JP2013079326A5 - - Google Patents

Description

Therefore, in order to produce an epoxy resin composition having a low dielectric constant (especially lower than 4.1) , it is necessary to reduce polar groups such as hydroxyl groups, and therefore it is necessary to use an epoxy resin having a large epoxy equivalent. When such a resin is used, since the cross-linked structure becomes 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.

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 group or alkylidene group, and ring C is an arylene group, cycloalkylene group, arylene-alkylene-arylene group or arylene-alkylidene-arylene group having 6 to 18 carbon atoms.

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、メチレン基、エチリデン基、プロピリデン基、-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).

However, T is a direct bond, a methylene group , an ethylidene group , a propylidene group , -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.

但し、Tは直接結合、メチレン基、エチリデン基、プロピリデン基、-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).

However, T is a direct bond, a methylene group , an ethylidene group , a propylidene group , -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.

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. The ring C is an arylene group, a cycloalkylene group, an arylene-alkylene-arylene group or an arylene-alkylidene-arylene group having 6 to 18 carbon atoms.

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.

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.

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 and a comparative example are shown and the resin composition of this invention is demonstrated 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.
However, the number in a table | surface represents a mass part. In Example 1-5, 100 parts by mass of methyl ethyl ketone (MEK) was used as a solvent, and in Example 6, 200 parts by mass of MEK was used.

[Comparative example]
About the resin composition of the compounding ratio shown by Table 2, the physical-property test was done like the Example except having used 200 mass parts of MEK as a solvent . However, the number in a table | surface represents a mass part.

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 represented by the general formula (I) was used (Comparative Example 2), it was confirmed that the dielectric constant was high . In the case of the resin composition, it was confirmed that it was excellent in low dielectric property.

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 exceeding 20 μm as a filler was used (Comparative Example 5), a film could not be produced.

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, a methylene group , an ethylidene group , a propylidene group , —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);

However, T is a direct bond, a methylene group , an ethylidene group , a propylidene group , -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);

However, T is a direct bond, a methylene group , an ethylidene group , a propylidene group , -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);

However, T is a direct bond, a methylene group , an ethylidene group , a propylidene group , -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, cycloalkylene group, arylene-alkylene-arylene group or arylene-alkylidene-arylene group having 6 to 18 carbon atoms.   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.