JP2005082793A - Polyphenylene ether-based resin composition, method for producing the same, and electronic circuit board given by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene ether-based resin composition having a low dielectric loss tangent, a high Q value, and a low dielectric constant in a high frequency band, to provide a method for producing the same, and to provide an electronic circuit board given by using the polyphenylene ether-based resin composition and capable of realizing high-speed communication of electronic equipment and information communication equipment, downsizing and weight saving thereof, large-amount high-speed processing of information, etc. <P>SOLUTION: This polyphenylene ether-based resin composition contains a polyphenylene ether-based resin having repeating units expressed by general formula (I) (R<SP>1</SP>and R<SP>2</SP>are each an alkyl or an aryl) as a main component and has a chloride ion content of ≤1500 ppm. The method for producing the composition and the electronic circuit board which is given by using the composition are provided, respectively. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyphenylene ether-based resin composition mainly composed of a polyphenylene ether-based resin having a low dielectric loss tangent, a high Q value and a low dielectric constant in a high frequency band, and a method for producing the same. Moreover, this invention relates to the board | substrate for electronic circuits which uses this polyphenylene ether-type resin composition.

  In recent years, with the trend toward broadband information communication and mobile / wireless information terminals, there is a strong demand for high-speed communication, downsizing and weight reduction, high-speed mass processing of information, and the like for electronic devices and information communication devices. Radio waves in the high frequency band from megahertz (MHz) to gigahertz (GHz) are used in portable mobile communications such as digital mobile phones, satellite communications, etc. In information communication equipment used as these communication means, Cases, circuit boards, and electronic components are being downsized and mounted with high density. Along with this, further performance improvement is required for circuit board materials used in electronic equipment and information communication equipment.

  The characteristics required as a circuit board material in a high frequency band include a low dielectric constant and a low dielectric loss tangent, or a high dielectric constant and a low dielectric loss tangent depending on the application. Low dielectric constant is required for demands such as high-speed propagation signal, suppression of signal transmission loss, thinning of wiring board, suppression of parasitic capacitance, etc. It is required for demands such as fine wiring patterns and built-in capacitor functions. Further, low dielectric loss tangent and high Q factor are required for demands such as suppression of signal transmission loss.

  Examples of circuit boards used in electronic devices, information communication devices, and the like include ceramic substrates and resin (organic polymer) substrates. When a resin is used as the substrate material, the dielectric constant can be reduced and the loss of a conductor forming a circuit can be reduced as compared with ceramic. Examples of resins used or expected for such circuit board materials include epoxy resins, phenol resins, polyimide resins, unsaturated polyester resins, fluororesins, polyphenylene ether resins, and the like.

  Epoxy resins and phenolic resins are commonly used as circuit board materials, but they are not sufficient for low dielectric loss tangent and low dielectric constant requirements in the high frequency band, and the water absorption rate of the resin The variation in dielectric characteristics due to the Polyimide resins, unsaturated polyester resins, and the like are materials that can be expected to meet the demands for low dielectric loss tangent and low dielectric constant, but there is also a problem that the dielectric characteristics greatly vary due to the water absorption rate of the resin. is there. A fluororesin is a material that can be most expected to have a low dielectric loss tangent and a low dielectric constant among resin materials, but has problems in workability due to the physical properties of the fluororesin itself.

  Under such circumstances, in recent years, polyphenylene ether resins have attracted attention as a new material for solving such problems, and application to copper-clad laminates has been attempted (see Patent Document 1).

  For example, Patent Document 1 discloses a curable polyphenylene ether resin composition and a cured sheet or film thereof. In the polyphenylene oxide disclosed in Patent Document 1, a substituent on the phenylene ring is an alkenyl group or alkynyl group having a specific structure.

  Patent Document 2 discloses a polyphenylene oxide resin-based LCR multilayer board, and Patent Document 3 discloses a high dielectric polyphenylene oxide-based resin composition. These polyphenylene oxides disclosed in Patent Document 2 and Patent Document 3 have a hydrocarbon group having 1 to 3 carbon atoms as a substituent on the phenylene ring. Among these, poly (2,6-dimethyl-1,4-phenylene ether) resin is a resin having a high dielectric loss tangent and a relative dielectric constant in a high frequency band, a small water absorption, and a relatively high heat resistance. It has excellent characteristics as a circuit board material.

  Further, Patent Document 4 discloses a composite dielectric substrate that can obtain a dielectric characteristic according to the purpose of use, such as a high dielectric constant and a high Q value in a high-frequency region. Body ceramic powder and polyvinyl benzyl ether in a predetermined ratio. Furthermore, Patent Document 5 discloses a composition having a high-frequency dielectric characteristic that increases the Q value without increasing the dielectric constant in the frequency range from 100 MHz to 10 GHz without impairing the excellent physical properties of the polyvinyl benzyl ether compound. This composition is a polyvinyl benzyl ether resin composition comprising a polyvinyl benzyl ether compound and a styrenic elastomer.

Japanese Patent Publication No. 6-78482 (Claims etc.) Japanese Patent Publication No. 6-82927 (claims, etc.) Japanese Patent Publication No. 8-11781 (Claims etc.) JP 2001-181460 A (Claims etc.) JP 2002-128977 A (claims, etc.)

  However, in consideration of the fact that radio waves used for information communication will shift to a high frequency band in the future, a resin composition capable of achieving further lower dielectric loss tangent, higher Q value, and lower dielectric constant. Is required.

  Accordingly, an object of the present invention is to provide a polyphenylene ether resin composition having a low dielectric loss tangent, a high Q value and a low dielectric constant in a high frequency band, and a method for producing the same. Another object of the present invention is to provide an electronic circuit board that uses this polyphenylene ether-based resin composition to realize high-speed communication, downsizing and weight reduction of electronic devices and information communication devices, mass information high-speed processing, and the like. It is to provide.

  As a result of intensive investigations on the relationship between the amount of chloride ions contained as impurities and dielectric properties during the synthesis of polyphenylene ether resins that have not been studied at all, the present inventors have determined that the chloride ion content and the Q value are The present inventors have found that there is a strong correlation between the two, and have completed the present invention.

（式中、Ｒ¹およびＲ²は各々独立にアルキル基またはアリール基を表す）で示される繰り返し単位を有するポリフェニレンエーテル系樹脂を主成分とし、塩素イオン含有量が１５００ｐｐｍ以下であることを特徴とするものである。 That is, the polyphenylene ether resin composition of the present invention has the following general formula (I),

(Wherein R ¹ and R ² each independently represents an alkyl group or an aryl group), the main component is a polyphenylene ether resin having a repeating unit, and the chloride ion content is 1500 ppm or less. To do.

（式中、Ｒ¹およびＲ²は各々独立にアルキル基またはアリール基を表す）で示されるフェノール系モノマーを塩化銅溶液中にて酸素を通気しながら重合させ、下記一般式（Ｉ）、

（式中、Ｒ¹およびＲ²は各々独立にアルキル基またはアリール基を表す）で示される繰り返し単位を有するポリフェニレンエーテル系樹脂の粗製物を得、次いで該粗製物を塩素イオンが１５００ｐｐｍ以下となるまで精製することを特徴とするものである。 Further, the production method of the present invention, in producing the polyphenylene ether-based resin composition, the following general formula (II),

(Wherein R ¹ and R ² each independently represents an alkyl group or an aryl group) are polymerized while aeration of oxygen in a copper chloride solution, and the following general formula (I),

(In the formula, R ¹ and R ² each independently represents an alkyl group or an aryl group) A crude product of a polyphenylene ether resin having a repeating unit is obtained, and then the crude product has a chlorine ion of 1500 ppm or less. It is characterized by refine | purifying to.

  Furthermore, the electronic circuit board of the present invention is characterized by containing the polyphenylene ether resin composition as a main component.

  According to the present invention, it is possible to provide a polyphenylene ether-based resin composition having a low dielectric loss tangent, a high Q value and a low dielectric constant in a high frequency band, and a method for producing the same. Moreover, according to this invention, the board | substrate for electronic circuits which uses this polyphenylene ether-type resin composition can be provided. This electronic circuit board contributes to high-speed communication, downsizing and weight reduction of electronic devices and information communication devices, mass information high-speed processing, and the like.

First, the polyphenylene ether resin composition that is the main component of the composition of the present invention will be described.
The polyphenylene ether resin of the present invention has a repeating unit represented by the following general formula (I). In the formula, R ¹ and R ² each independently represents an alkyl group or an aryl group. In the present invention, it is preferable that R ¹ is an alkyl group and R ² is an aryl group in order to obtain a higher Q value.

  Desirably, the aryl group includes a phenyl group. This aryl group may have various substituents, for example, a lower alkyl group such as methyl and ethyl, a lower alkoxy group such as methoxy and ethoxy, and a halogen atom.

The alkyl group is represented by C _n H _{2n + 1} and may be a linear structure or a branched structure. This alkyl group may have various substituents, for example, a lower alkoxy group such as methoxy and ethoxy, a halogen atom, and the like. With respect to the carbon number n of the alkyl group, when n = 11 or more, moldability when used as a resin material tends to deteriorate, and therefore an alkyl group of n = 1 to 10 is preferable. Moreover, the alkyl group of n = 4-10 is more preferable from a viewpoint that a dielectric constant smaller than poly (2, 6- dimethyl- 1, 4- phenylene ether) is obtained. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl and nonyl groups.

（式中、Ｒ¹およびＲ²は各々独立にアルキル基またはアリール基を表す）で示されるフェノール系モノマーを合成し、そのモノマーを重合させることにより得られる。モノマー及びポリマーの合成については、種々の方法を採ることができるが、本発明においては最終生成物に含まれる塩素イオン含有量が１５００ｐｐｍ以下、好ましくは１０００ｐｐｍ以下、より好ましくは７００ｐｐｍ以下となることが重要である。塩素イオン含有量が１０００ｐｐｍ以下のときに、例えば、Ｒ¹とＲ²がともにＣＨ₃基の場合、Ｑ値が５００以上の高い値となる。また、Ｒ¹がＣ₂Ｈ₅でＲ²がＣ₆Ｈ₅の場合には、塩素イオン含有量が１５００ｐｐｍ以下のときにＱ値が５００以上となる。そのため、本発明の製造方法では、上記一般式（ＩＩ）で示されるフェノールモノマーの重合反応終了後、塩素イオン含有量が１５００ｐｐｍ以下、好ましくは１０００ｐｐｍ以下、より好ましくは７００ｐｐｍ以下となるまで精製することが必要である。 The composition of the present invention has the following general formula (II), which is a monomer corresponding to a polyphenylene ether resin.

(Wherein, R ¹ and R ² each independently represents an alkyl group or an aryl group) are synthesized, and the monomer is polymerized. Various methods can be employed for the synthesis of the monomer and polymer. In the present invention, the chlorine ion content in the final product may be 1500 ppm or less, preferably 1000 ppm or less, more preferably 700 ppm or less. is important. When the chloride ion content is 1000 ppm or less, for example, when both R ¹ and R ² are CH ₃ groups, the Q value becomes a high value of 500 or more. When R ¹ is C ₂ H ₅ and R ² is C ₆ H ₅ , the Q value is 500 or more when the chlorine ion content is 1500 ppm or less. Therefore, in the production method of the present invention, after completion of the polymerization reaction of the phenol monomer represented by the general formula (II), purification is performed until the chlorine ion content is 1500 ppm or less, preferably 1000 ppm or less, more preferably 700 ppm or less. is required.

Although the molecular weight of the polyphenylene ether resin according to the present invention is not limited, for example, the weight average molecular weight (Mw) is about 1.0 × 10 ^{4 to} 1.0 × 10 ⁵ , and the number average molecular weight (Mn ) About 5.0 × 10 ^{3 to} 3.0 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of about 2-6.

  One or more of the polyphenylene ether resin compositions of the present invention can be used as they are as a substrate material for electronic circuits, but a styrene elastomer and / or a flame retardant may be blended. By blending the styrene elastomer, flexibility is imparted to the obtained substrate, adhesion strength with the metal foil in obtaining a resin substrate with metal foil is improved, and workability is also improved. Moreover, the flame-retardant request | requirement according to a use is satisfy | filled by the mixing | blending of a flame retardant.

  Styrenic elastomers are highly compatible with polyphenylene ether resins and have been selected as low dielectric constant and low dielectric loss tangent elastomers. The styrene elastomer is a styrene-polyolefin copolymer and has a styrene ratio of 50% or more, more preferably 50 to 80% by mass ratio. When the styrene ratio is less than 50%, the compatibility with the polyphenylene ether resin tends to be lowered. On the other hand, when the styrene ratio is larger than 80%, the flexibility of the obtained substrate tends to be lowered. Examples of the polyolefin phase include poly (polyethylene-propylene), polyethylene-polybutylene random copolymer, polybutadiene, and polyisoprene. The blending amount of the styrene-based elastomer is preferably about 95: 5 to 75:25, expressed as a blending ratio of polyphenylene ether resin: styrene-based elastomer. With such a blending amount, the blending effect of the styrenic elastomer can be obtained. One or more styrenic elastomers can be used.

  The flame retardant is blended as necessary when flame retardancy is required. Examples of the flame retardant include a chlorine flame retardant, a bromine flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, a metal salt flame retardant, and a silicone flame retardant. The blending amount of the flame retardant is preferably about 95: 5 to 70:30, expressed as a blending weight ratio of polyphenylene ether resin: flame retardant. With such a blending amount, a flame retardant effect is obtained. 1 type (s) or 2 or more types can be used for a flame retardant.

  When adding a styrene-type elastomer and / or a flame retardant to the polyphenylene ether-type resin composition of this invention, it is good to knead | mix these. The kneading may be performed using a known means such as a kneader, a kneader, a ball mill, a stirrer, or a roll. The polyphenylene ether resin composition of the present invention may be prepared by mixing a polyphenylene ether resin with a styrene elastomer and / or a flame retardant in a solvent and drying. As the solvent used at this time, aromatic volatile solvents such as toluene and xylene are preferable. Moreover, you may add another additive in the range which does not impair the objective of this invention.

Next, an electronic circuit board that can take various forms of the present invention will be described.
A resin substrate can be produced with the polyphenylene ether resin composition of the present invention as it is or with a composition obtained by blending this resin composition with a styrene elastomer and / or a flame retardant. Hereinafter, these compositions are collectively referred to as polyphenylene ether resin materials.

  There are various forms of resin substrates for electronic circuits. A resin substrate can be obtained by press-molding the polyphenylene ether resin material under heat and pressure. A solution obtained by dissolving the polyphenylene ether-based resin material in a solvent is applied to a cloth substrate such as a glass cloth, and dried to obtain a substrate coated product. The solution is also applied to a metal foil such as a copper foil. A metal foil coated product can be obtained by coating and drying. Further, the substrate coated product, the metal foil such as a copper foil, and the metal foil coated product are appropriately combined and superposed, and these are heated and pressed to obtain a substrate. These substrates can have a metal foil such as a copper foil on both sides or one side, or no metal foil depending on the combination, and can be multi-layered. Specifically, a substrate obtained by heat and pressure molding in a state in which two or more of the substrate coated products are stacked, one of the substrate coated products, or two or more of the substrate coated products Two or more double-sided metal-clad substrates and metal foil coated products obtained by hot-press molding sandwiched between metal foils in a stacked state are heated in a state where both outer side surfaces are metal foils. Examples thereof include a double-sided metal-clad substrate obtained by pressure forming. Furthermore, it is obtained by heat and pressure molding in a state where two or more of the base material coated product, the resin substrate obtained by heat and pressure press molding of the polyphenylene ether resin material, and the base material coated material are stacked. Examples thereof include a multilayer substrate obtained by heating and press-molding a metal foil coated product on one side or both sides of a substrate or a double-sided metal-bonded substrate so that the metal foil becomes an outer surface.

  When preparing a substrate coated product, first, using the polyphenylene ether resin material and an appropriate solvent, a coating solution having a polyphenylene ether resin content of 20 to 60% by mass is prepared. . As the solvent used in preparing the solution, aromatic volatile solvents such as toluene and xylene are preferable. The resin material and the solvent are mixed with a mixing stirrer, and heated, degassed, etc. as necessary to prepare a coating solution.

  The coating solution thus obtained is applied to a cloth substrate such as a glass cloth. A glass cloth is preferably used as the cloth substrate. Although commercially available glass cloths (for example, those manufactured by Asahi Sebel) can be used, E glass cloths, D glass cloths, etc. can be properly used as necessary to obtain desired electrical characteristics. . Moreover, according to the objectives, such as the applicability | paintability to a cross base material and adhesive strength improvement, you may perform the coupling process of a cross base material, etc. The coating method may be any known method such as a method of coating to a predetermined thickness using a known vertical coating machine, or a method of coating a cloth substrate by a known doctor blade method. What was coated by such a method is dried at 100-140 degreeC for 0.5 to 5 hours, and a base-material coated material is obtained.

For example, when a copper-clad substrate is prepared using this base material coated product, a single base material coated surface or both surfaces or a plurality of base materials so as to have a predetermined thickness. Heating by placing metal foil such as copper foil on both sides or one side of the layered coating, or on both sides or one side of a laminate on which a plurality of substrate coatings have been pre-heated and pressed. Compressed and integrated. The forming method may be performed by a known method such as hot pressing. As molding conditions, a temperature of 150 to 250 ° C., a pressure of 9.8 × 10 ^{5 to} 4.9 × 10 ⁶ Pa, and a press time of about 0.5 to 5 hours are preferable. At this time, a copper foil is generally used as the metal foil, but can be selected from a gold foil, a silver foil, an aluminum foil, and the like. Further, when it is desired to obtain sufficient peel strength, an electrolytic foil is used, and when high frequency characteristics are important, a rolled foil having a small skin effect due to surface irregularities is preferably used. About metal foil thickness, a thing of 8-80 micrometers is used according to the use of a board | substrate, a required characteristic, etc.

  Moreover, a metal foil coated product can be obtained by coating and drying the above coating solution on a metal foil such as the above copper foil by a doctor blade method or the like. A substrate can be produced from this coated metal foil.

Furthermore, a press-molded resin substrate can be produced using the polyphenylene ether resin material of the present invention. A solid powder of the resin material is press-molded in a mold at a temperature of 150 to 250 ° C., a pressure of 9.8 × 10 ^{5 to} 4.9 × 10 ⁶ Pa, a press time of 0.5 to 5 hours, and a substrate Get. The substrate thickness is preferably 0.5 to 5 mm, but is appropriately selected according to the desired thickness.

A multilayer substrate can be produced by forming the substrate coated product, the metal foil coated product, the substrate, the metal foil, and the like thus produced, in an appropriate combination. As molding conditions, a temperature of 150 to 250 ° C., a pressure of 9.8 × 10 ^{5 to} 4.9 × 10 ⁶ Pa, and a pressing time of 0.5 to 5 hours are preferable.

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

Example 1 and Example 2: Synthesis of poly (2-ethyl-6-phenyl-1,4-phenylene ether) Poly (2-ethyl-6-phenyl-1,4-phenylene ether) was synthesized by the following chemical reaction formula. Was synthesized through the following steps 1) to 6).

1) Synthesis of 2-phenylanisole (2) To a suspension of potassium carbonate (126 g, 912 mmol) in N, N-dimethylformamide (100 ml) under a nitrogen atmosphere, 2-phenylphenol (1) (50.2 g, 295 mmol). ) In N, N-dimethylformamide (50 ml) was added, and the mixture was stirred at 60 ° C. for 1 hour, and then cooled to room temperature. To this, iodomethane (34.5 ml, 554 mmol) was added dropwise and stirred at room temperature. After confirming the completion of the reaction by TLC analysis (thin layer chromatography), the salt was removed by Celite filtration. Hexane (200 ml) and water (200 ml) were added to the filtrate to carry out a liquid separation operation to obtain an organic layer and an aqueous layer. The aqueous layer was extracted with ethyl acetate, and the ethyl acetate layer was combined with the previously obtained organic layer, washed with saturated brine, and dried over anhydrous sodium sulfate. The organic liquid was concentrated and purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to obtain 2-phenylanisole (2) (48.5 g, 89%).

2) Synthesis of 2-methoxy-3-phenylbenzaldehyde (3) Under a nitrogen atmosphere, 2-phenylanisole (2) (20.0 g, 109 mmol) of N, N, N ′, N′-tetramethylethylenediamine (24. To the solution (6 ml, 163 mmol), a 1.59 M n-butyllithium hexane solution (102 ml, 163 mmol) was added dropwise and stirred at 50 ° C. for 4 hours. The reaction solution was cooled to −78 ° C. in a dry ice-acetone bath, N, N-dimethylformamide (12.6 ml, 163 mmol) was added dropwise, the dry ice-acetone bath was removed, and the temperature was gradually raised to room temperature. . After confirming the completion of the reaction by TLC analysis, 3M hydrochloric acid was added dropwise at 0 ° C. to stop the reaction (pH 7). The organic layer extracted with ethyl acetate was washed with saturated brine and dried over anhydrous sodium sulfate. The extract was concentrated and purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to give 2-methoxy-3-phenylbenzaldehyde (3) (16.9 g, 73%).

3) Synthesis of 2-phenyl-6-vinylanisole (4) To a suspension of phosphonium salt (42.3 g, 105 mmol) synthesized from iodomethane and triphenylphosphine in tetrahydrofuran THF (250 ml), potassium tert-butoxide (18. 3 g, 163 mmol) was added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. Then, a solution of 2-methoxy-3-phenylbenzaldehyde (3) (16.9 g, 79.7 mmol) in THF (10 ml) was added dropwise, Further stirring at room temperature. After confirming the completion of the reaction by TLC analysis, hexane (200 ml) was added, and the resulting precipitate was removed by celite filtration. The filtrate was concentrated and purified by silica gel column chromatography (hexane / ethyl acetate = 50/1) to obtain 2-phenyl-6-vinylanisole (4) (11.8 g, 70%).

NMR data of 2-phenyl-6-vinylanisole (4);
¹ H-NMR (CDCl ₃ ); δ = 3.38 (3H, s), 5.34 (1H, d, J = 11.1 Hz), 5.80 (1H, d, J = 17.8 Hz), 7.01-7.62 (9H, m)

4) Synthesis of 2-ethyl-6-phenylanisole (5) 5% Pt / C (520 mg, 0.0573 mmol) and 2-phenyl-6-vinylanisole (4) (6.02 g, 28.6 mmol) as a catalyst Of ethanol (30 ml) was stirred at 70 ° C. under 1 atm of hydrogen. After confirming the completion of the reaction by TLC analysis, nitrogen substitution was performed, and the catalyst was removed by filtration. The filtrate was concentrated and purified by silica gel column chromatography (hexane / ethyl acetate = 100/1) to obtain 2-ethyl-6-phenylanisole (5) (5.87 g, 97%).

NMR data for 2-ethyl-6-phenylanisole (5):
¹ H-NMR (CDCl ₃ ); δ = 1.28 (3H, t, J = 7.5 Hz), 2.74 (2H, q, J = 7.5 Hz), 3.35 (3H, s), 7.06-7.23 (2H, m), 7.29-7.47 (3H, m), 7.53-7.63 (2H, m)

5) Synthesis of 2-ethyl-6-phenylphenol (6) To a solution of 2-ethyl-6-phenylanisole (5) (5.32 g, 25.1 mmol) in methylene chloride (15 ml) under a nitrogen atmosphere, 2M A solution of boron bromide in methylene chloride (10 ml) was added dropwise at -78 ° C. After confirming the completion of the reaction by TLC analysis, the reaction solution was poured into water (100 ml) at 0 ° C. to stop the reaction. The mixture was extracted with diethyl ether, washed with saturated brine, and dried over anhydrous magnesium sulfate. The extract was concentrated and purified by silica gel column chromatography (hexane / ethyl acetate = 30/1) to give 2-ethyl-6-phenylphenol (6) (4.38 g, 88%).

NMR data of 2-ethyl-6-phenylphenol (6): ¹ H-NMR (CDCl ₃ ); δ = 1.27 (3H, t, J = 7.6 Hz), 2.71 (2H, q, J = 7.6 Hz), 5.25 (1 H, s), 6.93 (1 H, t, J = 7.5 Hz), 7.03-7.21 (2 H, m), 7.33-7.56. (5H, m)

6) Polymerization of 2-ethyl-6-phenylphenol (6) Oxygen was bubbled through a mixed solution of copper chloride (45.0 mg, 0.454 mmol) in nitrobenzene (6 ml) and pyridine (1.90 ml, 45.4 mmol). . After 5 minutes, a solution of 2-ethyl-6-phenylphenol (6) (300 mg, 1.51 mmol) in nitrobenzene (4 ml) was added dropwise over 5 minutes, and aeration was continued. After 3 hours, the aeration of oxygen was stopped, and methanol (5 ml) was poured to stop the reaction. The reaction solution was poured into a 1M hydrochloric acid-methanol solution (150 ml), stirred for 30 minutes, and a crude product was obtained by suction filtration. This crude product was dried under reduced pressure with a vacuum pump, dissolved in chloroform (3 ml), and the solution was added dropwise to 1M hydrochloric acid-methanol solution (150 ml) for reprecipitation. The resulting precipitate was filtered, washed and dried to obtain poly (2-ethyl-6-phenyl-1,4-phenylene ether) (103 mg, 35%). Mw by gel permeation chromatography (GPC) of (2-ethyl-6-phenyl-1,4-phenylene ether) was 8.8 × 10 ⁴ and Mn was 2.3 × 10 ⁴ . In addition, according to the grade of washing | cleaning of a deposit, two types of compositions with the chloride ion content contained in a final polymer 300 ppm (Example 1) and 1500 ppm (Example 2) were obtained.

7) Fabrication of substrate A predetermined amount of the obtained two kinds of poly (2-ethyl-6-phenyl-1,4-phenylene ether) resin compositions was packed in a 40 mm × 25 mm mold, and the molding temperature was 190 ° C. Heat press-molding was performed under molding conditions of a pressure of 2.9 × 10 ⁶ Pa and a press time of 1 hour to produce a substrate having a thickness of about 1 mm. A stick having a length of 40 mm, a width of 1 mm, and a thickness of 1 mm was cut out from the obtained substrate, and a relative dielectric constant ε and a Q value (= 1 / tan δ) at 5 GHz were obtained by a cavity resonator perturbation method.

Examples 3 to 5 and Comparative Examples 1 and 2: Synthesis of poly (2,6-dimethyl-1,4-phenylene ether) 2-methylphenol instead of 2-phenylphenol (1) in Example 1 as a starting material Then, in Example 1 (2), iodomethane was allowed to act instead of N, N-dimethylformamide to obtain 2,6-dimethylanisole. Thereafter, 2,6-dimethylphenol was obtained according to the processes of (5) and (6) of Example 1, and this was polymerized to obtain various poly (2,6-dimethyl-1,4-phenylene ether). It was. Mw and Mn by GPC of the obtained polymer are as shown in Table 1 below. Depending on the degree of washing of the precipitate, the chloride ion content contained in the final polymer is 0 ppm (Example 3), 700 ppm (Example 4), 1500 ppm (Example 5), 1600 ppm (Comparative Example 1) and Each composition of 2700 ppm (Comparative Example 2) was obtained.

Predetermined amounts of the five types of poly (2,6-dimethyl-1,4-phenylene ether) resin compositions obtained were packed in a 40 mm × 25 mm mold, a molding temperature of 250 ° C., a molding pressure of 2.9 × 10 ^6. Heat and pressure press molding was performed under molding conditions of Pa and a press time of 1.5 hours to produce a substrate having a thickness of about 1 mm. A stick having a length of 40 mm, a width of 1 mm, and a thickness of 1 mm was cut out from the obtained substrate, and a relative dielectric constant ε and a Q value (= 1 / tan δ) at 5 GHz were obtained by a cavity resonator perturbation method.

  The evaluation results for the polyphenylene ether resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 are shown in Table 1 below.

  From Table 1, it was clarified that in the polyphenylene ether-based resin composition, the Q value increases as the chlorine ion content decreases. In addition, the polyphenylene ether-based resin composition in which an aryl group is introduced at one of the 2,6-positions of the polyphenylene ring and the other is an alkyl group has a relatively higher Q value than both of the alkyl groups. It became clear. This result is shown in a graph as shown in FIG. 1, and it can be seen that there is a clear correlation between the chlorine ion content and the Q value.

It is a graph which shows the relationship between chloride ion content and Q value.

Claims (17)

The following general formula (I),

(Wherein R ¹ and R ² each independently represents an alkyl group or an aryl group), the main component is a polyphenylene ether resin having a repeating unit, and the chloride ion content is 1500 ppm or less. A polyphenylene ether resin composition. ^2. The polyphenylene ether-based resin composition according to claim 1, wherein, in the general formula (I), R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² represents an aryl group. 3. The polyphenylene ether-based resin composition according to claim 2, wherein, in the general formula (I), R ¹ represents an alkyl group having 4 to 10 carbon atoms, and R ² represents an aryl group. The polyphenylene ether-based resin composition according to claim 2 or 3, wherein R ² in the general formula (I) represents a phenyl group.   The polyphenylene ether-based resin composition according to any one of claims 1 to 4, wherein the chlorine ion content is 1000 ppm or less.   The polyphenylene ether resin composition according to any one of claims 1 to 5, comprising at least one of a styrene elastomer and a flame retardant. In producing the polyphenylene ether-based resin composition according to claim 1, the following general formula (II),

(Wherein R ¹ and R ² each independently represents an alkyl group or an aryl group) are polymerized while aeration of oxygen in a copper chloride solution, and the following general formula (I),

(In the formula, R ¹ and R ² each independently represents an alkyl group or an aryl group) A crude product of a polyphenylene ether resin having a repeating unit is obtained, and then the crude product has a chlorine ion of 1500 ppm or less. A method for producing a polyphenylene ether-based resin composition, wherein   The board | substrate for electronic circuits which contains the polyphenylene ether-type resin composition as described in any one of Claims 1-6 as a main body.   A substrate coated product obtained by coating the polyphenylene ether-based resin composition according to any one of claims 1 to 6 on a cloth substrate.   The substrate coated product according to claim 9, wherein the cloth substrate is a glass cloth.   A metal foil coated product obtained by coating the polyphenylene ether-based resin composition according to any one of claims 1 to 6 on a metal foil.   The metal foil coated product according to claim 11, wherein the metal foil is a copper foil.   The board | substrate for electronic circuits obtained by heat-press molding in the state which accumulated the 2 or more of the base material coated material of Claim 9 or 10.   A double-sided surface obtained by hot-press molding by sandwiching one of the substrate coated products according to claim 9 or 10 or two or more of the substrate coated materials between metal foils. Metal-clad electronic circuit board.   The board for a double-sided metal-bonded electronic circuit according to claim 14, wherein the metal foil is a copper foil.   A double-sided metal-bonded electronic circuit board obtained by heat-pressing two or more metal foil coated products according to claim 11 or 12 in a state where both outer side surfaces are metal foils.   The substrate according to claim 9 or 10, the substrate according to claim 13, or the metal according to claim 11 or 12 on one side or both sides of the double-sided metal-bonded substrate according to claim 14 or 15. A substrate for a multilayer electronic circuit obtained by heating and press-molding a foil coated product in a state where a metal foil is placed on an outer surface.

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