JP2007056170A - Polyphenylene ether resin composition, prepreg, and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which is used to obtain a printed circuit board improved in reliability, especially in insulation reliability, required in a printed circuit board of a low dielectric constant. <P>SOLUTION: The laminate comprises a polyphenylene ether resin composition containing a polyphenylene ether resin and silica balloons with an average particle diameter of 5 μm or less. The content of the silica balloons contained in the polyphenylene ether resin composition is 5-50 mass%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyphenylene ether resin composition, a prepreg, and a laminate using them for obtaining a laminate having a low dielectric constant and excellent insulation reliability.

  With recent miniaturization and performance enhancement of various electronic devices, printed wiring boards used in the electronic devices are required to have multiple layers and high-speed and large-capacity transmission. It has been demanded.

  On the other hand, the electronic device has recently been used in any environment, and even when used in a harsh environment, it is required to maintain the performance of the electronic device, and the print used in such an electronic device is required. Wiring boards are strongly required to have reliability, particularly insulation reliability.

As an insulating plate used for a printed wiring board having excellent dielectric properties in the high frequency region, Patent Document 1 listed below is obtained by thermal curing of a sheet-like substrate impregnated with a thermosetting resin containing hollow glass particles. An insulating plate suitable for manufacturing a printed wiring board having high heat resistance, high strength, and low dielectric constant, wherein the hollow glass particles have a surface hydroxyl group density of 0.5 particles / nm ² or more. Is disclosed.

However, in the printed wiring board using the insulating board as described above, a printed wiring board having high heat resistance, high strength, and low dielectric constant can be obtained, but the insulation reliability is not sufficient.
JP-A-8-46309

  The inventors of the present invention provide a polyphenylene ether resin composition, a prepreg, and a polyphenylene ether resin composition used for obtaining a low dielectric constant printed wiring board having improved reliability, particularly insulation reliability, which is required for a low dielectric constant printed wiring board. It aims at providing the laminated body using them.

  In order to solve the above problems, the inventors of the present invention provide a polyphenylene ether resin composition that is an insulating material of a laminate used in the manufacture of a printed circuit board having a low dielectric constant, wherein the resin composition has an average particle size of 5 μm. It has been found that a low dielectric constant printed wiring board having high reliability as well as a low dielectric constant can be produced by containing the following silica balloons at a specific ratio.

  That is, the polyphenylene ether resin composition according to claim 1 of the present invention is a polyphenylene ether resin composition containing a polyphenylene ether resin and a silica balloon having an average particle size of 5 μm or less, wherein the silica resin is contained in the polyphenylene ether resin composition. A polyphenylene ether resin composition comprising 5 to 50% by mass of a balloon. A prepreg is prepared by impregnating a prepreg-forming base material with such a polyphenylene ether resin composition, and a laminate obtained by laminating the prepreg with a metal foil is used as a printed circuit board having a low dielectric constant, reliability, In particular, it is used as a printed wiring board having excellent insulation reliability.

  The polyphenylene ether resin composition according to claim 2 is the polyphenylene ether resin composition according to claim 1, wherein the silica balloon has an average hollowness of 40 to 60% by volume. When the silica balloon has such an average hollowness, dielectric properties can be further enhanced.

  Moreover, the polyphenylene ether resin composition of Claim 3 is a polyphenylene ether resin composition of Claim 1 or Claim 2, wherein the silica balloon is treated with a coupling agent. By using such a silica balloon treated with a coupling agent, in addition to insulation reliability, solder heat resistance during moisture absorption can be improved. Moreover, when making a polyphenylene ether resin composition into a varnish at the time of immersing in a glass base material and producing a prepreg, the dispersibility of the silica balloon in a varnish is improved.

  The polyphenylene ether resin composition according to claim 4 is a polyphenylene ether resin composition according to any one of claims 1 to 3, wherein the polyphenylene ether resin composition contains spherical silica. By containing the spherical silica, the coefficient of thermal expansion can be reduced, and a printed wiring board excellent in dimensional stability can be obtained.

  The prepreg according to claim 5 is obtained by impregnating the prepreg-forming base material with the polyphenylene ether resin composition according to claims 1 to 4, and a laminate using such a prepreg. As a result, it is possible to obtain a laminate that can be used as a printed wiring board having a low dielectric constant and excellent insulation reliability.

  A laminate of claim 6 is formed by laminating the prepreg according to claim 5 and a metal foil and heating and compressing the laminate, and has a low dielectric constant and excellent insulation reliability. It is a laminate that can be used as a printed wiring board.

  By using the polyphenylene ether resin composition and the prepreg of the present invention, a laminate that can be used as a printed wiring board having a low dielectric constant and excellent insulation reliability can be obtained. The obtained laminate can be used as a printed wiring board having a low dielectric constant and excellent insulation reliability.

  The polyphenylene ether resin composition of the present invention is a polyphenylene ether resin composition containing a polyphenylene ether resin and a silica balloon having an average particle size of 5 μm or less, wherein the silica balloon is 5 to 50 mass in the polyphenylene ether resin composition. % Content.

  The polyphenylene ether resin used in the present invention is obtained by reducing the molecular weight of the high molecular weight polyphenylene ether resin represented by the structure of the following general formula (1) by a molecular weight reduction method described later.

(In the formula, n represents a repeating unit and is an integer of 200 to 400. R is H or a hydrocarbon group having 1 to 3 carbon atoms, and R may be the same group or different groups.)

  Examples of the high molecular weight polyphenylene ether resin represented by the general formula (1) include poly (2,6-dimethyl-1,4-phenylene oxide).

  The polyphenylene ether resin used in the present invention is suitable for molding, for example, the high molecular weight polyphenylene ether having a number average molecular weight (Mn) of about 13,000 to 25,000 synthesized by the method disclosed in US Pat. No. 4,059,568. In order to adjust the melt viscosity, the number average molecular weight can be obtained by reducing the molecular weight to about 2000 to 10,000.

  As a method for obtaining a polyphenylene ether resin having a reduced molecular weight, a known method for reducing the molecular weight, specifically, for example, the method of reducing the molecular weight by reacting a phenol species with a polyphenylene ether resin, “The Journal of Organic Chemistry. , 34,297-303 (1969) ", an improved known method thereof, and the like can be used.

  As the method, for example, the high molecular weight polyphenylene ether resin having a number average molecular weight of about 13,000 to 25,000 is a solvent together with a phenol species, a decomposition peroxide and, if necessary, a fatty acid metal salt such as cobalt naphthenate for promoting a decomposition reaction. The method of decomposing even the number average molecular weight to about 2000-10000 by making it react in is mentioned.

  Examples of the phenol species include phenol, cresol, xylenol, hydroquinone, bisphenol A, 2,6-dimethylphenol, 4,4′-dihydroxydiphenyl ether, and the like.

  Examples of the decomposed peroxide include di (t-butylperoxyisopropyl) benzene, benzoyl peroxide, 3,3 ′, 5,5′-tetramethyl-1,4-diphenoquinone chloranil, 2 4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobutyronitrile and the like.

  The polyphenylene ether resin used in the present invention is particularly a polyphenylene ether resin that is end-modified so as to have a structure represented by the following general formula (2) and has a number average molecular weight of 1000 to 7000. preferable.

(Wherein X represents an aryl group, (Y) _m represents a polyphenylene ether moiety, Z represents a phenylene group, an oxygen atom or a sulfur atom, R ^{1 to} R ³ independently represent a hydrogen atom, an alkyl group, An alkenyl group or an alkynyl group, m represents an integer of 1 to 100, n represents an integer of 1 to 6, and q represents an integer of 1 to 4.

  The aryl group represented by X is derived from the phenol species. Examples of the aryl group include a phenyl group, a biphenyl group, an indenyl group, and a naphthyl group, and a phenyl group is preferable. In addition, the aryl group of the present invention also includes a diphenyl ether group in which these aryl groups are bonded by an oxygen atom, a benzophenone group bonded by a carbonyl group, and a 2,2-diphenylpropane group bonded by an alkylene group. Included in the definition. Further, these aryl groups may be substituted with a general substituent such as an alkyl group (preferably a C1 to C6 alkyl group, particularly a methyl group), an alkenyl group, an alkynyl group or a halogen atom.

  Furthermore, in the general formula (2), a polyphenylene ether in which Z in the portion represented by the following general formula (3) is a phenylene group, n is 1, and the number average molecular weight is 3000 to 7000. Resins are particularly preferred.

(Wherein R ^{1 to} R ³ independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, Z represents a phenylene group, an oxygen atom or a sulfur atom, and n represents an integer of 1 to 6). )

  By using such a polyphenylene ether resin in the resin composition of the present invention, the resulting prepreg has excellent moldability, and the resulting laminate has improved heat resistance such as solder heat resistance, and further affects the transmission speed. Tends to be low.

  In the partial structure represented by the general formula (3), a halide of a compound having the partial structure, for example, halogenated methylstyrene, and the polyphenylene ether resin reduced in molecular weight are present in the presence of an alkali metal hydroxide. It can be performed by reacting with.

  As a specific example, for example, by dissolving a polyphenylene ether resin having a phenol group at the terminal and halogenated methylstyrene in an organic solvent such as toluene, and dropping an aqueous solution of an alkali metal hydroxide into this solution, An end-modified polyphenylene ether resin by ethenyl benzylation, which is an example of the structure, is obtained. At this time, the alkali metal hydroxide functions as a dehydrohalogenating agent (for example, a dehydrochlorinating agent), and this alkali metal hydroxide desorbs the hydrogen halide from the phenol group and halogenated methylstyrene, The structure represented by the general formula (2) is bonded to O instead of H of the phenol group (—OH) at the terminal of the polyphenylene ether resin. In addition, it is preferable that reaction temperature is 30-100 degreeC and reaction time is 0.5 to 20 hours.

  Examples of the halogenated methylstyrene include p-chloromethylstyrene, m-chloromethylstyrene, a mixture of p-chloromethylstyrene and m-chloromethylstyrene, p-bromomethylstyrene, m-bromomethylstyrene, A mixture of p-bromomethylstyrene and m-bromomethylstyrene or the like can be used. In particular, the halogenated methylstyrene is preferably at least one selected from the group consisting of p-chloromethylstyrene and m-chloromethylstyrene. When such a halogenated methylstyrene is used, the partial structure represented by the general formula (3) becomes at least one selected from the group consisting of a p-ethenylbenzyl group and an m-ethenylbenzyl group. The melting point and softening point of the ether resin can be arbitrarily changed. For example, when p-chloromethylstyrene is used, the symmetry becomes good, and a polyphenylene ether resin having a high melting point and a high softening point can be obtained. Also, a mixture of p-chloromethylstyrene and m-chloromethylstyrene Can be used to obtain a polyphenylene ether resin having a low melting point and a low softening point, and the workability during molding is improved.

  The alkali metal hydroxide is not particularly limited, and for example, potassium hydroxide, sodium hydroxide, a mixture thereof, and the like can be used. In addition, it is preferable that the mixture ratio of an alkali metal hydroxide is about 1.1-2.0 times mole with respect to 1 mol of phenol groups.

  In carrying out ethenyl benzylation, a phase transfer catalyst may be used. The phase transfer catalyst has a function of incorporating an alkali metal hydroxide and is soluble in both a phase composed of a polar solvent such as water and a phase composed of a nonpolar solvent such as an organic solvent. It is a catalyst that can move. When a phase transfer catalyst is not used, it is difficult to solubilize only alkali metal hydroxide in a nonpolar solvent, so halogenation is performed from polyphenylene ether resin and halogenated methylstyrene dissolved in the nonpolar solvent. It may take a long time to desorb hydrogen. However, in the presence of the phase transfer catalyst, the alkali metal hydroxide dissolved in the polar solvent is taken into the phase transfer catalyst and then transferred into the nonpolar solvent by the phase transfer catalyst. Hydroxides can be easily solubilized in nonpolar solvents, and ethenylbenzylation can be promoted. The phase transfer catalyst is not particularly limited, and for example, a quaternary ammonium salt such as tetra-n-butylammonium bromide can be used. In the presence of a phase transfer catalyst, the ethenyl benzylation reaction is preferably performed at a temperature of 100 ° C. or lower.

  By the method described above, a polyphenylene ether resin having at least one structure (substantially upper limit of 4) represented by the general formula (2) at the molecular end can be produced.

  In addition to the polyphenylene ether resin, the component forming the resin contained in the polyphenylene ether resin composition may contain a crosslinkable curing agent and other resins.

  Examples of the crosslinkable curing agent include triallyl isocyanurate (TAIC), triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl fumarate, diethylene glycol diallyl carbonate, triallyl phosphate, ethylene glycol diallyl ether, trimethylol Compounds such as allyl ether of propane, partially allyl ether of pentaerythritol, diallyl sebacate, allylated novolak, allylated resole resin are used. Among these, triallyl isocyanate is preferable from the viewpoint that the dielectric loss tangent which affects the variation in transmission time can be lowered.

  Further, the other resin is not particularly limited, but an epoxy resin is preferably used since it has excellent interlayer adhesion in the laminate.

  In addition, when an epoxy-type resin is included as said other resin, it is preferable that it is 10 mass% or less in the said resin component, Furthermore, it is preferable that it is 5 mass% or less.

  When the epoxy resin is contained in an amount exceeding 10% by mass, the dielectric loss tangent that affects the transmission speed tends to increase, which is not preferable.

  In the polyphenylene ether resin composition of the present invention, a silica balloon having an average particle size of 5 μm or less is contained as a component for improving dielectric properties.

Silica balloons are hollow particles made of silica (SiO ₂ ) as the main component, and the internal space of the hollow particles is a mixture such as nitrogen, oxygen, inert gas such as argon, or air. It contains gas.

  The term “mainly composed of silica” means that 98% or more of the material forming the silica balloon is silica.

  The silica balloon used in the present invention is a silica balloon having an average particle size of 5 μm or less, preferably 4 μm or less, and a polyphenylene ether resin composition containing such an average particle size silica balloon is used as an insulator. As a result, a laminate having both a low dielectric constant and insulation reliability can be obtained. The lower limit of the average particle diameter is not particularly limited as long as it can be produced.

  When the average particle size exceeds 5 μm, the insulation reliability tends to be lowered.

  The average particle diameter is measured by a laser diffraction particle size distribution measuring method, for example, using a CILAS Model 920L laser diffraction particle size distribution measuring apparatus or the like.

  The ratio of the hollow parts contained in the silica balloon (hereinafter also referred to as average hollow ratio) is preferably 40 to 60% by volume, and more preferably 50 to 60% by volume. When the average hollow ratio is less than 40% by volume, the ratio of hollow parts in the silica balloon tends to be too small to make it difficult to sufficiently reduce the dielectric constant, and when it exceeds 60% by volume. The silica balloon tends to crack during the production of the laminate, making it difficult to reduce the dielectric constant.

The average hollowness is measured by the pycnometer method and the ratio of the average specific gravity to the specific gravity of the material forming the silica balloon (1- (average specific gravity / specific gravity of the material forming the silica balloon)) × 100 (volume%) )
Is calculated by

  The specific gravity of the silica balloon is about 0.9 to 1.3, and further about 0.9 to 1.1.

  Specific examples of such a silica balloon include DBS series manufactured by Denki Kagaku Kogyo Co., Ltd.

  In addition, the silica balloon used in the present invention is further treated with a coupling agent, in addition to insulation reliability, improves solder heat resistance during moisture absorption, and adjusts the varnish of the polyphenylene ether resin composition. This is preferable from the viewpoint of improving dispersibility.

  As a coupling agent used for the silane coupling agent treatment, for example, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, or the like is used. Among these, in particular, a silane coupling agent that reduces silanol groups on the surface of the silica balloon and makes the surface hydrophobic, specifically, for example, vinyltrimethoxysilane, vinyltriethoxysilane, silazane, γ-glycol. Silane coupling agents such as sidoxypropylmethyldiethoxysilane are particularly preferred.

  In the polyphenylene ether resin composition of the present invention, the silica balloon is contained in an amount of 5 to 50% by mass, preferably 10 to 40% by mass. When the ratio is less than 5% by mass, the effect of reducing the dielectric constant is not sufficiently exhibited, and when it exceeds 50% by mass, the mechanical strength is lowered and the resin flowability is deteriorated.

  The polyphenylene ether resin composition of the present invention may contain other fillers and other components used as necessary in addition to the silica balloon as a filler component.

  Specific examples of the other filler include, for example, silica such as spherical silica, alumina, talc, mica, clay, bentonite, kaolin, calcium carbonate, calcium oxide, calcium sulfate, barium sulfate, zinc oxide, magnesium oxide, hydro Examples thereof include inorganic fillers such as talcite, mica, and glass beads, and organic fillers such as aramid fibers, liquid crystal polyester fibers, and phenol resin fibers.

  Among the fillers, it is preferable from the viewpoint that the thermal expansion coefficient of a laminate from which spherical silica is obtained can be reduced, and a laminate excellent in dimensional stability can be obtained.

  The polyphenylene ether resin composition of the present invention is prepared into a varnish for the purpose of impregnating the prepreg-forming substrate during the production of the prepreg. The method for preparing the varnish will be described below.

  The varnish of the polyphenylene ether resin composition is, for example, a resin varnish obtained by dissolving a resin component containing a polyphenylene ether resin in a heated organic solvent, further adding other components such as a reaction initiator, and stirring and mixing. After preparing and cooling, the silica balloon, other fillers, flame retardants, compatibilizing agents, and other additives are added and stirred and mixed.

  First, a resin varnish containing a resin component is prepared.

  The organic solvent is not particularly limited as long as it does not dissolve the resin component and adversely affects the reaction. For example, ketones such as methyl ethyl ketone, ethers such as dibutyl ether, esters such as ethyl acetate, dimethyl A suitable organic solvent such as amides such as formamide, aromatic hydrocarbons such as benzene, toluene and xylene, and chlorinated hydrocarbons such as trichloroethylene may be used singly or in combination. What is necessary is just to adjust suitably the density | concentration of the resin solid content of the said resin varnish according to the operation | work which impregnates a prepreg formation base material, for example, 20-80 mass% is suitable.

  Α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, peroxide Benzoyl, 3,3 ′, 5,5′-tetramethyl-1,4-diphenoquinone chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobuty Examples include rhonitrile. Among these, α, α′-bis (t-butylperoxy-m-isopropyl) benzene has a relatively high thermal decomposition temperature, and therefore accelerates curing at a time when curing is not required, such as when the prepreg is dried. This is preferable because the polyphenylene ether resin composition has high storage stability and low volatility, and therefore does not volatilize when the prepreg is dried or stored, and is stable.

  Moreover, the curing reaction can be further accelerated by further adding a carboxylic acid metal salt or the like as required.

  Next, to the obtained resin varnish, the silica balloon and other fillers used as necessary, a flame retardant, a compatibilizing agent, and the like are added and stirred and mixed to obtain a polyphenylene ether resin composition. A varnish is obtained.

  The stirring / mixing method is not particularly limited as long as the components are uniformly dissolved or dispersed in a solvent. Specifically, a planetary mixer, a ball mill, a bead mill, a roll mill, or the like is used. preferable.

  In addition, the well-known brominated organic compound normally used as a flame retardant is mainly used for the said flame retardant. Specifically, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromodiphenyl ethane, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene bis (Tetrabromophthalimide), a polycarbonate oligomer produced from tetrabromobisphenol A or a copolymer thereof with bisphenol, a brominated epoxy compound (for example, a monoepoxy compound obtained by reaction of brominated bisphenol A and epichlorohydrin), Poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A cyanuric and brominated phenol Compounds, brominated polystyrene, crosslinked brominated polystyrene, aromatic bromine compounds such as halogenated polymers and oligomers such as crosslinked brominated poly α- methyl styrene. Among these, decabromodiphenylethane is a non-reacted brominated organic compound containing a resin component containing polyphenylene ether, and does not dissolve in the solvent, but disperses it in an incompatible state in the resin. Since it exists, it is preferably used from the viewpoint of improving moisture resistance reliability and moisture absorption heat resistance.

  Furthermore, in the polyphenylene ether resin composition, as long as the effects of the present invention are not impaired, other substances contained in the usual thermosetting resin composition as necessary, for example, a heat stabilizer, an antistatic agent, an ultraviolet absorber, You may mix | blend a flame retardant, dye, a pigment, a lubricant, etc.

  The prepreg of the present invention can be obtained by impregnating a prepreg-forming base material with the varnish of the polyphenylene ether resin composition and further drying by heating to evaporate the organic solvent and semi-curing the polyphenylene ether resin in the base material. .

  As the prepreg-forming substrate, glass cloth made of glass fiber or woven fabric of organic fiber can be used, but glass cloth is used because it has excellent dimensional stability and high balance of performance such as high rigidity. It is preferable to use it.

  The prepreg-forming base material is preferably impregnated with the varnish of the polyphenylene ether resin composition so that the content of the polyphenylene ether resin composition in the prepreg is 40 to 95% by mass. If the proportion is less than 40% by mass, there is a risk of voids and scumming during molding, and it is difficult to obtain 95% by mass or more, so the substantial upper limit is this value.

  Examples of the method for producing the prepreg of the present invention include a method in which a prepreg-forming base material is impregnated with a varnish of the polyphenylene ether resin composition and then dried. Impregnation is performed by dipping or coating. Impregnation can be repeated a plurality of times as necessary.In this case, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations, and finally the desired composition and resin amount can be adjusted. is there.

  The base material impregnated with the varnish of the polyphenylene ether resin composition becomes a prepreg by being heated at a desired heating condition, for example, at 80 to 150 ° C. for 1 to 10 minutes.

  The laminate of the present invention is produced using the prepreg. That is, one or a plurality of the prepregs are stacked, and a metal foil such as a copper foil is stacked on both upper and lower surfaces or one surface of the prepreg. A metal foil-clad laminate can be produced.

  Then, by forming a circuit by etching the metal foil on the surface of the laminate thus produced, a printed wiring board having a conductor pattern as a circuit on the surface of the laminate can be obtained. . Since the printed wiring board thus obtained is formed using the above laminate, it has excellent dielectric characteristics and improved reliability, particularly insulation reliability.

  Furthermore, after using the laminate of the present invention as a printed wiring board for an inner layer, and applying a surface treatment to the metal foil of the conductor pattern, a plurality of printed wiring boards are stacked through the prepreg of the present invention, and the outermost layer thereof A multilayer printed wiring board having excellent dielectric characteristics and excellent insulation reliability can be obtained by stacking metal foils through the prepreg of the present invention and then heat-pressing and laminating and integrating them.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the examples.

  The main raw materials used in this example are summarized below.

High molecular weight polyphenylene ether resin: Polyphenylene ether having a number average molecular weight of 14,000 (“Noryl PX9701” manufactured by GE Plastics, Inc.)
Phenol species: bisphenol A
Decomposed peroxide: t-butylperoxyisopropyl monocarbonate (“Perbutyl I” manufactured by NOF Corporation)
Cobalt naphthenate solution: 8% solution dissolved in toluene Reaction initiator: Di (t-butylperoxyisopropyl) benzene ("Perbutyl P" manufactured by NOF Corporation)
Prepreg forming substrate: Glass cloth “WEA116E” manufactured by Nitto Boseki Co., Ltd.
Silica balloon: Sample name “DBS-0340” manufactured by Denki Kagaku Kogyo Co., Ltd., which is a silica balloon having an average particle diameter of 3 μm, an SiO ₂ content of 98% by mass or more, and an average hollowness of 50% by mass.
Glass balloon I: Product number “HSC110” manufactured by Potters Ballotini, which is a glass balloon having an average particle size of 10 μm, an SiO ₂ content of 55% by mass, and an average hollowness of 50% by volume
Glass balloon II: trade name “Glass Bubbles S38” manufactured by Sumitomo 3M Limited, which is a glass balloon having an average particle size of 40 μm, an SiO ₂ content of 70% by mass and an average hollowness of 80% by volume.
Spherical silica: Product number “SO25R” manufactured by Admatechs with an average particle size of 0.5 μm

Moreover, the evaluation method in a present Example is shown collectively below.
(Dielectric constant / dielectric loss tangent)
Based on JIS C6481, the dielectric property in 1 GHz of the double-sided copper clad laminated body I mentioned later was measured.
(Coefficient of thermal expansion)
A test piece is prepared by etching the copper foils on the front and back sides of a double-sided copper clad laminate I, which will be described later, and the test piece is used at a temperature of 75 to 120 ° C. using a TMA measuring device (manufactured by Seiko Instruments Inc.). The coefficient of thermal expansion at the time of temperature increase was measured.
(Flame retardance)
Flame retardancy was evaluated according to the flame retardancy test method of UL-94.
(PCT solder heat resistance)
The copper foils on the front and back sides of the double-sided copper clad laminate I described later were etched and subjected to pressure cooker treatment (121 ° C., humidity 100%, treatment for 2 to 4 hours). Then, after the treated double-sided copper clad laminate was immersed in a solder bath at 260 ° C. for 20 seconds, the time during which no abnormal appearance such as swelling occurred was evaluated.
(Insulation reliability)
A double-sided copper clad laminate II described later was subjected to a pressure cooker treatment (110 ° C., humidity 85%, treatment for 100 hours).
And the resistance value of the double-sided copper clad laminate after the treatment was measured, and the case where the resistance value was 10 ⁸ Ω or more was evaluated as “◯”, and the case where the resistance value was less than 10 ⁸ was evaluated as “X”.
(Appearance observation of prepreg)
The appearance of the obtained prepreg was visually observed. The case where no unevenness was generated was evaluated as “◯”, the case where a small amount of unevenness was generated as “Δ”, and the case where many unevenness was generated as “X”.

<Example 1>
(Low molecular weight high molecular weight polyphenylene ether resin)
200 g of toluene was placed in a 2000 mL flask equipped with a stirrer and a stirring blade. While controlling the flask at an internal temperature of 80 ° C., 100 g of high molecular weight polyphenylene ether resin, 4.3 g of bisphenol A, 2.94 g of decomposed peroxide “Perbutyl I” and 0.0042 g of cobalt naphthenate solution were added. A low molecular weight polyphenylene ether resin was prepared by stirring until the ether was completely dissolved.

  The low molecular weight polyphenylene ether obtained was reprecipitated with a large amount of methanol to remove impurities, and dried at 80 ° C. under reduced pressure for 3 hours to completely remove toluene.

(Ethenylbenzylation of low molecular weight polyphenylene ether resin)
200 g of the low-molecular-weight polyphenylene ether resin in a 1 L three-necked flask equipped with a temperature controller, a stirrer, a cooling facility, and a dropping funnel, chloromethylstyrene (ratio of p-chloromethylstyrene and m-chloromethylstyrene is 1) : 1; Tokyo Chemical Industry Co., Ltd. (15 g), tetra-n-butylammonium bromide 0.8 g and toluene 400 g were charged, dissolved by stirring, the liquid temperature was adjusted to 75 ° C., and an aqueous sodium hydroxide solution (sodium hydroxide 10 g / Water (10 g) was added dropwise over 20 minutes, and stirring was further continued at 75 ° C. for 4 hours. Next, after neutralizing the contents of the flask with a 10% aqueous hydrochloric acid solution, a large amount of methanol was added to obtain ethenylbenzylated polyphenylene ether as a precipitate. The precipitate filtrate is washed three times with a mixture of methanol 80 and water 20 and then treated at 80 ° C. for 3 hours under reduced pressure to remove ethenylbenzylated polyphenylene ether from which solvent and water have been removed. The resin was removed.

When the number average molecular weight of the obtained ethenylbenzylated polyphenylene ether resin was measured by GPC, the number average molecular weight (Mn) was 4200 and the molecular weight distribution (Mw / Mn) was 1.5. Incidentally, the number average molecular weight by gel permeation chromatography (GPC), TSK guard column H XL -4 G4000HXL 1 present, one G3000HXL, one G2000HXL, was measured using a column of two G1000HXL.

(Manufacture of prepreg)
70 parts by mass of the ethenylbenzylated polyphenylene ether resin was dissolved in 100 parts by mass of toluene controlled at 70 ° C. for 30 minutes. Thereafter, 2 parts by mass of a reaction initiator “perbutyl P” and 30 parts by mass of triallyl isocyanurate (TAIC) were added and cooled to room temperature. Next, 15 parts by mass of silica balloon and 18 parts by mass of flame retardant “decabromodiphenylethane” (manufactured by Albemarle Asano Co., Ltd., trade name “SAYTEX 8010”, Br content 82 mass%) are added, and 3000 rpm for 30 minutes. The resin varnish was prepared by stirring at
Next, after impregnating the obtained resin varnish into the prepreg-forming substrate, the solvent was removed by heating and drying at 130 ° C. for 3 minutes to obtain a prepreg having a resin content of 51 mass%.

(Manufacture of laminates)
Six prepregs obtained were stacked, 35 μm thick copper foil (ST foil) was placed on both sides, and heated and pressurized under the molding conditions of temperature 200 ° C., pressure 3.0 MPa (30 kg / cm ² ), 180 minutes. A double-sided copper-clad laminate I having a thickness of 0.75 mm was obtained.

On the other hand, a 35 μm-thick copper foil (ST foil) was placed on both surfaces of one prepreg obtained, and heated and pressed under molding conditions of a temperature of 200 ° C., a pressure of 3.0 MPa (30 kg / cm ² ), and 180 minutes, A double-sided copper-clad laminate II having a thickness of 0.13 mm was obtained.

  The obtained polyphenylene ether resin composition, double-sided copper-clad laminate I and double-sided copper-clad laminate II were evaluated according to the evaluation method described above. The results are shown in Table 1.

<Examples 2 and 3 and Comparative Examples 1 and 2>
A prepreg and a laminate were prepared and evaluated in the same manner as in Example 1 except that the varnish of the polyphenylene ether resin composition was obtained at the blending ratio in Table 1. The results are shown in Table 1.

<Examples 4 and 5>
A prepreg and a laminate were prepared and evaluated in the same manner as in Example 1 except that the varnish of the polyphenylene ether resin composition was obtained at the blending ratio in Table 1. The results are shown in Table 1.

  The silica balloon used in Example 4 is vinyltrimethoxysilane (product number “KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and the silica balloon used in Example 5 is The silica balloon was surface-treated using vinyltriethoxysilane (product number “KBE1003” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent.

  Although the insulation reliability of the double-sided copper-clad laminates of Examples 1 to 5 obtained using the polyphenylene ether resin composition containing a silica balloon having an average particle diameter of 3 μm was all good from the results of Table 1, the insulation reliability was ○. On the other hand, the insulation reliability of Comparative Example 1 using a glass balloon having an average particle diameter of 10 μm and Comparative Example 2 using a glass balloon having an average particle diameter of 40 μm was x. This shows that the insulation reliability of the laminated body obtained using the polyphenylene ether resin composition of this invention is excellent.

  Further, the silica balloons contained in the polyphenylene ether resin compositions of Examples 4 and 5 are those whose surfaces are treated with a silane coupling agent, but the laminate using these is a silica balloon that has not been treated. It can be seen that the heat resistance of the PCT solder and the appearance of the prepreg are superior to the laminates using the polyphenylene ether resin compositions of Examples 1 to 3.

Claims (6)

  A polyphenylene ether resin composition comprising a polyphenylene ether resin and a silica balloon having an average particle diameter of 5 μm or less, wherein the silica balloon is contained in the polyphenylene ether resin composition in an amount of 5 to 50% by mass. Polyphenylene ether resin composition.   The polyphenylene ether resin composition according to claim 1, wherein the silica balloon has an average hollowness of 40 to 60% by volume.   The polyphenylene ether resin composition according to claim 1 or 2, wherein the silica balloon is treated with a coupling agent.   The polyphenylene ether resin composition according to any one of claims 1 to 3, wherein the polyphenylene ether resin composition contains spherical silica.   A prepreg obtained by impregnating a prepreg-forming base material with the polyphenylene ether resin composition according to claim 1. The laminated body formed by laminating | stacking the prepreg of Claim 5, and metal foil, and heat-compressing.