prepreg of the present invention is 50 to 90 wt%. If it is lower than 50 wt%, sufficient moldability may not be ensured, and if it exceeds 90 wt%, the fluidity of the resin becomes too high during molding and the cloth may break. A more preferable range of the resin content is 60 to 80 wt%.

  A laminated board is manufactured by installing a conductor layer on both sides or one side of the cured prepreg produced as described above. For the installation of the conductor layer, it is preferable from the viewpoint of workability that the conductor foil is overlapped on the prepreg, heated and pressed by hot press, and simultaneously adhered to the conductor foil and cured of the prepreg. In addition, since the resin composition of this invention has low thermal expansibility, you may use the conductor foil with resin produced by apply | coating and drying the resin composition varnish on conductor foil instead of a prepreg. Since the conductor foil with resin does not include cloth or nonwoven fabric in the structure, drilling workability is further improved and laser drilling is easy.

  Using the prepreg or laminate of the present invention, a printed circuit board or a multilayer printed circuit board can be produced through the usual wiring processing, multilayering and interphase connection processes.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

  First, reagents and evaluation methods are shown.

(1) Synthesis of 1,2-bis (vinylphenyl) ethane (BVPE) In a 500 ml three-necked flask, 5.36 g (220 mmol) of granular magnesium for Grignard reaction (manufactured by Kanto Chemical) was taken, a dropping funnel, a nitrogen inlet tube and a septum. A cap was attached. The whole system was heated and dehydrated with a drier while stirring the magnesium particles with a stirrer under a nitrogen stream. 300 ml of dry tetrahydrofuran was taken into a syringe and injected through a septum cap. After cooling the solution to −5 ° C., 30.5 g (200 mmol) of vinylbenzyl chloride (manufactured by Tokyo Chemical Industry) was dropped over about 4 hours using a dropping funnel. After completion of the dropwise addition, stirring was continued at 0 ° C. for 20 hours.

  After completion of the reaction, the reaction solution was filtered to remove residual magnesium and concentrated with an evaporator. The concentrated solution was diluted with hexane, washed once with a 3.6% aqueous hydrochloric acid solution and three times with pure water, and then dehydrated with magnesium sulfate. The dewatered solution was purified by passing through a short column of silica gel (Wako Gel C300 manufactured by Wako Pure Chemical Industries, Ltd.) / Hexane, and finally the desired BVPE was obtained by vacuum drying. The obtained BVPE is 1,2-bis (p-vinylphenyl) ethane (PP body, solid), 1,2-bis (m-vinylphenyl) ethane (mm body, liquid), 1- (p-vinyl). The yield was 90% with a mixture of phenyl) -2- (m-vinylphenyl) ethane (mp form, liquid).

^{When the} structure was examined by ¹ H-NMR, it was consistent with literature values (6H-vinyl: α-2H (6.7), β-4H (5.7, 5.2); 8H-aromatic (7.1 7.4); 4H-methylene (2.9)). The obtained BVPE was used as a crosslinking component.

(2) Synthesis of thermosetting polyphenylene ether (compound of general formula (1)) To a two-necked flask containing a stirrer, di-μ-hydroxobis [(N, N, N ′, N′-tetramethylethylenediamine ) Copper (II)] dichloride: 0.464 g (1.0 mmol), water: 4 ml, tetramethylethylenediamine: 1 ml were added and stirred. After the stirring was stopped, a flask was prepared by dissolving 2,6-dimethylphenol: 9.90 g (81.0 mmol) and 2-allyl-6-methylphenol: 1.34 g (9.0 mmol) in toluene: 50 ml (milliliter). And stirred at 500-800 rpm in an oxygen atmosphere of 40 ml / min (milliliter per minute) or 50 ml / min. The mixture was stirred for 6 hours under an oxygen atmosphere.

  After completion of the reaction, the reaction mixture was precipitated in a large excess of hydrochloric acid / methanol, washed with methanol, dissolved in toluene, and insoluble matter was filtered off. After dissolving again in toluene, it was reprecipitated in a large excess of hydrochloric acid / methanol, washed with methanol, and then vacuum dried at 120 ° C./2 hours, 150 ° C./30 minutes to obtain a white solid. The molecular weight and molecular weight distribution of the solid were Mn = 15000 and Mw / Mn = 1.7.

(3) Other reagents Thermosetting polyphenylene ether (compound of general formula (2)), OPE2St, styrene equivalent number average molecular weight 2200, manufactured by Mitsubishi Gas Chemical Co., Ltd. Bismaleimide: BMI-5100, 3, 3′-dimethyl -5,5'-diethyl-4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd. High molecular weight polybutadiene: RB810, styrene-equivalent number average molecular weight 130,000, 1,2-bond 90% or more, JSR Corporation Manufactured hydrogenated styrene-butadiene copolymer:
Tuftec ™ H1043, styrene content 67 wt%, Mn 76000, elongation at break 20%, Asahi Kasei Chemicals Co., Ltd. Tuftec ™ H1051, styrene content 42 wt%, Mn 75000, elongation at break 600, Asahi Kasei Chemicals Tuftec ™ H1031, styrene content 30 wt%, Mn 53000, elongation at break 650%, Asahi Kasei Chemicals Corp. Tuftec ™ H1052, styrene content 20 wt%, Mn72000, elongation at break 700%, Asahi Kasei Chemicals ( Tuftec ™ H1221, styrene content 12% by weight, Mn 71000, elongation at break 980%, Asahi Kasei Chemicals Corporation Tuftec ™ H1272, styrene content 35% by weight, Mn 74000, elongation 950%, Asahi Kasei Ke Cured Co., Ltd. Curing catalyst: 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 (abbreviation 25B), manufactured by NOF Corporation Flame retardant: SAYTEX 8010, 1,2-bis (Pentabromophenyl) ethane, average particle size 1.5 μm, Albemarle Japan Co., Ltd. silicon oxide filler: Admafine, average particle size 0.5 μm, Co., Ltd. Admatechs Coupling agent: KBM-503 , Γ-methacryloxypropyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Copper foil: AMFN1 / 2Oz, copper foil with coupling treatment, thickness 18 μm, Rz≈2.1 μm, composite cloth manufactured by Nikko Materials Co., Ltd .: Quartz fiber Φ7μm = 60wt%, Polypropylene fiber Φ20μm = 40wt%: Shin-Etsu quartz Co., Ltd. Thin quartz cloth: Quartz fiber Φ7μm, 40 fibers in the yarn, warp 60 / 25mm, 43 wefts / 25mm, manufactured by Shin-Etsu Quartz Co., Ltd. (3) Surface treatment of glass cloth Immerse the glass cloth in 0.5 wt% KBM503 methanol solution for 1 hour, then remove the glass cloth from the methanol solution And dried by heating at 100 ° C. for 30 minutes.

(4) Preparation method of varnish A predetermined amount of coupling agent and filler were stirred in a methyl ethyl ketone solution for 2 hours by a ball mill, and the filler was subjected to a coupling treatment. Then, a predetermined amount of resin material, flame retardant, curing catalyst, and toluene were added, and stirring was continued for about 8 hours until the resin component was completely dissolved to prepare a varnish. The varnish concentration was 45 to 65 wt%.

(5) Preparation method of cured product (resin plate) After applying resin varnish to PET film and drying at room temperature overnight and at 100 ° C. for 10 minutes, this was peeled off and inside a PTFE thickness 1.0 mm spacer Then, it was pressurized and heated by a vacuum press to obtain a cured product. The curing condition was that the pressure was increased from room temperature to 2 MPa under vacuum, the temperature was increased at a constant rate (6 ° C./min), and the temperature was maintained at 180 ° C. for 60 minutes.

(6) Preparation method of prepreg After the cloth was dipped in the varnish, the gap between the slits having a predetermined gap was vertically pulled up at a constant speed and then dried. The amount of resin applied was adjusted by the slit gap. The drying conditions were 100 ° C./10 minutes.

(7) Method for producing copper-clad laminate Four prepregs produced as described above were laminated, the upper and lower surfaces were sandwiched with copper foil, and were cured by pressing and heating with a vacuum press. The curing conditions were a pressure from room temperature to 6 MPa, a temperature increase at a constant rate (6 ° C./min), and a hold at 180 ° C. for 60 minutes.

(8) Measurement of relative dielectric constant and dielectric loss tangent A value of 10 GHz was measured by a cavity resonance method (8722ES type network analyzer, manufactured by Agilent Technologies: Cavity Resonator, manufactured by Kanto Electronics Application Development). A sample prepared from a copper clad laminate was prepared by cutting out copper to a size of 1.0 × 80 mm. A sample prepared from a resin plate was cut out from the resin plate to a size of 1.0 × 1.5 × 80 mm.

(9) Evaluation of thermal expansion coefficient As for the thermal expansion coefficient, a value in the thickness direction (Z direction) of the laminate was observed under a nitrogen atmosphere using a TM9300 type thermomechanical tester manufactured by ULVAC-RIKO. As a sample, a laminate was cut into a size of 5 × 5 mm and annealed at 175 ° C. to obtain a sample. The rate of temperature increase was 10 ° C./min, and the thermal expansion coefficient between 50 and 100 ° C. was determined.

(10) Solvent resistance The copper foil was removed from the cured laminate by etching, cut into a size of 20 × 20 mm, and then dried at 110 ° C. for 2 hours to obtain a sample. After observing the initial weight of the sample, it was immersed in toluene at room temperature for 20 hours. Then, the sample was taken out from toluene, dried at 110 ° C. for 2 hours, and the weight of the sample after treatment was observed. The elution rate was determined by calculation of (initial weight−weight after treatment) / initial weight × 100, and a sample having an elution rate of 0.1 wt% or more was regarded as defective.

(11) Measurement of elongation at break The measurement of elongation at break was performed in accordance with Japanese Industrial Standard (JIS K6251).

  The sample used was a No. 3 dumbbell, the tensile speed was 500 mm / min, and the change in elongation until the sample broke was measured.

(12) Measurement of peel strength Peel strength was measured in accordance with Japanese Industrial Standard (JIS C6481).

Tables 1 and 2 show the configurations and characteristics of Examples and Comparative Examples.
(Examples 1-3)
Examples 1 to 3 are examples of resin compositions in which 20 parts by weight of an elastomer having a breaking elongation of 700% or more is added as a high molecular weight component. Since the addition amount of the filler is high and the content of the high molecular weight component in the resin component is low, the thermal expansion coefficient in the thickness direction of the laminate is 30 ppm / despite the use of the composite cloth containing the olefin fiber. A low thermal expansibility of the ℃ level was confirmed. In addition, as an effect of blending an elastomer having an elongation at break of 700% or more, a high peel strength of 0.7 kN / m or more was confirmed in spite of using a copper foil having a small surface roughness Rz of 2.1 μm. It was.
(Examples 4 to 6)
Examples 4-6 are the examples which changed the component of the crosslinking adjuvant. In the system in which the polyfunctional styrene compound BVPE is added as a crosslinking aid, the dielectric loss tangent is particularly reduced among the dielectric properties of the laminate. It is confirmed that the system in which a bismaleimide compound having a specific structure is added as a crosslinking aid has a lower varnish viscosity than other systems. In the system in which polybutadiene is added as a crosslinking aid, it is confirmed that the varnish viscosity has increased.

From the above, it was confirmed that the addition of a crosslinking aid can improve the dielectric properties and adjust the varnish viscosity.
(Example 7)
Example 7 is an example using a thin quartz cloth. It was confirmed that the thermal expansion can be further reduced by using a thin quartz cloth that does not contain olefin fibers. It was also confirmed that the prepreg per layer can be made thin, and the amount of chemical substances used per unit area can be reduced.
(Comparative Examples 1-3)
Comparative Examples 1 to 3 are examples of resin compositions in which 20 parts by weight of an elastomer having a breaking elongation of 650% or less is added as a high molecular weight component. Since an elastomer having a low elongation at break was blended, the peel strength was as low as 0.5 kN / m or less.
(Comparative Example 4)
Comparative Example 4 is an example of a resin composition having an increased amount of high molecular weight components. By increasing the amount of the high molecular weight component, the peel strength was as high as 0.7 kN / m, but the coefficient of thermal expansion was increased and the solvent resistance was decreased. An increase in the high molecular weight component is not preferable from the viewpoint of low thermal expansion and improved solvent resistance.

（実施例８）
実施例８では、実施例７のプリプレグを用いて作製したアンテナ回路内蔵高周波基板を作製した。工程を図２に示した。

(Example 8)
In Example 8, the antenna circuit built-in high frequency board produced using the prepreg of Example 7 was produced. The process is shown in FIG.

  (A) The prepreg of Example 7 was cut into 10 × 10 cm and laminated 10 sheets to obtain a laminated prepreg 2, which was sandwiched between two copper foils 1. While pressing at a pressure of 5 MPa by a vacuum press, the temperature was increased under vacuum at a temperature increase rate of 6 ° C./min, and maintained at 230 ° C. for 1 hour to produce a double-sided copper-clad laminate 101. Next, the double-sided copper-clad laminate 101 was immersed in an etching solution at 30 ° C. (ammonium persulfate peroxide 200 g / liter, sulfuric acid 50 g / liter) for 10 minutes to reduce the thickness of the copper layer to 8 μm.

  (B) Photoresist antenna pattern 3 was formed by laminating a photoresist (HS425 manufactured by Hitachi Chemical Co., Ltd.) on one side of double-sided copper-clad laminate 101, and a mask was applied to the through-hole portion for connecting the antenna circuit and exposed. Next, a photoresist (Hitachi Chemical HS425) is laminated on the surface of the remaining copper foil 1 to form a photoresist through-hole pattern 4, the antenna test pattern is exposed, and the unexposed portion of the photoresist on both sides is 1% carbonic acid. Developed with sodium solution.

  (C) The copper foil exposed with an etching solution of 5% sulfuric acid and 5% hydrogen peroxide was removed by etching to produce an antenna pattern 5 and a through-hole pattern 6 on the double-sided copper-clad laminate 101. Residual photoresist was removed with 3% sodium hydroxide solution.

  (D) A copper foil 103 was laminated on one side of the through-hole pattern 6 via one prepreg 102, and multilayered by pressing under the same conditions as in (A) above.

  (E) The wiring pattern 7 (wiring circuit) and the through hole pattern 106 were processed on the newly installed conductor layer (copper foil 103) by the same method as in the above (B) and (C).

  (F) Through-holes 8 were formed by a carbon dioxide laser using the outer-layer through-hole pattern 106 as a mask.

(G) A silver paste 9 is introduced into the through hole 8 to connect the antenna pattern 5 (antenna circuit) and the wiring on the back surface (wiring pattern 7), and an antenna-embedded printed wiring board having a shield layer directly under the antenna circuit. Produced.
(Examples 9 to 10)
Examples 9 and 10 are examples in which the amount of filler component added was changed. As shown in Table 3, it was confirmed that increasing the filler component promoted the low thermal expansion of the laminate, and the high peel strength was maintained by the effect of the elastomer component having a high elongation at break.

  The resin composition, prepreg, laminate and printed board of the present invention are thin, lightweight, excellent in workability, low dielectric loss tangent, and low dielectric loss. Therefore, high frequency compatible electronic devices such as high speed servers, routers, millimeter wave radars, etc. It is suitable for the insulating member.

It is a graph which shows the relationship between the elongation at break of a high molecular weight component, and peel strength. It is a schematic cross section showing the manufacturing process of the antenna built-in substrate.

Explanation of symbols

  1: Copper foil, 2: Laminated prepreg, 3: Photoresist antenna pattern, 4: Photoresist through hole pattern, 5: Antenna pattern, 6: Through hole pattern, 7: Wiring pattern, 8: Through hole, 9: Silver paste 101: Double-sided copper-clad laminate.

Claims (14)

  A resin composition containing 70 to 90 parts by weight of a crosslinking component, 10 to 30 parts by weight of a high molecular weight component, and 150 to 400 parts by weight of an inorganic filler, and the elongation at break of the high molecular weight component is 700% or more. A resin composition characterized by being.   The resin composition according to claim 1, comprising 251 to 400 parts by weight of the inorganic filler.   The cross-linking component is a curable polyphenylene ether compound, the high-molecular-weight component is a hydrogenated styrene elastomer, and the inorganic filler is a spherical silicon oxide filler. Resin composition. The curable polyphenylene ether is a compound represented by the following general formula (1) or the following general formula (2) and having a styrene-equivalent number average molecular weight of 1000 to 15000 in GPC measurement. Resin composition.

(General formula (1) represents a random copolymer of a phenol derivative, and l and m are polymerization degrees represented by an integer of 1 or more. R1 to R7 are hydrogen atoms or hydrocarbons having 1 to 9 carbon atoms. Represents a group, and at least one of R3 to R6 is a hydrocarbon group containing an unsaturated hydrocarbon group having 2 to 9 carbon atoms, and the general formula (2) represents a polymer of a phenol derivative, n and o are polymerization degrees represented by an integer of 1 or more, R8 is an organic group having 1 or more carbon atoms, R9 to R16 are hydrogen atoms or hydrocarbon groups having 1 to 9 carbon atoms, R17 to R18. Represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms.)   The styrene elastomer has a total hydrocarbon skeleton, has a styrene-equivalent number average molecular weight of 50,000 to 100,000 in GPC measurement, and a styrene content of 10 to 40% by weight. Resin composition.   The average particle size of the spherical silicon oxide filler is 0.2 to 3 μm, and at least one selected from vinyl-based, methacrylate-based, acrylate-based, and styrene-based silane coupling agents is supported on the surface thereof. The resin composition according to claim 3. Furthermore, the flame retardant represented by General formula (3) or (4) is contained, The resin composition of Claim 3 characterized by the above-mentioned.

Furthermore, a polyfunctional styrene compound represented by the following general formula (5), a bismaleimide compound represented by the following general formula (6), and a 1,2-polybutadiene compound having a repeating unit represented by the following general formula (7) The resin composition according to claim 3, comprising at least one crosslinking aid selected from the group consisting of:

(General formula (5) represents a polyfunctional styrene compound having a plurality of styrene groups, p represents an integer of 2 or more, R21 represents a hydrocarbon skeleton, and the polystyrene-equivalent weight average molecular weight in GPC measurement is 1000 or less. In the general formula (6), R22 represents a hydrocarbon group having 1 to 4 carbon atoms, q represents an integer of 1 to 4. The general formula (7) has a repeating unit of 1,2-butadiene. Represents a compound, r is the degree of polymerization, and represents an integer greater than or equal to 1. The number average molecular weight in terms of styrene in GPC measurement is 100,000 to 200,000.)   A prepreg comprising a cloth or a nonwoven fabric impregnated with the resin composition according to claim 1.   The prepreg according to claim 9, wherein the cloth or the nonwoven fabric contains quartz fibers.   The prepreg according to claim 9 or 10, wherein the cloth or the nonwoven fabric contains a polyolefin fiber.   A laminate having a conductor layer on one side or both sides of a cured product of the prepreg according to claim 9.   A printed circuit board comprising conductor wiring on one side or both sides of a cured product of the prepreg according to claim 9.   A multilayer printed circuit board comprising a plurality of printed circuit boards according to claim 13 which are laminated and bonded through the prepreg according to claim 9 to form an interlayer wiring.

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