JP2013079326A - Resin composition, build-up insulating body containing the composition, and prepreg using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which does not impair resin properties and has excellent low-dielectric properties even when a polytetrafluoroethylene filler is blended therewith.SOLUTION: The resin composition contains: an epoxy resin represented by formula (I); a phenol resin represented by specific formula, as a curing agent; and a polytetrafluoroethylene filler, wherein, in formula, n represents an integer of 0-50, and A represents at least one bivalent group selected from a group of specific formulae.

Description

  The present invention relates to a resin composition, and more specifically, it contains a specific epoxy resin, a specific phenol resin, and a polytetrafluoroethylene filler having a specific particle size, and does not impair the original properties of the resin, and has a low dielectric constant and heat resistance. The present invention relates to a resin composition having a high value.

Epoxy resin compositions have excellent electrical performance and adhesive strength, and thus have various uses in the electric / electronic field. However, the epoxy resin has a problem that the dielectric constant increases when the epoxy ring is opened and a hydroxyl group is generated during curing.
In particular, in order to increase the heat resistance of the material, it is necessary to use an epoxy resin with a small epoxy equivalent to make the cross-linked structure dense, but since the generation of hydroxyl groups is increased accordingly, the dielectric constant is further increased. There is a tendency.

Therefore, in order to produce an epoxy resin composition having a low dielectric constant, it is necessary to reduce the number of polar groups such as hydroxyl groups, so it is necessary to use an epoxy resin having a large epoxy equivalent. Since the cross-linked structure is sparse, the heat resistance tends to be low.
Thus, in a material using an epoxy resin, it is very difficult to obtain a composition that satisfies both heat resistance and low dielectric constant.

  On the other hand, polytetrafluoroethylene has a dielectric constant of 2.1, is extremely low among resins, and has excellent insulating properties and chemical resistance, and is therefore useful as an insulating material.

However, as an epoxy resin composition for a flexible printed wiring board, a resin composition containing biphenyl type epoxy resin and novolac type phenol resin as essential components (Patent Documents 1 and 2), and biphenyl type epoxy resin and biphenyl type phenol resin Is disclosed as an essential component (Patent Document 3), but these documents do not describe the use of a combination of polytetrafluoroethylene fillers.
As described above, polytetrafluoroethylene is difficult to be used as a resin composition because of poor adhesion and compatibility with other resins, so that there is no example used in this field yet.

JP 2004-346256 A JP 2004-359849 A JP 2003-105059 A

Accordingly, a first object of the present invention is to provide a resin composition having excellent low dielectric constant and heat resistance, as well as not deteriorating the properties of the resin even when a polytetrafluoroethylene filler is blended. is there.
A second object of the present invention is to provide a build-up insulator excellent in low dielectric constant and heat resistance.
The third object of the present invention is to provide a prepreg excellent in low dielectric constant and heat resistance.

  As a result of intensive studies in order to achieve the above-mentioned various purposes, the present inventors have obtained a blend of a specific epoxy resin and a specific phenol resin using a polytetrafluoroethylene filler having a specific particle diameter. The present inventors have found that the obtained resin composition can achieve the above object, and have reached the present invention.

但し、上記式中のｎは0〜50の整数、Aは下記群(A)から選択される少なくとも一種の二価の基であり、Yは水素原子、炭素原子数1〜10のアルキル基、炭素原子数2〜10のアルケニル基又は下記式(Y)で表される基である。

但し、X_１〜X₄は、それぞれ独立して、水素原子又は炭素原子数1〜10のアルキル基である。

但し、Tは直接結合、メチレン、エチリデン、プロピリデン、-O-、-S-又は-SO₂-である。

但し、上式中のｍは0〜400の整数、Aは前記群(A)から選択される少なくとも一種の二価の基であり、Ｚは水素原子又は炭素原子数1〜10のアルキル基、炭素原子数2〜10のアルケニル基又は下記式(Z)で表わされる基である。

但し、Tは直接結合、メチレン、エチリデン、プロピリデン、-O-、-S-又は-SO₂-である。 That is, the present invention relates to an epoxy resin represented by the following formula (I), a phenol resin represented by the following formula (II), and a polytetrafluoroethylene filler having an average particle size of 0.01 to 20 μm by a laser diffraction particle size distribution measuring method. A resin composition containing the resin composition, an insulating material for buildup containing the resin composition, and a prepreg for printed circuit boards.

However, n in the said formula is an integer of 0-50, A is at least 1 type of bivalent group selected from the following group (A), Y is a hydrogen atom, a C1-C10 alkyl group, An alkenyl group having 2 to 10 carbon atoms or a group represented by the following formula (Y).

However, X ₁ to X ₄ are each independently hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

T is a direct bond, methylene, ethylidene, propylidene, -O-, -S- or -SO _2- .

However, m in the above formula is an integer of 0 to 400, A is at least one divalent group selected from the group (A), Z is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, An alkenyl group having 2 to 10 carbon atoms or a group represented by the following formula (Z).

T is a direct bond, methylene, ethylidene, propylidene, -O-, -S- or -SO _2- .

但し、式中のｎは0〜50の整数、X_１〜X₄は、それぞれ独立して、水素原子又は炭素原子数1〜10のアルキル基であり、Yは水素原子又は炭素原子数1〜10のアルキル基、炭素原子数2〜10のアルケニル基又は下記式(Y)で表される基である。

但し、Tは直接結合、メチレン、エチリデン、プロピリデン、-O-、-S-又は-SO₂-である。 The epoxy resin is preferably an epoxy resin represented by the following formula (I-1).

However, an integer wherein n 0 to 50, X ₁ to X ₄ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Y is 1 hydrogen atom or a carbon atoms And a group represented by the following formula (Y): an alkyl group having 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms.

T is a direct bond, methylene, ethylidene, propylidene, -O-, -S- or -SO _2- .

但し、上式中のmは０〜400の整数、X_１〜X₄は、それぞれ独立して、水素原子又は炭素原子数1〜10のアルキル基であり、Ｚは水素原子又は炭素原子数1〜10のアルキル基、炭素原子数2〜10のアルケニル基又は下記式(Z)で表される基である。

但し、Tは直接結合、メチレン、エチリデン、プロピリデン、-O-、-S-又は-SO₂-である。 The phenol resin is preferably a phenol resin represented by the following formula (II-1).

However, m in the above formula is an integer of 0 to 400, X _{1 to} X ₄ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Z is a hydrogen atom or 1 carbon atom. An alkyl group having ˜10, an alkenyl group having 2 to 10 carbon atoms, or a group represented by the following formula (Z).

T is a direct bond, methylene, ethylidene, propylidene, -O-, -S- or -SO _2- .

但し、式中のR¹、R²及びR³は水素原子、又は炭素原子数1〜8のアルキル基若しくはシクロアルキル基、又はハロゲン原子、S¹及びS²は、直接結合、又は炭素原子数1〜4のアルキレン基若しくはアルキリデン基であり、環Cは炭素原子数6〜18のアリーレン基、シクロアルキレン基、アリーレン−アルキレン−アリーレン基又はアリーレン−アルキリデン−アリーレン基である。 The resin composition may further contain a reactive flame retardant, and the reactive flame retardant is preferably a phosphate amide compound represented by the following general formula (III).

However, in the formula, R ¹ , R ² and R ³ are a hydrogen atom, or an alkyl or cycloalkyl group having 1 to 8 carbon atoms, or a halogen atom, and S ¹ and S ² are a direct bond or the number of carbon atoms 1 to 4 alkylene groups or alkylidene groups, and ring C is an arylene group having 6 to 18 carbon atoms, a cycloalkylene group, an arylene-alkylene-arylene group, or an arylene-alkylidene-arylene group.

  According to the present invention, even if a polytetrafluoroethylene filler is blended, a resin composition having properties that the properties of the resin are not impaired and the dielectric constant is low can be obtained.

但し、上記式（I）中のｎは0〜50の整数である。ｎが50を超えると粘度が高くなりすぎて、溶剤に溶解させるのが困難になる。 Hereinafter, the resin composition of the present invention will be described in detail.
The resin composition of the present invention contains an epoxy resin represented by the following general formula (I).

However, n in the said formula (I) is an integer of 0-50. When n exceeds 50, the viscosity becomes too high and it becomes difficult to dissolve in a solvent.

但し、X_１〜X₄は、それぞれ独立して、水素原子又は炭素原子数1〜10のアルキル基である。
また、Ｙは水素原子、炭素原子数1〜10のアルキル基、炭素原子数2〜10のアルケニル基又は下記式(Y)で表される基である。

但し、Tは直接結合、メチレン、エチリデン、プロピリデン、-O-、-S-又は-SO₂-である。
本発明の樹脂組成物に使用される前記式(I)で表わされるエポキシ樹脂は、1種のみであっても、2種以上であってもよい。 A in the above formula (I) is at least one divalent group selected from the following group (A).

However, X ₁ to X ₄ are each independently hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Y is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a group represented by the following formula (Y).

T is a direct bond, methylene, ethylidene, propylidene, -O-, -S- or -SO _2- .
The epoxy resin represented by the formula (I) used in the resin composition of the present invention may be only one type or two or more types.

上記式（I-1）中のn、X₁〜X₄及びYは、前述した通りである。 In particular, in order to obtain a cured resin having a low dielectric constant, it is preferable to use an epoxy resin represented by the following general formula (I-1) as the epoxy resin.

In the above formula (I-1), n, X _{1 to} X ₄ and Y are as described above.

In the present invention, other epoxy resins may be used in combination with the epoxy resin as long as the effects of the present invention are not impaired.
Examples of other epoxy resins include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, bisphenol F, methylene bis (orthocresol), ethylidene bisphenol, Bisphenol A, isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3- Tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolak, ethylphenol novolak, butylphenol novolak Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, Polyglycidyl ether of polyhydric alcohols such as sorbitol or bisphenol A and ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer Acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endo Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as tylenetetrahydrophthalic acid; homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl Epoxy compounds having a glycidylamino group such as -N-glycidylamino) phenyl) methane and diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Epoxidized products of cyclic olefin compounds such as carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, Epoxidized styrene-butadiene copolymer Epoxidized conjugated diene polymer compound and the like; heterocyclic compounds such as triglycidyl isocyanurate.
The amount of the epoxy resin other than the epoxy resin of the formula (I) used is 0 to 90% by mass of the total epoxy resin in the resin composition.

  In addition, these epoxy resins are those internally crosslinked by a prepolymer of terminal isocyanate, or those having a high molecular weight with polyhydric active hydrogen compounds such as polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphates, etc. But you can.

上記式(II)中のｍは0〜400の整数である。ｍが400を超えると粘度が高くなりすぎて、溶剤に溶解させるのが困難になる。
上記式(II)中のAは前記群(A)から選択される少なくとも一種の二価の基である。 The resin composition of the present invention contains a phenol resin represented by the following general formula (II).
The phenol resin is used as a curing agent for the resin composition.

M in the above formula (II) is an integer of 0 to 400. When m exceeds 400, the viscosity becomes too high and it becomes difficult to dissolve in a solvent.
A in the formula (II) is at least one divalent group selected from the group (A).

但し、Tは直接結合、メチレン、エチリデン、プロピリデン、-O-、-S-又は-SO₂-である。
本発明の樹脂組成物に使用される前記式(II)で表わされるフェノール樹脂は、1種のみであっても、2種以上であってもよい。 Z in the above formula (II) is a hydrogen atom, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, or a group represented by the following formula (Z).

T is a direct bond, methylene, ethylidene, propylidene, -O-, -S- or -SO _2- .
The phenol resin represented by the formula (II) used in the resin composition of the present invention may be only one type or two or more types.

上記式(II-1)中のm、X₁〜X₄及びZは、前述した通りである。 In particular, in order to obtain a cured resin having a low dielectric constant, it is preferable to use a phenol resin represented by the following general formula (II-1).

M, X _{1 to} X ₄ and Z in the above formula (II-1) are as described above.

In the present invention, other phenol resins may be used in combination with the phenol resin as long as the effects of the present invention are not impaired.
Examples of other phenol resins include phenol resins synthesized from phenols and aldehydes. Examples of the phenols include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol, resorcin, catechol, and hydroquinone. 2,2-bis (4-hydroxyphenyl) propane, 4,4′-thiodiphenol, dihydroxydiphenylmethane, naphthol, terpenephenol, phenolized dicyclopentadiene, and the like. Examples of the aldehydes include formaldehyde. It is done.
The amount of the epoxy resin other than the epoxy resin of the formula (II) used is 0 to 90% by mass of the total phenol resin in the resin composition.

The average particle diameter of the polytetrafluoroethylene filler contained in the resin composition of the present invention by the laser diffraction particle size distribution measurement method needs to be 0.01 to 20 μm, and preferably 0.03 to 10 μm.
When the average particle size is less than 0.01 μm, it becomes difficult to mix a large amount with the resin, and when it exceeds 20 μm, it is difficult to produce a thin film.

  The amount of the epoxy resin, the phenol resin and the polytetrafluoroethylene filler can be appropriately changed according to the use, but the amount of the total phenol resin used is 5 to 150 parts by mass with respect to 100 parts by mass of the total epoxy resin. It is preferably 10 to 100 parts by mass. Moreover, it is preferable that the usage-amount of the said polytetrafluoroethylene filler is 5-100 mass parts with respect to 100 mass parts of all the epoxy resins, and it is especially preferable that it is 8-50 mass parts.

但し、式中のR¹、R²及びR³は水素原子又は炭素原子数1〜8のアルキル基若しくはシクロアルキル基、又はハロゲン原子、S¹及びS²は直接結合、炭素原子数1〜4のアルキレン基、アルキリデン基であり、環Cは炭素原子数6〜18のアリーレン基、シクロアルキレン基、アリーレン−アルキレン−アリーレン基又はアリーレン−アルキリデン−アリーレン基である。 The resin composition of the present invention preferably further contains a reactive flame retardant, and examples of the reactive flame retardant that can be used are represented by the following general formulas (III) to (V). Phosphorus-based reactive flame retardants.

However, in the formula, R ¹ , R ² and R ³ are a hydrogen atom or an alkyl or cycloalkyl group having 1 to 8 carbon atoms, or a halogen atom, S ¹ and S ² are direct bonds, and 1 to 4 carbon atoms. And ring C is an arylene group having 6 to 18 carbon atoms, a cycloalkylene group, an arylene-alkylene-arylene group or an arylene-alkylidene-arylene group.

但し、式中のR¹は水素原子、又は炭素原子数1〜8のアルキル基若しくはシクロアルキル基、又はハロゲン原子である。

However, R < ¹ > in a formula is a hydrogen atom, a C1-C8 alkyl group or a cycloalkyl group, or a halogen atom.

但し、式中のR¹は水素原子、又は炭素原子数1〜8のアルキル基若しくはシクロアルキル基、又はハロゲン原子である。

However, R < ¹ > in a formula is a hydrogen atom, a C1-C8 alkyl group or a cycloalkyl group, or a halogen atom.

Among these reactive flame retardants, it is preferable to use a phosphoric acid amide compound represented by the general formula (III) in order to lower the dielectric constant.
Moreover, the usage-amount of the said reactive flame retardant is 5-100 mass parts with respect to 100 mass parts of all the epoxy resins, and it is preferable that it is 8-50 mass parts.

Furthermore, in the resin composition of the present invention, another epoxy resin curing agent may be used in combination with the phenol resin as long as the effects of the present invention are not impaired.
By using in combination with other curing agents, the viscosity and curing characteristics of the resulting curable composition, or the physical properties after curing can be controlled.
Examples of other curing agents that can be used in the present invention include latent curing agents, acid anhydrides, polyamine compounds, and the like. In particular, the resin composition of the present invention is a one-component curable composition that is easy to handle. From the viewpoint of producing a product, it is preferable to use a latent curing agent.

  Examples of the latent curing agent include dicyandiamide, hydrazide, imidazole compound, amine adduct, sulfonium salt, onium salt, ketimine, acid anhydride, and tertiary amine.

  Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, 2 , 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride and the like.

  Examples of the polyamine compound include aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine; mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (aminomethyl) cyclohexane, 3, Alicyclic polyamines such as 9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, aliphatic amines having an aromatic ring such as m-xylenediamine; m-phenylene Diamine, 2,2-bis (4-aminophenyl) propane, diaminodiphenylmethane, diaminodiphenylsulfone, α, α-bis (4-aminophenyl) -p-diisopropylbenzene, 2,2-bis (4-aminophenyl) Aromatic polyamines such as -1,1,1,3,3,3-hexafluoropropane; 2-methylimidazole, 2-phenylimidazole, 2-undecylimida Sol, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2- Phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-undecyl) Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2 ′ -Methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxy Methylimidazole, 2-phenyl-4-hydroxymethy -5-methylimidazole, various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the imidazoles and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, Examples include imidazole compounds such as salts with polyvalent carboxylic acids such as naphthalenedicarboxylic acid, maleic acid, and oxalic acid; and triazole compounds such as 2-phenyl-4-hydroxy-5-methyltriazole.

In the present invention, other fillers can be used in combination with the polytetrafluoroethylene filler as long as the effects of the present invention are not impaired.
Examples of other fillers include glass fillers, calcium carbonate, aluminum hydroxide, magnesium hydroxide, alumina, silicon nitride, silicon carbide, mica, talc, kaolin clay, silica, barium sulfate, and other various organic materials. Commonly used fillers such as filler, glass fiber, wollastonite, alumina fiber, ceramic fiber, and fibrous fillers such as various whiskers can be used.

If necessary, other additives can be added to the resin composition of the present invention.
Examples of such additives include plasticizers such as natural waxes, synthetic waxes and metal salts of long chain aliphatic acids, release agents such as acid amides, esters and paraffins, nitrile rubber, butadiene rubber, acrylic Stress relaxation agents such as rubber silicon rubber, silane coupling agents, titanate coupling agents, aluminum coupling agents, coupling agents such as zirconium coupling agents, coloring agents such as dyes and pigments, oxidation stabilizers, Light stabilizer, moisture resistance improver, thixotropy imparting agent, ion adsorbent, diluent, antifoaming agent, other various resins, tackifier, antistatic agent, lubricant, ultraviolet absorber, alcohols, ether , Acetals, ketones, esters, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, keto Esters and ester ethers, and organic solvents such as aromatic solvents.

  The insulator for buildup of the present invention can be obtained by applying the resin composition of the present invention to a base film and then drying it to make the resin composition semi-cured.

The prepreg for a printed circuit board of the present invention is obtained by applying the resin composition of the present invention to a substrate such as a glass cloth by a known method and then drying it to make the resin composition semi-cured.
Moreover, a copper-clad laminate is obtained by laminating the prepreg of the present invention and a copper foil, and heating and pressing so that the resin composition is completely cured by a known method.
The number of prepregs can be changed as required.
EXAMPLES Hereinafter, although an Example is shown and the resin composition of this invention is demonstrated still in detail, this invention is not limited by these.

[Examples 1 to 6]
The resin composition having the blending ratio shown in Table 1 was dispersed using a bead mill, applied to an IPC standard 1037 glass cloth so as to have a thickness of 45 μm, and dried at 130 ° C. for 10 minutes to prepare a prepreg.

A copper foil was laminated on both surfaces of the obtained prepreg, and then cured by pressurizing at a pressure of 30 kg / cm ² and a final temperature of 190 ° C. for 90 minutes using a vacuum press machine to obtain a laminate.
The copper foil peeling strength of the obtained laminate was measured according to JIS C6481.

After all the copper foil of the laminate was removed using an etching solution, the glass transition point, thermal expansion coefficient, dielectric constant and dielectric loss tangent of the substrate were measured by the following methods.
<Glass transition point (Tg)>
Using a DMS 6100 manufactured by SII, measurement was performed in a measurement range of 30 ° C. to 350 ° C. (temperature increase at 5 ° C./min), and the peak of tan δ was taken as the glass transition point.

<Coefficient of thermal expansion (CTE)>
Using TII / SS 6100 manufactured by SII, measurement in the XY direction was performed in the range of 30 ° C. to 300 ° C. (temperature increase at 10 ° C./min), and the coefficient of thermal expansion from 40 ° C. to 125 ° C. was α1.

<Dielectric constant and dielectric loss tangent>
The measurement was performed under the conditions of an applied voltage of 500 mV and a frequency of 1 GHz by using an impedance / material analyzer E4991A manufactured by Agilent Technologies.

<Combustion test>
Panasonic Electric Works R-1566 from which the copper foil has been removed, the prepreg laminated on the top and bottom of the 0.8 mm substrate, and further sandwiched by the copper foil, using a vacuum press machine, pressure 30 kgf / cm ² , 190 ° C., The laminate was obtained by applying pressure and curing for 90 minutes.
All the copper foil of the obtained laminate was removed using an etching solution, and a combustion test was performed under conditions according to UL-94.

[Comparative example]
About the resin composition of the compounding ratio shown by Table 2, the physical property test was done similarly to the Example.

反応性難燃剤−２：下記のリン系化合物

非反応性難燃剤：下記のリン酸エステル化合物

硬化剤：２-フェニル-４-ヒドロキシ-５-メチルトリアゾール The compounds shown in Tables 1 and 2 are as follows.
Epoxy resin 1: NC-3000H (Nippon Kayaku Co., Ltd. biphenylene aralkyl epoxy resin)
Epoxy resin 2: HP-7200 (DIC dicyclopentadiene type epoxy resin)
Epoxy resin 3: EP-4100E (Adeka bisphenol A epoxy resin)
Phenolic resin 1: MEH-7851H (Maywa Kasei Co., Ltd. biphenylene aralkyl type phenolic resin)
Phenolic resin 2: GDP-6115H (dicyclopentadiene type phenolic resin manufactured by Gunei Chemical Industry Co., Ltd.)
Phenolic resin 3: PSM-4326 (Novolak type phenolic resin manufactured by Gunei Chemical Industry Co., Ltd.)
PTFE filler 1: TFW-3000 (polytetrafluoroethylene filler manufactured by Seishin Co., Ltd .: average particle size 3μm)
PTFE filler 2: Teflon (registered trademark) 6C-J (Mitsui / DuPont Fluorochemical Co., Ltd. polytetrafluoroethylene fine powder: average particle size 400 μm)
PP filler: PPW-5 (polypropylene filler manufactured by Seishin Corporation)
Silica: SO-C2 (spherical silica manufactured by Admatechs)
Aluminum hydroxide: C-301 (Aluminum hydroxide manufactured by Sumitomo Chemical Co., Ltd.)
Reactive flame retardant-1: The following phosphoric acid amide compound

Reactive flame retardant-2: The following phosphorus compounds

Non-reactive flame retardant: The following phosphate ester compounds

Curing agent: 2-phenyl-4-hydroxy-5-methyltriazole

Tables 3 and 4 show the test results of the examples and comparative examples.

  As is apparent from Tables 1 and 2, when a silica filler was used without using a polytetrafluoroethylene filler (Comparative Example 1), a phenol resin other than the phenol resin of the general formula (II) was used as a curing agent. In the case (Comparative Example 3), when an epoxy resin other than the epoxy resin of the general formula (I) was used (Comparative Example 2), the increase in dielectric constant was confirmed in all cases, but the resin of the present invention In the case of the composition, it was confirmed that it was excellent in low dielectric properties.

In addition, it was confirmed that the composition (Comparative Example 4) containing polypropylene filler instead of polytetrafluoroethylene filler was unsuitable for use as an electronic material because the polypropylene filler melted when dried at 130 ° C. It was.
In addition, when a resin composition containing polytetrafluoroethylene having a particle size of more than 20 μm as a filler was used (Comparative Example 5), a lamination failure occurred, and a laminated substrate could not be produced.

  The resin composition of the present invention can be used for electronic materials such as pastes, B-stage films, resin-coated copper foils or prepregs for printed circuit boards, particularly high-frequency multilayer boards, build-up insulating materials, etc. It is extremely useful.

Claims (8)

It contains an epoxy resin represented by the following formula (I), a phenol resin represented by the following formula (II), and a polytetrafluoroethylene filler having an average particle size of 0.01 to 20 μm by a laser diffraction particle size distribution measurement method. A resin composition characterized by

However, n in the said formula (I) is an integer of 0-50, A is at least 1 type of bivalent group selected from the following group (A), Y is a hydrogen atom and C1-C10. An alkyl group, an alkenyl group having 2 to 10 carbon atoms, or a group represented by the following formula (Y);

However, X ₁ to X ₄ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

Where T is a direct bond, methylene, ethylidene, propylidene, —O—, —S— or —SO ₂ —;

Wherein m is an integer of 0 to 400, A is at least one divalent group selected from the group (A), Z is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, An alkenyl group having 2 to 10 carbon atoms or a group represented by the following formula (Z);

T is a direct bond, methylene, ethylidene, propylidene, -O-, -S- or -SO _2- . The resin composition according to claim 1, wherein the epoxy resin is an epoxy resin represented by the following formula (I-1).

However, an integer wherein n 0 to 50, X ₁ to X ₄ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Y is 1 hydrogen atom or a carbon atoms 10 alkyl groups, alkenyl groups having 2 to 10 carbon atoms, or groups represented by the following formula (Y);

T is a direct bond, methylene, ethylidene, propylidene, -O-, -S- or -SO _2- . The resin composition according to claim 1 or 2, wherein the phenol resin is a phenol resin represented by the following formula (II-1).

However, m in the above formula is an integer of 0 to 400, X _{1 to} X ₄ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Z is a hydrogen atom or 1 carbon atom. Or an alkyl group having 10 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a group represented by the following formula (Z);

T is a direct bond, methylene, ethylidene, propylidene, -O-, -S- or -SO _2- .   Furthermore, the resin composition in any one of Claims 1-3 containing a reactive flame retardant. The resin composition according to claim 4, wherein the reactive flame retardant is a phosphoric acid amide compound represented by the following general formula (III):

Wherein R ¹ , R ² and R ³ are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or a halogen atom, and S ¹ and S ² are direct bonds or alkylene having 1 to 4 carbon atoms. And ring C is an arylene group having 6 to 18 carbon atoms, a cycloalkylene group, an arylene-alkylene-arylene group or an arylene-alkylidene-arylene group.   Furthermore, the resin composition in any one of Claims 1-5 containing the curing catalyst for epoxy resins.   The insulating material for buildups containing the resin composition as described in any one of Claims 1-6.   A prepreg for a printed circuit board containing the resin composition according to any one of claims 1 to 6.