JP2006056981A - Resin composition, and sheet, prepreg-like material, metallic foil-clad sheet, laminated board, electrical insulation material and resist material each using the resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition with high heat resistance and high dielectric constant and low dielectric loss tangent in high-frequency region, and to provide sheets, prepreg-like materials, metallic foil-clad sheets, laminated boards, electrical insulation materials and resist materials each using the resin composition. <P>SOLUTION: The resin composition comprises a polyester, an epoxy resin, a curing promoter and dielectric powder, wherein the polyester is composed of an aromatic polycaroxylic acid residue having an aryloxycarbonyl group or arylcarbonyloxy group on the molecular chain end and an aromatic polyhydroxy compound residue. This resin composition has a dielectric constant of at least 4 and a Q-value of at least 250. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin composition, a sheet using the same, a prepreg-like material, a sheet with a metal foil, a laminate, an electrical insulating material, and a resist material.

  In recent years, with the development of electronic and information communication equipment, various characteristics have been demanded more severely for printed circuit boards, electronic components and the like. For example, there is a demand for miniaturization of a printed circuit board, and as a specific method there is a demand for shortening the signal wavelength. As shown in Equation 1, the wavelength is shorter as the dielectric constant is higher, and the circuit can be downsized.

(Formula 1)
(Wavelength) = (speed of light) / {(frequency) × (dielectric constant) ^1/2 }

  Further, since printed boards and the like are often used in devices (for example, portable terminals) including a high-frequency circuit that handles a high frequency exceeding 1 [GHz], reduction of transmission loss in a high-frequency region is required. The transmission loss is obtained as the sum of dielectric loss and conductor loss as shown in Equation 2. As shown in Formula 3, the dielectric loss is lower as the dielectric constant and dielectric loss tangent are lower. For this reason, transmission loss can be reduced by lowering the dielectric constant and the dielectric loss tangent.

(Formula 2)
(Transmission loss) = (Dielectric loss) + (Conductor loss)

(Formula 3)
(Dielectric loss) = (Coefficient) x (Frequency) x (Dielectric constant) ^1/2 x (Dielectric loss tangent)

  By the way, an epoxy resin excellent in electrical characteristics, mechanical characteristics, adhesiveness, and the like is used as an insulating material for multilayer boards used for printed boards, electronic components, and the like. In addition, compounds having active hydrogen such as amine compounds and phenol compounds are used as curing agents for epoxy resins. However, when an epoxy resin is cured using a curing agent having these active hydrogens, a highly polar hydroxy group is generated by the reaction between the epoxy group and the active hydrogen, which may lower the dielectric loss tangent. Have difficulty.

  For this reason, a method of using, for example, an ester compound composed of a carboxylic acid and an aromatic hydroxy compound as a curing agent for an epoxy resin has been proposed so as not to generate a highly polar hydroxyl group (for example, Patent Document 1). reference). This method utilizes the fact that the ester bond of an ester compound comprising a carboxylic acid and an aromatic hydroxy compound has a high reaction activity with respect to the epoxy group, and the epoxy resin is cured using this ester compound as a curing agent. In this case, since a highly polar hydroxy group is not generated, the obtained cured product can exhibit a low dielectric loss tangent.

  However, since an active ester bond exists only at the end of the molecule or molecular chain of the ester compound, even when the epoxy resin is cured using this ester compound as a curing agent, its crosslinking density does not increase, In addition, no hydrogen bond is formed inside the cured product. For this reason, the epoxy resin hardened | cured material which has high glass transition temperature (Tg) which can endure lead-free soldering was not able to be obtained.

  Among ester compounds that have high reaction activity with respect to epoxy groups, as ester compounds that give cured epoxy resins with high glass transition temperatures, all ester bonds that form molecular chains are reactive with epoxy groups. There are known polyfunctional polyesters having, for example, a polyfunctional polyester obtained from an aromatic dicarboxylic acid and an aromatic dihydroxy compound (see, for example, Patent Document 2). When such an epoxy resin is cured using such a polyfunctional polyester as a curing agent, since all ester bonds that form molecular chains can participate in the curing reaction, the crosslinking density of the cured epoxy resin is high. Thus, the glass transition temperature can be increased.

  However, since both ends of the molecular chain of such a polyfunctional polyester are highly polar hydroxy groups or carboxy groups, when this polyfunctional polyester is used as a curing agent for an epoxy resin, the hydroxy groups are In addition to remaining in the cured product, the carboxy group reacts with the epoxy group to form a hydroxy group. For this reason, it has been difficult to lower the dielectric loss tangent of the cured epoxy resin. In addition, if unreacted carboxy groups remain in the cured product, the low molecular weight aromatic dicarboxylic acid having carboxy groups is liberated by hydrolysis due to moisture absorption, and the dielectric loss tangent increases in a high humidity environment. . Furthermore, when phthalic acid or bisphenol having no bulky structure is used as the aromatic dicarboxylic acid or aromatic dihydroxy compound, the resulting polyester is easily crystallized, and the solvent for the resin composition containing the polyester Solubility in water is not sufficiently obtained.

  In addition, as in the case of the polyfunctional polyester, the ester compound in which all ester bonds forming a molecular chain can participate in the curing reaction includes both an aromatic polyvalent carboxylic acid and an aromatic polyvalent hydroxy compound. There is a polyester obtained by esterifying a hydroxy group with a monocarboxylic acid of a polyester having a hydroxy group at the terminal (see, for example, Patent Document 3). When such a polyester is used as a curing agent to cure the epoxy resin, the glass transition temperature can be increased, and the hydroxy group at the end of the molecular chain is esterified with a monocarboxylic acid, so the epoxy resin is cured. When produced, a highly polar hydroxy group is not produced.

However, since the molecular chain end of such a polyester is an alkylcarbonyloxy group or an arylcarbonyloxy group, when this polyester is used as a curing agent, a low molecular weight carboxylic acid is easily liberated by hydrolysis. Therefore, the dielectric loss tangent is not lowered, and the dielectric loss tangent increases in a high humidity environment. In addition, the dielectric constant increases.
JP 62-53327 A JP-A-5-51517 JP-A-10-101775

  Thus, a resin composition using a conventional ester compound as a curing agent has heat resistance that can withstand lead-free soldering, and cannot realize a high dielectric constant and a low dielectric loss tangent in a high frequency region. . Therefore, there has been a demand for a resin composition capable of realizing dielectric properties according to the intended use, such as excellent heat resistance, high dielectric constant and low dielectric loss tangent in a high frequency region, and a sheet using the same.

The present invention has been made in view of the above circumstances, and a resin composition capable of realizing dielectric properties according to the purpose of use, a sheet using the same, a prepreg-like material, a sheet with metal foil, a laminate, an electrical insulation It is an object to provide a material for use and a resist material.
Further, the present invention is a resin composition excellent in heat resistance and having a high dielectric constant and a low dielectric loss tangent in a high frequency region, a sheet using the same, a prepreg-like material, a sheet with metal foil, a laminate, an electrical insulating material, And it aims at providing a resist material.

In order to achieve the above object, the resin composition according to the first aspect of the present invention comprises:
Polyester comprising an aromatic polyvalent carboxylic acid residue and an aromatic polyvalent hydroxy compound residue having an aryloxycarbonyl group or an arylcarbonyloxy group at the molecular chain end, an epoxy resin, a curing accelerator, and a dielectric And having a dielectric constant of at least 4 and a Q value of at least 250.

  The aromatic polyvalent hydroxy compound residue is at least one group selected from the group consisting of groups represented by the following formulas (1) to (4), and the aromatic polyvalent carboxylic acid residue is It is at least one group selected from the group consisting of groups represented by formulas (5) to (7), and the aryloxycarbonyl group or the aryl group in the arylcarbonyloxy group is represented by the following formulas (8) to (10 And at least one aryl group selected from the group consisting of groups represented by

（１）

（式（１）中、ｋは０または１である。）

(1)

(In formula (1), k is 0 or 1.)

（２）

(2)

(In formula (2), Y represents an oxygen atom, a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, or a biphenyl group. Represents a methylene group substituted with a 9-fluorenyl group, a methylene group substituted with a phenyl group, a naphthyl group, or a biphenyl group with an alkyl group having 1 to 4 carbon atoms. n and m each represents an integer of 1 to 3)

（３）

(3)

（４）

(4)

（５）

(5)

（６）

(6)

（７）

(7)

(In the formula, A, B, D, E, and G are substituents, and each represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. A, e, and g each represent B and d each represent an integer of 0 to _3. X represents a single bond, —S—, —O—, —CO—, —CH ₂ —, —C (CH ₃ ) _2. -, or -SO ₂ - represents a).

（８）

(8)

（９）

(9)

（１０）

(10)

(In the formula, P, Q, R, T, and U are substituents and each represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or a halogen atom. P, r Is an integer of 0-5, q, t is an integer of 0-4, u is an integer of 0-3, Z is a single bond, —O—, —CO—, —CH ₂ —, —C (CH ₃ ) _2- or -SO _2- .

The dielectric powder preferably has a dielectric constant of 15 to 10,000 and a Q value of 300 to 100,000.
The dielectric powder is, for example, MgTiO ₃ , ZnTiO ₃ , Zn ₂ TiO ₄ , CaTiO ₃ , SrZrO ₃ , BaTi ₂ O ₅ , BaTiO ₄ , Ba ₂ Ti ₉ O ₂₀ , Ba ₂ (Ti, Sn) ₉ O _20. , ZrTiO ₄ , (Zr, Sn) TiO ₄ , BaNd ₂ Ti ₅ O ₁₄ , BaNd ₂ Ti ₄ O ₁₂ , BaSm ₂ TiO ₁₄ , BaO—CaO—Nd ₂ O ₃ —TiO ₂ system, BaO—SrO—Nd ₂ O ₃ —TiO ₂ system, Bi ₂ O ₃ —BaO—Nd ₂ O ₃ —TiO ₂ system, PbO—BaO—Nd ₂ O ₃ —TiO ₂ system, (Bi ₂ O ₃ , PbO) —BaO—Nd ₂ O _3- TiO ₂ system, La ₂ Ti ₂ O ₇ , Nd ₂ Ti ₂ O ₇ , (Li, Sm) TiO ₃ , Ba (Mg _1/3 Nd _2/3 ) O ₃ Ba (Zn _1/3 Ta _2/3 ) O ₃ , Ba (Zn _1/3 Nd _2/3 ) O ₃ , Sr (Zn _1/3 Nd _2/3 ) O ₃ , or one of these Including a combination of

The dielectric powder is preferably blended in an amount of 15 to 65 parts by volume with respect to 100 parts by volume of the total amount of the resin composition.
The dielectric powder is preferably blended so that the dielectric constant of the resin composition is 1 or more and the Q value is 10 or more.

It is preferable to include at least one of a styrene elastomer and a polybutadiene polymer.
Moreover, it is preferable that a flame retardant is further included. The flame retardant preferably contains at least one of a brominated aromatic flame retardant and ethane-1,2-bis (bentabromophenyl).

  The sheet according to the second aspect of the present invention is obtained by coating the resin composition according to the first aspect containing a flame retardant on a metal foil or film and semi-curing the resin composition.

  The sheet according to the third aspect of the present invention is obtained by laminating the sheets according to the second aspect or by stacking and curing a plurality of sheets.

  The prepreg-like material according to the fourth aspect of the present invention is obtained by impregnating an impregnated base material with the resin composition according to the first aspect including a flame retardant.

  The impregnated substrate is made of, for example, an E glass glass cloth, a D glass glass cloth, an NE glass glass cloth, an H glass glass cloth, a T glass glass cloth, and a polytetrafluoroethylene porous film. Selected from the group. For example, when glass cloth is selected as the impregnated substrate, it is preferable that the dielectric constant is at least 5 and the Q value is at least 200.

  The sheet according to the fifth aspect of the present invention is characterized in that one or more prepreg-like materials according to the fourth aspect of the present invention are stacked and cured.

  The sheet with metal foil according to the sixth aspect of the present invention is characterized in that one or more prepreg-like materials according to the fourth aspect of the present invention are stacked, and the metal foil is stacked on top and bottom to be cured. To do.

  The laminated board according to the seventh aspect of the present invention is characterized by being cured by sandwiching an impregnated base material between sheets according to the second aspect of the present invention.

  The electrical insulating material according to the eighth aspect of the present invention is obtained from the resin composition according to the first aspect of the present invention.

  The resist material according to the ninth aspect of the present invention is obtained from the resin composition according to the first aspect of the present invention.

  According to the present invention, there are provided a resin composition capable of realizing dielectric properties according to the purpose of use, a sheet using the same, a prepreg-like material, a sheet with metal foil, a laminate, a material for electrical insulation, and a resist material. can do.

  Hereinafter, the resin composition of the present invention, a sheet using the same, a prepreg-like material, a sheet with metal foil, a laminate, an electrical insulating material, and a resist material will be described.

  The resin composition of the present invention comprises an epoxy resin and a polyester comprising an aromatic polyvalent carboxylic acid residue and an aromatic polyvalent hydroxy compound residue having an aryloxycarbonyl group or an arylcarbonyloxy group at the molecular chain terminal ( Hereinafter, it is referred to as “polyester (A)”), a curing accelerator, and a dielectric powder. The resin composition of the present invention has a dielectric constant of at least 4 and a Q value of at least 250. By setting the dielectric constant and the Q value to be higher than those values, the wavelength shortening effect can be obtained without reducing the Q value. This resin composition preferably has a dielectric constant of 4 to 200 and a Q value of 250 to 2000.

  The epoxy resin used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule. For example, cresol novolak, phenol novolak, α-naphthol novolak, β-naphthol novolak, bisphenol A novolak, biphenyl novolak, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, biphenol, tetramethylbiphenol, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenolfluorene), dihydroxynaphthalene, etc. Glycidyl ether type epoxy resin of polyphenol, dicyclopentadiene novolac type epoxy resin obtained from dicyclopentadienyl diphenol and epichlorohydrin, naphtha Range all aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, triphenyl type epoxy resins, tetraphenyl type epoxy resins, polypropylene glycol, hydrogenated bisphenol A and other alcohol-based glycidyl ether type epoxy resins, hexahydrophthalic anhydride and dimer acid And the like, glycidyl ester type epoxy resin made from glycidyl ester, glycidyl amine type epoxy resin made from amine such as diaminodiphenylmethane, alicyclic epoxy resin, benzopyran type epoxy resin, and mixtures thereof.

  Among them, cresol novolac type epoxy resin, cresol novolac glycidyl ether type epoxy resin, phenol novolac type epoxy resin, naphthol novolac type epoxy resin, biphenyl novolac type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, triphenyl type epoxy When a resin, a tetraphenyl type epoxy resin, a dicyclopentadiene novolak type epoxy resin, a naphthalene type epoxy resin, and a brominated epoxy resin are used, a resin composition giving a cured product having excellent heat resistance can be obtained.

  The polyester (A) used in the present invention is a polyester comprising an aromatic polyvalent carboxylic acid residue and an aromatic polyvalent hydroxy compound residue having an aryloxycarbonyl group or an arylcarbonyloxy group at the molecular chain end. It can be suitably used as a curing agent for epoxy resins. This is because the ester bond of the polyester (A) has a high reaction activity with respect to the epoxy group, and when the polyester (A) is used as a curing agent, a highly polar hydroxy group is not generated. The resulting cured epoxy resin exhibits a low dielectric loss tangent. Furthermore, an increase in dielectric constant is suppressed.

  In addition, since polyester (A) also has an ester bond reactive to epoxy groups inside the molecular chain, the epoxy resin cured product using polyester (A) as a curing agent has a high crosslinking density and a glass transition. The temperature is high.

  When the polyester (A) has an aryloxycarbonyl group at the molecular chain end, a low molecular weight carboxylic acid that increases the dielectric loss tangent even if the ester bond at the crosslinking point of the resulting cured epoxy resin is hydrolyzed by moisture absorption. Does not liberate, and the resulting cured epoxy resin exhibits a low dielectric loss tangent even under high humidity conditions. Furthermore, an increase in dielectric constant is suppressed.

  Further, when the aromatic polyvalent hydroxy compound is an aromatic dihydroxy compound that gives at least one group selected from the group consisting of groups represented by formulas (1) to (4) as a residue, the formula (1) ) To (4) all have a bulky aromatic ring or alicyclic structure in the molecule, so the polyester (A) is suppressed from crystallization of the molecular chain and dissolved in an organic solvent. Excellent in properties. For this reason, when dissolving the resin composition containing polyester (A) in a solvent or adjusting a varnish, the amount of the solvent used may be small.

（１）

（式（１）中、ｋは０または１である。）

(1)

(In formula (1), k is 0 or 1.)

（２）

（式（２）中、Ｙは酸素原子、メチレン基、炭素数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、または該フェニル基、該ナフチル基、あるいは該ビフェニル基に更に炭素数１〜４のアルキル基が核置換したメチレン基を表す。ｎおよびｍは、各々１〜３の整数を表す。）

(2)

(In formula (2), Y represents an oxygen atom, a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, or a biphenyl group. Represents a methylene group substituted with a 9-fluorenyl group, a methylene group substituted with a phenyl group, a naphthyl group, or a biphenyl group with an alkyl group having 1 to 4 carbon atoms. n and m each represents an integer of 1 to 3)

（３）

(3)

（４）

(4)

  It is also preferable to use a polyester (A) having an aromatic dihydroxy compound residue represented by the following general formula (11). In this case, since the polyester (A) has an aromatic dihydroxy compound residue having a bromine atom represented by the general formula (11), the cured product of the resin composition containing the polyester (A) is excellent. Show flame retardancy.

（１１）

（式（１１）中、Ｊは−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、または−ＳＯ_２−からなる群から選ばれる二価の基を表す。）

(11)

(In formula (11), J represents a divalent group selected from the group consisting of —CH ₂ —, —C (CH ₃ ) ₂ —, or —SO ₂ —).

  The polyester (A) used in the present invention is prepared by, for example, polycondensing an aromatic polyvalent carboxylic acid and an aromatic polyvalent hydroxy compound to synthesize a polyester having a carboxy group or a hydroxyl group at both ends, It is obtained by esterifying the carboxy group with an aromatic monohydroxy compound or the hydroxyl group with an aromatic monocarboxylic acid. The polyester (A) can also be produced by a transesterification reaction or a Schotten-Baumann reaction other than the dehydration esterification reaction. In general, since the reactivity of an aromatic hydroxy compound is low, the transesterification reaction or the Schotten-Baumann reaction is preferably used.

  When utilizing the Schotten-Baumann reaction, there are an interfacial polycondensation method in which the reaction is carried out at the interface and a solution polycondensation method in which the reaction is carried out in a homogeneous solution. In the interfacial polycondensation method, an organic solution phase containing an acid halide of an aromatic polycarboxylic acid and an acid halide of an aromatic monocarboxylic acid is brought into contact with an aqueous phase containing an aromatic polyhydroxy compound, and an acid Polyester (A) can be obtained by interfacial polycondensation in the presence of a scavenger. In the solution polycondensation method, a solution containing an acid halide of an aromatic polyvalent carboxylic acid and an acid halide of an aromatic monocarboxylic acid and a solution containing an aromatic polyvalent hydroxy compound are used as an acid scavenger. A polyester (A) is obtained by mixing in the presence and dehydrohalogenation reaction.

  Hereinafter, the polyester (A) used in the present invention will be specifically described with reference to a production method utilizing the Schotten-Baumann reaction. The aromatic polyvalent hydroxy compound used for the production of the polyester (A) may be any compound having two or more aromatic hydroxy groups. For example, it is represented by the above formulas (1) to (4) and (11). Specific examples thereof include aromatic polyvalent hydroxy compounds represented by the following formulas (12) to (16).

（１２）

（式（１２）中、ｋは０または１である。）

(12)

(In the formula (12), k is 0 or 1.)

（１３）

（式（１３）中、Ｙは酸素原子、メチレン基、炭素数１〜４のアルキル基で置換されたメチレン基、フェニル基で置換されたメチレン基、ナフチル基で置換されたメチレン基、ビフェニル基で置換されたメチレン基、９−フルオレニル基で置換されたメチレン基、または該フェニル基、該ナフチル基、あるいは該ビフェニル基に更に炭素数１〜４のアルキル基が核置換したメチレン基を表す。ｎおよびｍは、１〜３の整数を表す。）

(13)

(In formula (13), Y represents an oxygen atom, a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, or a biphenyl group. Represents a methylene group substituted with a 9-fluorenyl group, a methylene group substituted with a phenyl group, a naphthyl group, or a biphenyl group with an alkyl group having 1 to 4 carbon atoms. n and m represent an integer of 1 to 3.)

（１４）

(14)

（１５）

(15)

（１６）

（式（１６）中、Ｊは−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、または−ＳＯ_２−からなる群から選ばれる二価の基を表す。）

(16)

(In formula (16), J represents a divalent group selected from the group consisting of —CH ₂ —, —C (CH ₃ ) ₂ —, or —SO ₂ —).

  Among the aromatic polyvalent hydroxy compounds represented by the above formulas (12) to (16), the polyester (A) obtained using the aromatic polyvalent hydroxy compound represented by the formula (12) is a curing agent. Since the epoxy resin cured product has a hydrophobic alicyclic structure in the structure, it absorbs less water and exhibits stable dielectric properties even in a high humidity environment.

  However, those aromatic polyhydroxy compounds represented by the formula (12) having an average value of k exceeding 0.2 may cause gelation when dissolved in a solvent to synthesize polyester. In the case of using the aromatic polyvalent hydroxy compound represented by the formula (12), one having an average value of k in the range of 0 to 0.2 is used, or the formula (13) to ( It is preferable to use a mixture with the aromatic dihydroxy compound represented by 16). When used together with the aromatic dihydroxy compound represented by the formulas (13) to (16), the amount of the aromatic polyhydroxy compound represented by the formula (12) is appropriately adjusted according to the value of k. For example, when k is 1, the amount of the aromatic polyhydroxy compound represented by the formula (12) used when synthesizing the polyester (A) is the same as the aromatic polyhydroxy compound used. It is preferable to set it as 20 mol% or less with respect to the whole quantity.

  Since the epoxy resin cured product using the polyester (A) obtained by using the aromatic dihydroxy compound represented by the general formula (16) as a curing agent has a bromine atom in the structure, the epoxy resin cured product is heated. Hydrogen bromide is generated when decomposed, and the cured epoxy resin has flame retardancy due to the oxygen blocking effect of hydrogen bromide and the effect of capturing highly active free radicals during combustion and reducing the combustion energy.

  However, when only the aromatic dihydroxy compound represented by the general formula (16) is used when synthesizing the polyester (A), the crystallinity of the polyester (A) increases, and the polyester (A) In addition to the aromatic dihydroxy compound represented by the general formula (16), an aromatic polyvalent compound that provides sufficient solvent solubility may not be obtained. It is preferable to use a hydroxy compound in combination. It is preferable that the usage-amount of the aromatic dihydroxy compound represented by General formula (16) at this time is the range of 30-60 mass% with respect to the aromatic polyvalent hydroxy compound whole quantity to be used.

  Examples of the aromatic polyvalent hydroxy compound that gives sufficient solvent solubility include compounds represented by the above formulas (12) to (15). However, when the aromatic polyhydroxy compound represented by the formula (12) is used together with the aromatic dihydroxy compound represented by the general formula (16), the aromatic polyhydroxy compound represented by the formula (12) is: It is preferable to use one having an average value of k in the range of 0 to 0.2, or to mix with an aromatic dihydroxy compound represented by the formulas (13) to (16). As described above.

  In the case of producing the polyester (A) using the Schotten-Baumann reaction, the aromatic polyvalent carboxylic acid is used in the form of an acid halide. As the halogen of the acid halide used here, chlorine or bromine is generally used. The aromatic polyvalent carboxylic acid used in the form of acid halide may be a compound having two or more carboxy groups, such as trimesic acid, trimellitic acid, pyromellitic acid, or the following general formula (17) to And aromatic dicarboxylic acid represented by (19).

（１７）

(17)

（１８）

(18)

（１９）

（一般式（１７）〜（１９）中、Ａ、Ｂ、Ｄ、Ｅ、Ｇは置換基を表し、各々炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、またはハロゲン原子を表す。ａ、ｅ、ｇは各々０〜４の整数を表し、ｂ、ｄは各々０〜３の整数を示す。Ａ〜Ｇで表される置換基は、それぞれ、すべて同一であっても異なっていてもよい。Ｘは単結合、−Ｓ−、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、または−ＳＯ_２−を表す。）

(19)

(In the general formulas (17) to (19), A, B, D, E, and G represent substituents, and each represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. A, e, and g each represent an integer of 0 to 4, and b and d each represent an integer of 0 to 3. The substituents represented by A to G are all the same or different. X represents a single bond, —S—, —O—, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, or —SO ₂ —.

  Among the aromatic polycarboxylic acids, the polyester (A) obtained from the acid halide of the aromatic dicarboxylic acid represented by the general formulas (17) to (19) has excellent solubility in various solvents. Moreover, the epoxy resin hardened | cured material which uses this polyester (A) as a hardening | curing agent shows a high glass transition temperature and a low dielectric loss tangent. Examples of the aromatic dicarboxylic acid represented by the general formulas (17) to (19) include isophthalic acid, terephthalic acid, 1,4-, 2,3-, or 2,6-naphthalenedicarboxylic acid. . Among these, polyester (A) obtained by using a mixture of isophthalic acid and terephthalic acid is particularly excellent in solubility in various solvents.

  Examples of the aromatic monohydroxy compound include aromatic monohydroxy compounds represented by the following general formulas (20) to (22).

（２０）

(20)

（２１）

(21)

（２２）

（一般式（２０）〜（２２）中、Ｐ、Ｑ、Ｒ、Ｔ、Ｕは置換基を表し、各々炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ニトロ基、またはハロゲン原子を表す。ｐ、ｒは０〜５の整数、ｑ、ｔは０〜４の整数、ｕは０〜３の整数を示す。Ｐ〜Ｕで表される置換基は、それぞれ、すべて同一であっても異なっていてもよい。Ｚは単結合、−Ｏ−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、または−ＳＯ_２−を表す。）

(22)

(In General Formulas (20) to (22), P, Q, R, T, and U each represent a substituent, each having an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or Represents a halogen atom, p and r are integers of 0 to 5, q and t are integers of 0 to 4 and u is an integer of 0 to 3. The substituents represented by P to U are all the same. Z may be a single bond, —O—, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, or —SO ₂ —.

  Examples of aromatic monohydroxy compounds represented by the general formulas (20) to (22) include phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, o-phenylphenol, p- Phenylphenol, 2-benzylphenol, 4-benzylphenol, 4- (α-cumyl) phenol, α-naphthol, β-naphthol and the like can be mentioned. Among these, epoxy resin cured products using polyester (A) using α-naphthol, β-naphthol, o-phenylphenol, p-phenylphenol, 4- (α-cumyl) phenol as a curing agent are particularly low dielectric loss tangents. Have

  As the solvent used in the organic solution phase when the polyester (A) is produced by the interfacial polycondensation method, an acid halide of an aromatic polyvalent carboxylic acid is dissolved, inert to the acid halide, and non-phase with water. Any solvent may be used, and examples thereof include toluene and dichloromethane. An aromatic polyvalent hydroxy compound and an alkali as an acid scavenger are dissolved in the aqueous phase.

  Solvents used in the production by the solution polymerization method include an acid halide of aromatic polyvalent carboxylic acid, an aromatic polyhydroxy compound, and an aromatic monohydroxy compound, and is inert to the acid halide. Any solvent can be used, and toluene, dichloromethane and the like can be used. Moreover, pyridine, triethylamine, etc. can be used as an acid scavenger used for a polycondensation reaction.

  The obtained polyester (A) is preferably purified by operations such as washing and reprecipitation to reduce the impurity content. If impurities such as monomers, halogen ions, alkali metal ions, alkaline earth metal ions, or salts remain in the polyester (A), it causes a increase in dielectric loss tangent.

  The number average molecular weight in terms of polystyrene of the polyester (A) is preferably in the range of 550 to 7000. If the number average molecular weight is less than 550, the crosslinking density of the epoxy resin cured product may not be sufficiently high, and the effect on the glass transition temperature may be insufficient. In some cases, gelation may occur.

  As a hardening accelerator used for this invention, a well-known and usual epoxy resin hardening accelerator can be used. For example, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole and 2-undecylimidazole, and organic such as triphenylphosphine and tributylphosphine Phosphine compounds, organic phosphite compounds such as trimethyl phosphite, triethyl phosphite, phosphonium salts such as ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, Benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene-7 ( (Hereinafter abbreviated as DBU) and the like, and salts of DBU with terephthalic acid or 2,6-naphthalenedicarboxylic acid, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahexyl Quaternary ammonium salts such as ammonium bromide and benzyltrimethylammonium chloride, 3-phenyl-1,1-dimethylurea, 3- (4-methylphenyl) -1,1-dimethylurea, chlorophenylurea, 3- (4- Chlorophenyl) -1,1-dimethylurea, urea compounds such as 3- (3,4-dichlorophenyl) -1,1-dimethylurea, alkalis such as sodium hydroxide and potassium hydroxide, potassium phenoxide and potassium acetate Etc. What crown salts of ether and the like, which may be used alone or plural. Of these, imidazole compounds are preferably used.

  The dielectric powder used in the present invention needs to have a higher dielectric constant (ε) and Q value than the base resin in a high frequency region of 1 GHz. As the dielectric powder, it is preferable to use a dielectric ceramic powder having a dielectric constant of 15 or more and a Q value of 300 or more. The dielectric constant is 15 to 1000, particularly about 15 to 500, and Q More preferably, the value is in the range of 300 to 100,000.

Specifically, MgTiO ₃ {ε = 17, Q = 22000}, ZnTiO ₃ {ε = 26, Q = 800}, Zn ₂ TiO ₄ {ε = 15, Q = 700}, CaTiO ₃ {ε = 170, Q = 1800}, SrZrO ₃ {ε = 30, Q = 1200}, Ba ₂ Ti ₉ O ₂₀ {ε = 90, Q = 1700}, Ba ₂ (Ti, Sn) ₉ O ₂₀ {ε = 37, Q = 5000}, ZrTiO ₄ {ε = 39, Q = 7000}, (Zr, Sn) TiO ₄ {ε = 38, Q = 7000}, BaNd ₂ Ti ₅ O ₁₄ {ε = 83, Q = 2100}, BaNd ₂ Ti ₄ O ₁₂ {ε = 92, Q = 1700}, BaSm ₂ TiO ₁₄ {ε = 74, Q = 2400}, BaO—CaO—Nd ₂ O ₃ —TiO ₂ system {ε = 90, Q = 2200}, BaO—SrO—Nd ₂ O ₃ —TiO ₂ system {ε = 90, Q = 1700}, Bi ₂ O ₃ —BaO—Nd ₂ O ₃ —TiO ₂ system {ε = 88, Q = 2000}, PbO—BaO—Nd ₂ O ₃ — TiO ₂ system {ε = 90, Q = 5200}, (Bi ₂ O ₃ , PbO) —BaO—Nd ₂ O ₃ —TiO ₂ system {ε = 105, Q = 2500}, La ₂ Ti ₂ O ₇ {ε = 44, Q = 4000}, Nd ₂ Ti ₂ O ₇ {ε = 37, Q = 1100}, (Li, Sm) TiO ₃ {ε = 81, Q = 2050}, Ba (Mg _1/3 Nd _{2 / 3} ) O ₃ {ε = 25, Q = 35000}, Ba (Zn _1/3 Ta _2/3 ) O ₃ {ε = 30, Q = 14000}, Ba (Zn _1/3 Nd _2/3 ) O _{3 {ε = 41, Q = 9200} }, Sr (Zn 1/3 Nd 2/3) O 3 {ε = 40, = 4000 as a main component composition of}, may be used one or two or more kinds.

  The shape of the dielectric powder may be any of crushed, spherical, cylindrical, needle-like, and indeterminate, and can be properly used depending on the required physical properties, etc. One or more types may be blended and mixed .

  The particle size of the dielectric powder is preferably in the range of 0.01 to 100 μm, more preferably in the range of 0.2 to 20 μm in terms of average particle size. When the particle size is smaller than the above range, the viscosity of the paste is increased and the melt viscosity is increased, which may cause poor sheet formation and poor adhesion during formation of the multilayer substrate. If the particle size is larger than the above range, the dielectric powder may settle when the paste is produced, and dispersion may not be sufficient. Further, the particle size of the dielectric powder needs to be smaller than the thickness of the sheet to be formed. Specifically, the average particle size of the dielectric powder is preferably 1/2 or less of the sheet thickness.

  The compounding amount of the epoxy resin and polyester (A) contained in the resin composition of the present invention is such that the aryloxycarbonyl group or arylcarbonyloxy group in the polyester (A) is 0 with respect to 1 mol of the epoxy group in the epoxy resin. A blending amount of 15 to 5 mol is preferable, and a blending amount of 0.5 to 2.5 mol is more preferable. When the blending amount of the polyester (A) is outside this range, the curing reaction of the epoxy resin by the polyester (A) does not proceed sufficiently, and the effect on the dielectric loss tangent and the glass transition temperature becomes insufficient.

  It is preferable that the compounding quantity of a hardening accelerator is the range of 0.01-5 mass parts with respect to 100 mass parts of epoxy resins. When the blending amount of the curing accelerator is less than 0.01 parts by mass, the curing reaction rate is slow, and when it exceeds 5 parts by mass, self-polymerization of the epoxy resin occurs and the curing reaction of the epoxy resin by the polyester (A) is inhibited. Sometimes.

  About the compounding ratio of the dielectric powder and the resin composition, for example, when the total amount of the solid content of the resin composition and the dielectric powder is 100 parts by volume, it may be in the range of 15 to 65 parts by volume. The dielectric constant, the Q value, and other physical properties can be selected as appropriate. When the blending amount is less than the above range, it is difficult to obtain the effect of improving the dielectric constant and Q value by adding the dielectric powder. Specifically, the dielectric constant of the resin composition is preferably increased by 1 or more by blending the dielectric powder, and the Q value is preferably increased by 10 or more, but when the blending amount is less than the above range, The dielectric constant does not increase by 1 or more, and the Q value does not increase by 10 or more. On the other hand, when the blending amount is larger than the above range, it becomes difficult to form a paste, and at the same time, an increase in melt viscosity is caused, which may cause poor sheet formation and poor adhesion during formation of the multilayer substrate.

  Furthermore, you may use a well-known flame retardant for the flame retardance of an epoxy resin as needed. As the flame retardant, known and commonly used flame retardants such as brominated aromatic, condensed phosphate ester, metal hydroxide, antimony, and phosphorus can be used. In particular, brominated aromatic flame retardants have bromine atoms in the structure, so hydrogen bromide is generated when the epoxy resin cured product is thermally decomposed, and the oxygen blocking effect of hydrogen bromide and high activity during combustion. With the effect of trapping free radicals and reducing combustion energy, excellent flame retardancy can be imparted to the resin composition. Moreover, it is preferable because it is difficult to deteriorate the transmission loss of the cured product of the resin composition. A particularly preferred flame retardant from this point of view is ethane-1,2-bis (bentabromophenyl).

  Furthermore, a flexibility imparting material such as a styrene-based elastomer and a polybutadiene-based polymer may be used for the purpose of improving the handleability when formed into a sheet and lowering the elastic modulus of the cured product. As the styrenic elastomer, styrene and one or more selected from polybutadiene, polyisoprene, poly (ethylene / butylene), poly (ethylene / propylene), poly (vinyl / isopropylene), and polyethylene are used. A diblock copolymer or a triblock copolymer is mentioned. Further, as the polybutadiene-based polymer, a polymer obtained by epoxidizing a part of double bonds of 1,2-polybutadiene or 1,4-polybutadiene can be used.

  When a resin composition is coated on a metal foil or film and semi-cured to produce a sheet (details of the production method will be described later), if the flexibility of the resin composition is insufficient, cracking and handling properties will occur. There are cases where problems such as lowering of resin and dropping of resin (powder falling) occur during cutting. Therefore, when the above-described flexibility imparting material is added to the resin composition, when the resin composition is semi-cured to the B stage state, the semi-cured material exhibits excellent flexibility, You can prevent problems.

  It should be noted that the flexibility imparting material is not essential, and it is not necessary to add it in applications where flexibility is not required for the semi-cured product. Examples of such uses include use of impregnating a resin composition into an impregnated base material such as glass cloth to produce a prepreg-like material.

  The flexibility imparting material is preferably added in an amount of 5 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin. If the amount of the flexibility-imparting material is less than the above, there is almost no modification effect of the resin composition, and the brittle physical properties may not be improved. In addition, if the above is exceeded, the original physical properties of the resin composition cannot be exhibited, the solid content concentration cannot be increased when blended in a solvent, the solution viscosity is increased, and there is a risk of problems such as an increase in water absorption. There is.

  Although the organic solvent used for the resin composition of this invention changes with kinds of epoxy resin to be used, what is necessary is just a thing which can melt | dissolve an epoxy resin, polyester (A), and a hardening accelerator uniformly. Examples include amide solvents such as N-methylpyrrolidone, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, Examples include ether solvents such as 1,3-dioxolane and anisole, aromatic hydrocarbon solvents such as toluene and xylene, and monoether glycol solvents such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether. It can be used by mixing.

  The resin composition of the present invention is, for example, a desired type such as polyester (A), epoxy resin, curing accelerator, dielectric powder, organic solvent, flame retardant added as necessary, and flexibility imparting material. And an amount of additives can be prepared by mixing uniformly.

  The liquid mixture of the resin composition thus obtained can be cured and molded by a known and commonly used thermosetting method. For example, the varnish is prepared by the above mixed solution, and the varnish is applied to a substrate such as a metal foil or a film and poured into a mold, or impregnated into an impregnated substrate such as a glass cloth substrate, and then dried by heating. And the like, after removing the solvent and pre-curing the resin, press molding while heating again.

  The resin composition of the present invention can be applied to a metal foil or film and semi-cured to obtain a sheet. Examples of the metal foil include copper foil, gold foil, silver foil, aluminum foil, nickel-chrome foil, nickel foil and the like. Examples of the film include polyester such as polyethylene terephthalate and polyimide. Further, the sheets can be bonded together, or a plurality of sheets can be stacked and cured to form a sheet.

  Moreover, the impregnating substrate can be impregnated with the resin composition of the present invention to obtain a prepreg-like material. Here, the impregnated base material is a porous base material for impregnating the liquid composition such as the varnish, and in particular, a glass cloth of E glass, a glass cloth of D glass, a glass cloth of NE glass, H A glass cloth made of glass, a glass cloth made of T glass, and a porous film of polytetrafluoroethylene are preferred.

  For example, when glass cloth is selected as the impregnated substrate, it is preferable that the prepreg-like material has a dielectric constant of at least 5 and a Q value of at least 200. By setting the dielectric constant and the Q value to be higher than those values, the wavelength shortening effect can be obtained without reducing the Q value.

  One or more prepreg materials can be stacked and cured to form a sheet. In addition, one or more prepreg-like materials can be stacked, and a metal foil can be stacked on top and bottom to be cured to obtain a sheet with metal foil. Further, an impregnated base material is sandwiched between sheets and cured to obtain a laminate.

  Since such a sheet, a prepreg-like material, a sheet with metal foil, a laminate, an electrical insulating material, and a resist material are manufactured using the resin composition of the present invention, a high dielectric constant, a low dielectric loss tangent It has high heat resistance and flame retardancy, and the dielectric constant and dielectric loss tangent are unlikely to increase even in a high humidity environment.

  There is no particular limitation on the coating method at the time of producing the sheet or the sheet with metal foil, and a known method may be used. Specific examples include a doctor blade method, a spin coating method, a curtain coating method, a spray coating method, and a screen printing method.

  Although the film thickness obtained is not particularly limited, it is preferably in the range of 1 to 1000 μm, and more preferably in the range of 1 to 100 μm from the viewpoint of film formability and economy. Specifically, if it is 1 μm or less, it is difficult to form a continuous film, although depending on the substrate, and if the film thickness is 1000 μm or less, there are problems that it takes a very long time to dry the solvent and a smooth coated surface cannot be obtained.

  As described above, according to the present embodiment, an aromatic polyvalent carboxylic acid residue having an aryloxycarbonyl group or an arylcarbonyloxy group at the molecular chain end and an aromatic polyvalent hydroxy compound residue are comprised. By using polyester (A) as a curing agent for the epoxy resin composition, a highly polar hydroxy group is not generated during curing, and a cured resin product having a low dielectric loss tangent is obtained. The cured product does not liberate a low molecular weight carboxylic acid that increases the dielectric loss tangent by hydrolysis accompanying moisture absorption, and exhibits a low dielectric loss tangent even under high humidity conditions. Furthermore, an increase in dielectric constant is suppressed. In addition, since the polyester chain (A) is used as a curing agent for the epoxy resin because the ester bond having an activity reactive to the epoxy group is also present in the molecular chain, the crosslinking density of the cured epoxy resin is increased, and the glass transition temperature. And a cured product excellent in heat resistance can be obtained. Further, since the dielectric powder is included so that the dielectric constant is at least 4 and the Q value is at least 250, a high dielectric constant and a low dielectric loss tangent can be realized. In addition, the dielectric constant and the Q value can be freely controlled according to the purpose, such as obtaining a wavelength shortening effect without lowering the Q value.

  Hereinafter, the present invention will be described more specifically with reference to examples.

<Synthesis Example 1>
Into a reaction vessel, 1000 ml of water and 20 g of sodium hydroxide were placed, and in a nitrogen stream, the amounts of aromatic monohydroxy compound and aromatic polyhydroxy compound of the amount shown in the column of Synthesis Example 1 in Table 1 were charged, and Ferdler The mixture was stirred for 1 hour at 300 rpm with a blade. Next, a solution prepared by dissolving the acid halide of the aromatic polyvalent carboxylic acid in an amount shown in the column of Synthesis Example 1 in Table 1 in 1000 ml of methylene chloride was dropped into a reaction vessel maintained at 30 ° C. over 15 seconds. Stirring was continued for 4 hours. The resulting mixture is allowed to stand and remove to remove the aqueous phase, and the remaining methylene chloride phase is washed with a 0.5% strength aqueous sodium hydroxide solution and the aqueous phase is removed three times. Washing with ionic water and removal of the aqueous phase were repeated three times. After the washed methylene chloride phase was concentrated to 400 ml, 1000 ml of heptane was added dropwise over 15 seconds, and the precipitate was washed with methanol, filtered and dried to obtain polyester (A1).

<Synthesis Examples 2 and 3>
In the synthesis example 1, instead of the aromatic monohydroxy compound and the aromatic polyhydroxy compound in the amount shown in the synthesis example 1 column of Table 1, the fragrance in the amount shown in the synthesis examples 2 and 3 column of Table 1 Polyesters (A2) and (A3) were obtained in the same manner as in Synthesis Example 1 except that an aromatic monohydroxy compound and an aromatic polyvalent hydroxy compound were used.

<Synthesis Example 4>
1000 ml of water and 20 g of sodium hydroxide are placed in a reaction vessel, and an aromatic monohydroxy compound in the amount shown in the column of Synthesis Example 4 in Table 1 is charged in a nitrogen stream, and 1 at 300 revolutions per minute by a Faddler blade. Stir for hours. Next, a solution prepared by dissolving an acid halide of an aromatic polyvalent carboxylic acid in an amount shown in the column of Synthesis Example 4 in Table 1 in 1000 ml of methylene chloride was dropped into a reaction vessel maintained at 30 ° C. over 15 seconds. Stirring was continued for 4 hours. The resulting mixture is allowed to stand and remove to remove the aqueous phase, and the remaining methylene chloride phase is washed with a 0.5% strength aqueous sodium hydroxide solution and the aqueous phase is removed three times. Washing with ionic water and removal of the aqueous phase were repeated three times. After the methylene chloride phase after washing was concentrated to 400 ml, 1000 ml of heptane was added dropwise over 15 seconds, and the precipitate was washed with methanol, filtered and dried to obtain ester (B1).

<Synthesis Example 5>
In a reaction vessel, 1000 ml of water and 20 g of sodium hydroxide were placed, and in a nitrogen stream, the amounts of aromatic monocarboxylic acid and aromatic polyvalent hydroxy compound shown in the column of Synthesis Example 5 in Table 1 were charged, and Ferdler The mixture was stirred for 1 hour at 300 rpm with a blade. Next, a solution prepared by dissolving an acid halide of an aromatic polyvalent carboxylic acid in an amount shown in the column of Synthesis Example 5 in Table 1 in 1000 ml of methylene chloride was dropped into a reaction vessel maintained at 30 ° C. over 15 seconds. Stirring was continued for 4 hours. The resulting mixture is allowed to stand and remove to remove the aqueous phase, and the remaining methylene chloride phase is washed with a 0.5% strength aqueous sodium hydroxide solution and the aqueous phase is removed three times. Washing with ionic water and removal of the aqueous phase were repeated three times. After the methylene chloride phase after washing was concentrated to 400 ml, 1000 ml of heptane was added dropwise over 15 seconds, and the precipitate was washed with methanol, filtered and dried to obtain polyester (A4).

<Synthesis Example 6>
In Synthesis Example 5, instead of the aromatic polyvalent hydroxy compound and aromatic monocarboxylic acid in the amount shown in Synthesis Example 5 in Table 1, the amount of aromatic polyvalent in the amount shown in Synthesis Example 6 in Table 1 was used. A polyester (A5) was obtained in the same manner as in Synthesis Example 5 except that a monovalent hydroxy compound and an aromatic monocarboxylic acid were used.

<Synthesis Example 7>
Into a reaction vessel, 400 ml of tetrahydrofuran was placed, in a nitrogen stream, 11 g of triethylamine and 5.1 g of resorcinol were dissolved, and a solution prepared by dissolving 5.1 g of isophthalic acid chloride in 100 ml of tetrahydrofuran was added dropwise over 30 minutes while cooling with ice. After stirring for 4 hours, a solution prepared by dissolving 19.9 g of p-acetoxybenzoic acid chloride in 100 ml of tetrahydrofuran was added dropwise. After completion of dropping, the solution was poured into a 5% strength aqueous sodium carbonate solution, and the precipitate was filtered with suction, washed with water and methanol, dried under reduced pressure, and polyester (H1) represented by the following formula (23) ( The number average molecular weight 2900) was obtained.

（２３）

(23)

<Synthesis Example 8>
1000 ml of water and 20 g of sodium hydroxide were placed in a reaction vessel, and 45.7 g of bisphenol A and 1.2 g of tetrabutylammonium bromide were dissolved in a nitrogen stream. To a reaction vessel kept at 30 ° C., 1000 ml of a methylene chloride solution in which 32.5 g of isophthalic acid chloride and 8.1 g of terephthalic acid chloride were dissolved was dropped in 30 seconds. After stirring for 1 hour, the mixture was allowed to stand for liquid separation, and the aqueous phase was removed. The remaining methylene chloride phase was washed with a 0.5% strength aqueous sodium hydroxide solution and the aqueous phase was removed three times. Further, washing with deionized water and removal of the aqueous phase were repeated three times. After the methylene chloride phase after washing was concentrated to 400 ml, 1000 ml of heptane was added dropwise over 15 seconds, and then the precipitate was washed with methanol, filtered and dried to obtain a polyester represented by the following formula (24) ( H2) (number average molecular weight 8600) was obtained.

（２４）

(24)

<Synthesis Example 9>
A reaction vessel was charged with a solution of 152 g of trimethylhydroquinone in a mixed solvent of 500 g of toluene and 200 g of ethylene glycol monoethyl ether, and 4.6 g of p-toluenesulfonic acid was added to the solution, and 64 g of benzaldehyde was added dropwise. It stirred at 120 degreeC for 15 hours, distilling a water | moisture content. Next, the precipitated crystals were cooled and filtered, and washed repeatedly with water until the filtrate became neutral to obtain dihydroxybenzopyran represented by the following formula (25).

（２５）

(25)

<Synthesis Example 10>
A reaction vessel was charged with 187 g of dihydroxybenzopyran represented by the above formula (25), 463 g of epichlorohydrin, 53 g of n-butanol, and 2.3 g of tetraethylbenzylammonium chloride, dissolved in a nitrogen stream, and co-resisted at a temperature of 65 ° C. After reducing the pressure to boiling, 82 g of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours and stirred for 30 minutes. Unreacted epichlorohydrin was distilled off under reduced pressure, and then 550 g of methyl isobutyl ketone and 55 g of n-butanol were added to the resulting solution. 15 g of 10% aqueous sodium hydroxide solution was added and reacted at 80 ° C. for 2 hours. The reaction product was washed with water to obtain a benzopyran type epoxy resin represented by the following formula (26).

（２６）

(26)

The aromatic polyvalent hydroxy compounds shown in Table 1 each represent the following.
DHDBP: Dihydroxybenzopyran (in formula (13), Y is a methylene group substituted with a phenyl group, n and m are both 3, and the aromatic represented by formula (25) obtained in Synthesis Example 9 Polyvalent hydroxy compound, hydroxy group equivalent 187 g / eq).
DCPDDP: dicyclopentadienyl diphenol “DPP-6085” manufactured by Japan Petroleum Corporation (aromatic dihydroxy compound in which the average value of k is 0.16 in formula (12), hydroxy group equivalent 165 g / eq).
DHDN: dihydroxy dinaphthalene (aromatic dihydroxy compound represented by the formula (14). Hydroxy group equivalent 143 g / eq) manufactured by Tokyo Chemical Industry Co., Ltd.

<Examples 1-15>
The polyesters A1 to A5 and the ester B1 obtained in Synthesis Examples 1 to 3 and 5 to 6 are used as curing agents, and these curing agents and epoxy resins, curing accelerators, dielectric powders, solvents, and flame retardants as necessary. Styrene-based elastomers and the like were mixed at 25 ° C. with the composition shown in Table 2 to prepare a varnish composed of a resin composition.

<Comparative Examples 1-8>
The varnish which consists of a resin composition was produced using the method similar to an Example with the composition shown in Table 3. FIG.

  The epoxy resins, curing accelerators, dielectric powders, flame retardants, and styrenic elastomers shown in Tables 2 and 3 respectively represent the following. Moreover, the numerical value of the column of the epoxy resin of Table 2 and Table 3, a hardening | curing agent, a hardening accelerator, dielectric powder, a solvent, a flame retardant, and a styrene-type elastomer represents mass (g).

EPICLON HP-7200H: a dicyclopentadiene novolac type epoxy resin (epoxy equivalent 280 g / eq) manufactured by Dainippon Ink and Chemicals, Inc.
Benzopyran-type epoxy resin (epoxy equivalent 265 g / eq).
DMAP: 4-dimethylaminopyridine.
BaNd ₂ Ti ₄ O ₁₂ dielectric powder: manufactured by TDK Corporation (average particle size 1.6 μm, ε = 92, Q = 1700).
MgTiO ₃ dielectric powder: manufactured by Kyoritsu Material (ε = 17, Q = 22000).
Ba ₂ Ti ₉ O ₂₀ dielectric powder: manufactured by TDK Corporation (average particle size 1.7 μm, ε = 39, Q = 9000).
KBM573: A silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.
SAYTEX 8010: Ethane-1,2-bis (pentabromophenyl) manufactured by Albemarle Corporation.
KRATON G1701: a styrene-ethylene-propylene diblock copolymer made of Kraton polymer.

  Using the resin compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 8, semi-cured sheets, RCCs, prepreg-like sheets, and cured products of Examples 1 to 15 and Comparative Examples 1 to 8 by the following method Sheets, cured sheets with double-sided copper foil, cured sheets with glass cloth, cured sheets with glass cloth with double-sided copper foil, and cured sheets with glass cloth with double-sided copper foil were produced.

[Semi-cured sheet, semi-cured sheet with one side copper foil (RCC)]
The varnish composed of the resin composition obtained in Examples 1 to 15 and Comparative Examples 1 to 8 was coated by controlling the gap with a doctor blade using a horizontal coating machine (manufactured by Hirano Techseed).
A polyethylene terephthalate sheet (thickness 50 μm) or 18 μm electrolytic copper foil (Nikko Materials JTC foil) is used for the support, the gap is 100 to 150 μm, the speed is 0.3 m / min, and the drying is hot air at 120 ° C./5 minutes. It performed by drying and wound up with the roll to roll. This was cut into a size of 100 × 100 mm to obtain a semi-cured sheet with a single-sided PET support and a semi-cured sheet with a single-sided copper foil having an insulating layer thickness of 50 μm.
For Comparative Examples 1 to 8, a semi-cured sheet with a PET support on one side and a semi-cured sheet with a copper foil on one side with a copper foil on one side were prepared by the same procedure.

[Prepreg sheet]
Using a vertical impregnation coating apparatus (manufactured by Ichikin Engineering Co., Ltd.), a glass cloth (1080 type, E glass, manufactured by Asahi Shovel Co., Ltd.) is impregnated with the varnish comprising the resin composition obtained in Examples 1-15. Coating was performed. The coating speed was 0.3 m / min, the gap was 300 μm, the drying conditions were 80 ° C./5 minutes + 120 ° C./5 minutes, and the film was wound up by a roll to roll. Furthermore, it cut | judged to 100x100 mm and obtained the prepreg-like sheet | seat which concerns on Examples 1-15 of thickness 100 micrometers.
For Comparative Examples 1 to 8, prepreg-like sheets were produced by the same procedure.

[Hardened material sheet]
The semi-cured sheets according to Examples 1 to 15 and Comparative Examples 1 to 8 were attached on a hot plate heated to 100 ° C., and the support removal was repeated 16 times to obtain a thick semi-cured sheet having a thickness of 0.8 mm. Furthermore, using a high-temperature vacuum press (KVHC type, manufactured by Kitagawa Seiki Co., Ltd.), 4 ° C./min→130° C./60 min keep → 4 ° C./min→190° C./3 hours, pressure 1 MPa Pressed. The thickness of the obtained cured product sheet was 0.7 mm.

[Curing sheet with double-sided copper foil]
The semi-cured sheets with the copper foils according to Examples 1 to 15 and Comparative Examples 1 to 8 are overlapped with the insulating layer (resin layer), and a high-temperature vacuum press (KVHC type, manufactured by Kitagawa Seiki Co., Ltd.) is used. 4 ° C./min→130° C./60 minutes keep → 4 ° C./min→190° C./3 hours, high pressure vacuum press was performed under the conditions of 2 MPa pressure. The thickness of the obtained cured sheet with double-sided copper foil was 0.12 mm.

[Hardened glass cloth sheet]
Eight prepreg-like sheets according to Examples 1 to 15 and Comparative Examples 1 to 8 were stacked and kept at 4 ° C./minute→130° C./60 minutes using a high-temperature vacuum press (KVHC type, manufactured by Kitagawa Seiki Co., Ltd.) → High-temperature vacuum pressing was performed under the conditions of 4 ° C./min→190° C./3 hours and a pressure of 1 MPa. The thickness of the obtained glass cloth-containing cured product sheet was 0.7 mm.

[Hardened glass cloth sheet with double-sided copper foil]
18 μ-thick electrolytic copper foil (manufactured by Nikko Materials Co., Ltd., JTC foil) is superimposed on the upper and lower surfaces of the prepreg sheets according to Examples 1 to 15 and Comparative Examples 1 to 8, and high temperature vacuum press (KVHC type, Kitagawa Seiki) 4 ° C./min→130° C./60 min keep → 4 ° C./min→190° C./3 hours under a pressure of 2 MPa. The thickness of the obtained glass cloth-containing cured sheet with double-sided copper foil was 0.1 mm.

[Hardened glass cloth sheet 2 with double-sided copper foil]
A glass cloth (1080 type, E glass, manufactured by Asahi Shovel Co.) is sandwiched between semi-cured sheets with copper foil according to Examples 1 to 15 and Comparative Examples 1 to 8, and a high-temperature vacuum press (KVHC type, Kitagawa Seiki Co., Ltd.) 4 ° C./min→130° C./60 minutes keep → 4 ° C./min→190° C./3 hours under a pressure of 2 MPa. The thickness of the obtained glass cloth-containing cured sheet with double-sided copper foil was 0.15 mm.

  The RCC, cured product sheet, and glass cloth-containing cured product sheet produced as described above were evaluated by the following methods. The results are shown in Table 4.

(Coating property)
About the semi-hardened sheet | seat (RCC) with a single-sided copper foil, the applicability of the coating by the doctor blade using the horizontal type coating machine (made by Hirano Tech Seed) was evaluated by visual observation. As a result of visual observation, good ones were marked with ◯, and other ones with x.

(Press fluidity)
About single-sided copper foil semi-cured sheet (RCC), cut into 100mm square, press at 4 ℃ / min → 130 ℃ / 60min, pressure of 2MPa with high temperature vacuum press, and calculate by the following formula did. Judgment criteria were ○ when the outflow rate was 5% or more, and x when it was less.
Outflow rate (%) = (sheet area after pressing−sheet area before pressing) × 100 / sheet area before pressing

(RCC flexibility)
About the semi-cured sheet with single-sided copper foil (RCC), each cut to 100 mm square, wound around a stainless steel rod with a diameter of 2 mm at 25 ° C. so that the insulating layer is on the outside, and those that are not cracked or peeled off. Those not so were marked with x.

(Dielectric properties)
About a hardened | cured material sheet and a glass cloth containing hardened | cured material sheet | seat, the epoxy resin hardened | cured material after storing for 24 hours in 23 degreeC and a humidity 50% room | chamber interior after absolute drying by the perturbation method which is a TDK original measuring method, and 85 degreeC / 85 After absorbing water for 96 hours in a% RH constant temperature and humidity chamber, the dielectric constant and Q value (reciprocal of dielectric loss tangent) at 2 GHz of the cured epoxy resin stored for 24 hours in a 50% humidity room were measured.

(Copper foil peeling (peel strength) test)
Based on JIS C 6481, the strength of the cured product sheet and the glass cloth-containing cured product sheet was measured when the foil having a width of 10 mm was peeled off at a speed of 50 mm / min.

(Bending strength / elastic modulus)
The cured product sheet was cut into 25 × 50 × 0.8 mm and measured by a method based on JIS C 6481.

(Glass transition temperature (Tg))
About the hardened | cured material sheet | seat and the glass cloth containing hardened | cured material sheet | seat, the temperature of the peak value of tan-delta in 1 Hz was measured as a glass transition temperature with the viscoelasticity spectrometer "DMS200" by Seiko Electronic Industry Co., Ltd.

(UL-94 flame resistance test)
About the hardened | cured material sheet | seat and the glass cloth containing hardened | cured material sheet | seat, the thing which passed was set to V-0 by the vertical combustion test based on the specification of UL-94, and the disqualified thing was set to x.

(Solder heat resistance test)
About the hardened | cured material sheet | seat and the glass cloth containing hardened | cured material sheet | seat, the state of the epoxy resin hardened | cured material immersed for 120 second in a 300 degreeC solder bath was evaluated visually by the method based on JIS-C-6481. When there was no blistering or cracking by visual inspection, the circle was marked with ○, and when blistering or cracking occurred, x was marked.

  As is clear from the results shown in Table 4, in the various sheets of Examples 1 to 15 produced using the resin composition of the present invention, the printed sheet has a high dielectric constant and Q value, and has a peel strength, It was confirmed that various physical properties required for materials for electronic parts are excellent. In Examples 1 and 9, the RCC flexibility was evaluated as x, but this was due to strict evaluation based on the evaluation criteria, and no problem occurred in actual use.

Claims (19)

  Polyester comprising an aromatic polyvalent carboxylic acid residue and an aromatic polyvalent hydroxy compound residue having an aryloxycarbonyl group or an arylcarbonyloxy group at the molecular chain end, an epoxy resin, a curing accelerator, and a dielectric A resin composition comprising a powder, having a dielectric constant of at least 4 and a Q value of at least 250. The aromatic polyvalent hydroxy compound residue is at least one group selected from the group consisting of groups represented by the following formulas (1) to (4), and the aromatic polyvalent carboxylic acid residue is It is at least one group selected from the group consisting of groups represented by formulas (5) to (7), and the aryloxycarbonyl group or the aryl group in the arylcarbonyloxy group is represented by the following formulas (8) to (10 The resin composition according to claim 1, wherein the resin composition is at least one aryl group selected from the group consisting of groups represented by:

(1)

(In formula (1), k is 0 or 1.)

(2)

(In formula (2), Y represents an oxygen atom, a methylene group, a methylene group substituted with an alkyl group having 1 to 4 carbon atoms, a methylene group substituted with a phenyl group, a methylene group substituted with a naphthyl group, or a biphenyl group. Represents a methylene group substituted with a 9-fluorenyl group, a methylene group substituted with a phenyl group, a naphthyl group, or a biphenyl group with an alkyl group having 1 to 4 carbon atoms. n and m each represents an integer of 1 to 3)

(3)

(4)

(5)

(6)

(7)

(In the formula, A, B, D, E, and G are substituents, and each represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. A, e, and g each represent B and d each represent an integer of 0 to _3. X represents a single bond, —S—, —O—, —CO—, —CH ₂ —, —C (CH ₃ ) _2. -, or -SO ₂ - represents a).

(8)

(9)

(10)

(In the formula, P, Q, R, T, and U are substituents and each represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or a halogen atom. P, r Is an integer of 0-5, q, t is an integer of 0-4, u is an integer of 0-3, Z is a single bond, —O—, —CO—, —CH ₂ —, —C (CH ₃ ) _2- or -SO _2- .   The resin composition according to claim 1, wherein the dielectric powder has a dielectric constant of 15 to 10,000 and a Q value of 300 to 100,000. The dielectric powder is MgTiO ₃ , ZnTiO ₃ , Zn ₂ TiO ₄ , CaTiO ₃ , SrZrO ₃ , BaTi ₂ O ₅ , BaTiO ₄ , Ba ₂ Ti ₉ O ₂₀ , Ba ₂ (Ti, Sn) ₉ O ₂₀ , ZrTiO. ₄ , (Zr, Sn) TiO ₄ , BaNd ₂ Ti ₅ O ₁₄ , BaNd ₂ Ti ₄ O ₁₂ , BaSm ₂ TiO ₁₄ , BaO—CaO—Nd ₂ O ₃ —TiO ₂ system, BaO—SrO—Nd ₂ O ₃ -TiO _{2 system, Bi 2 O 3 -BaO-Nd} 2 O 3 -TiO 2 _{system, PbO-BaO-Nd 2 O} 3 -TiO 2 _{system, (Bi 2 O 3, PbO} ) -BaO-Nd 2 O 3 - TiO ₂ , La ₂ Ti ₂ O ₇ , Nd ₂ Ti ₂ O ₇ , (Li, Sm) TiO ₃ , Ba (Mg _1/3 Nd _2/3 ) O ₃ , Ba ( Zn _1/3 Ta _2/3 ) O ₃ , Ba (Zn _1/3 Nd _2/3 ) O ₃ , Sr (Zn _1/3 Nd _2/3 ) O ₃ , or a combination thereof The resin composition according to claim 1, wherein the resin composition is contained.   The resin composition according to any one of claims 1 to 4, wherein the dielectric powder is blended in an amount of 15 to 65 parts by volume with respect to 100 parts by volume of the total amount of the resin composition.   6. The dielectric powder according to claim 1, wherein the dielectric powder is blended so that a dielectric constant of the resin composition is increased by 1 or more and a Q value is increased by 10 or more. Resin composition.   The resin composition according to claim 1, further comprising at least one of a styrene elastomer and a polybutadiene polymer.   The resin composition according to any one of claims 1 to 7, further comprising a flame retardant.   9. The resin composition according to claim 8, wherein the flame retardant contains at least one of a brominated aromatic flame retardant and ethane-1,2-bis (bentabromophenyl).   A sheet obtained by applying the resin composition according to claim 8 or 9 to a metal foil or film and semi-curing the sheet.   A sheet obtained by laminating the sheets according to claim 10 or by stacking and curing a plurality of sheets.   A prepreg-like material obtained by impregnating an impregnated base material with the resin composition according to claim 8 or 9.   The impregnated base material is selected from the group consisting of a glass cloth of E glass, a glass cloth of D glass, a glass cloth of NE glass, a glass cloth of H glass, a glass cloth of T glass, and a polytetrafluoroethylene porous film. The prepreg-like material according to claim 12, which is selected. Glass cloth is selected as the impregnated base material,
The prepreg-like material according to claim 12, wherein the dielectric constant is at least 5 and the Q value is at least 200.   A sheet obtained by stacking and curing one or more prepreg-like materials according to any one of claims 12 to 14.   A sheet with metal foil, wherein one or more prepreg-like materials according to any one of claims 12 to 14 are stacked, and metal foils are stacked on top and bottom to be cured.   A laminate obtained by curing an impregnated base material between sheets according to claim 10.   An electrically insulating material obtained from the resin composition according to any one of claims 1 to 9.   A resist material obtained from the resin composition according to claim 1.