JPH11130939A - Epoxy resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition improved in heat resistance, dielectric properties and galvanic corrosion resistance by mixing a methine-bonded alkyl- substituted polyfunctional epoxy resin with a curing agent having an active ester group, a cure accelerator, an inorganic or organic hollow particles having voids in insides and an antioxidant. SOLUTION: This composition contains an epoxy resin having at least two epoxy groups and represented by formula I (wherein R1 is H or a 1-4C alkyl; R2 is a 1-4C alkyl; and n is 0-10) and a curing agent being a compound represented by formula II (wherein R1 is H or a 1-4C alkyl; R2 is a 1-4C alkyl; X is a 1-4C alkyl, formula III or formula IV; and n and m are each 1-10). It is desirable that 100 pts.wt. epoxy resin is compounded with 50-150 pts.wt. curing agent, 0.1-5 pts.wt., per 100 pts.wt., in total, epoxy resin and curing agent, cure accelerator, 1-50 pts.wt., per 100 pts.wt. total resin component, hollow particles and 0.1-20 pts.wt., per 100 pts.wt. epoxy resin, antioxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition having excellent dielectric properties, water resistance and heat resistance, which is useful as a resin for a laminated board, a casting resin for electrical insulation, and a resin for various adhesives. The cured product.

[0002]

2. Description of the Related Art Conventionally, epoxy resins having excellent adhesiveness, mechanical properties, heat resistance, chemical resistance, electrical properties, etc. have been widely used as resins for laminates. In recent years, as the density of printed wiring boards has increased and the number of layers has increased, there has been a strong demand for improved heat resistance of laminated boards for the purpose of improving mounting productivity and reliability. Also, in electronic equipment such as computers, transmission characteristics such as signal propagation delay and occurrence of crosstalk on printed wiring boards have become a problem due to higher speed and higher frequency of signals. Materials having a low dielectric constant are required. However, the dielectric constant of the conventional epoxy resin laminate based on glass cloth is 4.7 to 5.0.
High transmission characteristics could not be obtained.

In order to improve the heat resistance of the epoxy resin laminate, a method of curing a polyfunctional epoxy resin with dicyandiamide, a method of curing with a polyfunctional phenol resin, and the like are used.

The following proposals have been made for the purpose of improving the dielectric properties of an epoxy resin laminate having excellent heat resistance. For example, epoxy resin is disclosed in
No. 35425, poly 4-methyl-1-
Pentene, a phenol-added butadiene polymer disclosed in JP-A-61-126162;
There is a method of reacting with a polybutadiene modified with a carboxyl group at the terminal as disclosed in JP-A-187736, a propargyl etherified aromatic hydrocarbon as disclosed in JP-A-4-13717, and the like. Also, Japanese Patent Application Laid-Open No. 57-8309
Japanese Patent Application Laid-Open No. 3-84040 discloses a method in which hollow particles are mixed in a resin layer as disclosed in Japanese Patent Application Laid-Open No. 0-203594, and a fluororesin powder described in Japanese Patent Application Laid-Open No. 2-203594 is blended. As disclosed in Japanese Patent Application Laid-Open No. 4-24986, an aromatic polyamide fiber is used as a base material, and a method in which a glass cloth base fluororesin prepreg and a glass cloth base epoxy resin prepreg are used in an overlapping manner.

[0005]

However, the dicyandiamide curing system has a drawback of increasing the water absorption, and it is difficult to satisfy the high insulation reliability for semiconductor package applications. In particular, the occurrence of metal migration (electrolytic corrosion) in which metal constituting wiring, circuit patterns, electrodes, etc. migrates on or in an insulating material due to the action of a potential difference in a high-humidity environment within the insulating material. It has become. In addition, in the case of the polyfunctional phenol-cured resin, the cured resin becomes rigid, and minute cracks are likely to occur during drilling of through holes, and there is concern that metal migration may occur from these minute cracks. I can't satisfy her.

Further, Japanese Patent Application Laid-Open No. Sho 60-135425,
JP-A-61-126162 and JP-A-62-18
No. 7736, poly-4-methyl-1-pentene, phenol-added butadiene polymer,
The method of reacting a hydrocarbon polymer such as a terminal carboxyl group-modified polybutadiene with an epoxy resin has a problem that the inherent heat resistance of the epoxy resin is impaired although the dielectric constant is lowered. Also, the method of reacting with propargyl etherified aromatic hydrocarbons disclosed in Japanese Patent Application Laid-Open No. Hei 4-13717 has a problem that the heat resistance is high but the cost is extremely high because a special resin is used. Was.

Further, a method of mixing hollow particles in a resin layer, a method of blending a fluororesin powder, a method of blending a fluororesin powder, and the like as disclosed in JP-A-57-83090 and JP-A-2-203594. No. 84040 and JP-A-4-24-2
In the method using an aromatic polyamide fiber on a substrate as described in JP-A-4986 or the method using a glass cloth substrate with a fluororesin prepreg laminated thereon, the dielectric constant of the laminated plate is low, but the conventional glass cloth is used. There was a problem that the mechanical properties were lower than that of the base epoxy resin laminate.

The present invention can reduce the dielectric constant of a laminate or the like at a relatively low cost without impairing the heat resistance and mechanical properties of a conventional epoxy resin laminate, and suppress the occurrence of metal migration. An object of the present invention is to provide an epoxy resin composition which maintains high insulation reliability and a cured product using the same. Here, an epoxy resin laminate is shown as an example, but the same applies to a cast resin for electrical insulation and a resin for various adhesives.

[0009]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have disclosed, as a curing agent for an epoxy resin disclosed in JP-A-6-172988 or the like, one or more active esters in one molecule. Focusing on methods of lowering the dielectric constant using a compound having a group, and methods of improving the dielectric constant and heat resistance by blending various additives, improve (reduce) high heat resistance and dielectric properties, and furthermore, improve corrosion resistance. We studied diligently for the purpose of improvement. As a result, a methine-bonded alkyl-substituted polyfunctional epoxy resin represented by the formula 1 as a main component of the epoxy resin, a compound having one or more active ester groups in one molecule as a main component of the curing agent, and a void therein. The inventors have found that heat resistance, dielectric properties, and corrosion resistance can be improved by using inorganic or organic hollow particles and an antioxidant as an additive, and have completed the present invention.

[0010] That is, the present invention relates to (A) two molecules per molecule.
Epoxy resin composition containing epoxy resin having at least two epoxy groups, (B) curing agent, (C) curing accelerator, (D) inorganic or organic hollow particles having voids therein, and (E) antioxidant (A) an epoxy resin having two or more epoxy groups in one molecule is a methine-bonded alkyl-substituted polyfunctional epoxy resin represented by the formula 1:
(B) An epoxy resin composition in which the curing agent is a compound represented by Formula 2 and having one or more active ester groups in one molecule.

[0011]

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[0012]

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Further, the present invention relates to (A) 100 to 100 parts by weight of an epoxy resin having two or more epoxy groups per molecule, (B) 50 to 150 parts by weight of a curing agent, (A) and (B)
(C) 0.1 to 5
Parts by weight, (D) 1 to 50 parts by weight of the inorganic or organic hollow particles having voids therein and 100 to 100 parts by weight of the (E) antioxidant per 100 parts by weight of the epoxy resin. A preferred epoxy resin composition contains 1 to 20 parts by weight.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin (A) having two or more epoxy groups in one molecule used in the epoxy resin composition of the present invention is a methine-bonded alkyl-substituted polyfunctional epoxy resin represented by the formula 1. As a main component. The methine bond type alkyl-substituted polyfunctional epoxy resin represented by the formula 1 can be obtained by one method of glycidyl etherification of a condensate of an alkyl-substituted phenol and an aromatic aldehyde. Further, as an epoxy resin having two or more epoxy groups in one molecule, epoxy resin represented by the above formula 1 and other bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, phenol novolak type epoxy resin, bromine A mixture of at least one selected from a phenolized novolak type epoxy resin, a cresol novolak type epoxy resin, a biphenyl type epoxy resin and a phenol salicylaldehyde novolak type epoxy resin can be used. The mixing ratio of the methine-bonded alkyl-substituted polyfunctional epoxy resin and the other epoxy resin may be 1 to 70 parts by weight of the other epoxy resin per 100 parts by weight of the methine-bonded alkyl-substituted polyfunctional epoxy resin. preferable. If it is less than 1 part by weight, the compounding effect is poor, and if it exceeds 70 parts by weight, the dielectric properties and Tg (glass transition temperature) are undesirably reduced.

The methine-bonded alkyl-substituted polyfunctional epoxy resin used in the present invention can be obtained by subjecting a condensate of an alkyl-substituted phenol and an aromatic aldehyde to glycidyl etherification. As the alkyl-substituted phenol used in this synthesis, it is preferable to use at least one selected from cresols, t-butylphenol, 2,5-xylenol, and 3-methyl-6-t-butylphenol. On the other hand, it is preferable to use at least one kind of aromatic aldehyde selected from salicylaldehyde and p-hydroxybenzaldehyde.

The condensation of an alkyl-substituted phenol with an aromatic aldehyde is carried out at a ratio of 0.8 to 2.0 mol of the aromatic aldehyde compound per mol of the alkyl-substituted phenol at a temperature of 180 ° C. using a known phenol novolak. The reaction is carried out in the presence of an acidic catalyst for resin synthesis, for example, a mineral acid such as hydrochloric acid, sulfuric acid or phosphoric acid, an organic acid such as oxalic acid or toluenesulfonic acid, or a salt such as zinc acetate. Thereafter, a glycidyl etherification reaction is performed on the condensate using epichlorohydrin to obtain a methine-bonded alkyl-substituted polyfunctional epoxy resin in which a condensate of an alkyl-substituted phenol and an aromatic aldehyde is glycidyl-etherified.

As the curing agent (B) used in the present invention, a compound represented by the formula (2) having one or more active ester groups in one molecule is used as a main component.

The compound having one or more active ester groups in one molecule is a compound in which a phenolic hydroxyl group of a polyfunctional phenol compound is esterified with an aromatic acid or a fatty acid. Specific examples of the active esterified phenol compound include an aromatic or fatty acid esterified phenol novolak resin represented by Formula 2. Specifically, acetylated phenol novolak resin, benzoylated phenol novolak resin, propionylated phenol novolak resin, butyrylated phenol novolak resin, alkylbenzoylated phenol novolak resin, acetylated cresol novolak resin,
Examples include benzoylated cresol novolak resin, propionylated cresol novolak resin, butyrylated cresol novolak resin, and alkylbenzoylated cresol novolak resin. As represented by Formula 2, all of the phenolic hydroxyl groups may be left without being esterified, or a non-esterified polyfunctional phenol compound may remain. The compound having one or more active ester groups in one molecule can be obtained by esterifying a polyfunctional phenol compound with an acid anhydride or an acid chloride of an aromatic or aliphatic carboxylic acid.

The (B) curing agent includes 1 represented by the formula 2
A mixture of at least one compound selected from phenol novolak, bisphenol A novolak, cresol novolak, and tetrabromobisphenol A may be used together with a compound having one or more active ester groups in the molecule. The mixing ratio of the compound having one or more active ester groups in one molecule represented by the formula 2 and the polyfunctional phenol is based on 100 parts by weight of the compound having one or more active ester groups in one molecule. It is preferable to use 5 to 150 parts by weight of the polyfunctional phenol. If the amount is less than 5 parts by weight, the compounding effect is poor, and if it exceeds 150 parts by weight, the dielectric properties deteriorate, which is not preferable.

The compounding amount of the compound having one or more active ester groups in one molecule represented by the formula (2) of the present invention depends on the content of the aromatic acid or fatty acid ester group and the phenol remaining without being esterified. Although it depends on the content of the acidic hydroxyl group, it is considered that both the aromatic acid or fatty acid ester group and the remaining phenolic hydroxyl group react with the epoxy group of the epoxy resin, and the equivalent derived from the content of both is equivalent to the equivalent as a curing agent. Is equivalent to Therefore, the compounding amount of the aromatic acid or fatty acid esterified phenol compound is, like the ordinary non-esterified polyhydric phenol compound, 0.1 to the epoxy equivalent of the epoxy resin.
A 6-1.4 equivalent ratio is desirable. Usually epoxy resin 10
It is desirable to mix the compound having one or more active ester groups in one molecule with the other curing agent in an amount of 50 to 150 parts by weight per 0 parts by weight. If the compounding amount of the compound having one or more active ester groups in one molecule and the other curing agent is less than 50 parts by weight or more than 150 parts by weight, the effect of improving the heat resistance and the dielectric properties is reduced.

In the epoxy resin composition of the present invention, (C) a curing accelerator is used for accelerating the curing reaction between the epoxy resin and the curing agent and improving the heat resistance, water absorption and dielectric properties of the resin. It has been confirmed that most of the curing accelerators conventionally used for the curing reaction between an epoxy resin and various curing agents accelerate the curing reaction between the epoxy resin and the curing agent of the epoxy resin composition of the present invention. Have been. Specific examples of the curing accelerator used in the epoxy resin composition of the present invention include tertiary amines such as dimethylbenzylamine and tris (dimethylaminomethyl) phenol, 1-methylimidazole, 2-methylimidazole, and 2-ethyl- Imidazoles such as 4-methylimidazole, N-
Pyridines such as dimethylaminopyridine, Lewis acids such as boron trifluoride monoethylamine complex, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5 diazabicyclo [4,3,0] -5 And bases such as nonene. Among them, at least one or more selected from 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole and N-dimethylaminopyridine has a strong curing accelerating action and has good Tg and dielectric properties. . The compounding amount of the curing accelerator is 0.1% with respect to 100 parts by weight of the total of the epoxy resin (A) and the curing agent (B).
It is preferable to use from 5.0 to 5.0 parts by weight. If the amount is less than 0.1 part by weight, the curing reaction is slow, and if the amount exceeds 5.0 parts by weight, the storage stability deteriorates, which is not preferable.

As the inorganic or organic hollow particles (D) having voids therein, which are blended in the epoxy resin composition of the present invention, hollow particles having a particle size of 0.1 μm to 100 μm are preferably used. When the particle diameter is 0.1 μm or less, the contribution to improving the dielectric properties is poor, and when the particle diameter exceeds 100 μm, the mechanical properties and the heat resistance of the cured resin material deteriorate, which is not preferable. Representative examples of the hollow particles include hollow glass beads mainly composed of inorganic glass and hollow polymers mainly composed of organic styrene. These materials are not particularly limited as long as they have a particle size of 0.1 μm to 100 μm. It is preferable that the compounding amount is 1 to 50 parts by weight based on 100 parts by weight of the resin such as the epoxy resin and the curing agent. If the amount is less than 1 part by weight, the compounding effect is poor, and if the amount exceeds 50 parts by weight, the mechanical properties of the cured resin material and the adhesiveness are unfavorably reduced.

As the (E) antioxidant used in the epoxy resin composition of the present invention, a phenolic antioxidant, a sulfur organic compound antioxidant, and the like are used. Phenolic antioxidants include 1,2,3-trihydroxybenzene, butylated hydroxyanisole, 2,6-di-t
Monobutyl-based compounds such as -butyl-4-ethylphenol and 2,2'-methylene-bis- (4-methyl-6-t
-Butylphenol), bisphenols such as 4,4'-thiobis- (3-methyl-6-t-butylphenol) and 1,3,5-trimethyl-2,4,6 tris (3,5-di-t- Butyl-4-hydroxybenzylbenzene, tetrakis- [methylene-3- (3'-5'-
Di-t-butyl-4'-hydroxyphenylpropionate] methane and the like. Examples of the sulfur organic antioxidant include diuralyl thiopropionate, distearyl thiodipropionate, and the like.
Some of these antioxidants may be used in combination, and the compounding amount is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin. If the amount is less than 0.1 part by weight, no improvement in insulating properties is observed, and if it exceeds 20 parts by weight, the insulating properties tend to decrease.

In the epoxy resin composition of the present invention, a brominated flame retardant, a filler and other additives can be blended as required. As the filler to be blended as necessary, usually, an inorganic filler is suitably used, and fused silica, glass, alumina, zircon, calcium silicate, calcium carbonate, silicon nitride, boron nitride, beryllia, zirconia, titanate Potassium, aluminum silicate, magnesium silicate and the like are used as powders or spherical beads. Also, whiskers, single crystal fibers, glass fibers and the like can be blended. When compounded in the epoxy resin composition of the present invention, the compounding amount of the filler is epoxy resin,
10 to 3 with respect to the total of 100 parts by weight of the curing agent and the curing accelerator
It is preferable to add 00 parts by weight. If the amount is less than 10 parts by weight, the compounding effect is poor, and if it exceeds 300 parts by weight, the adhesiveness may be reduced.

The epoxy resin composition of the present invention can be cured by heating to obtain a cured product having a low dielectric constant.
That is, the epoxy resin composition of the present invention is dissolved in a solvent to form a varnish, impregnated into a glass cloth substrate, and dried to prepare a prepreg. Next, a metal foil-clad laminate can be obtained by laminating several prepregs and metal foil on the upper, lower, or one surface thereof and then heating and pressing them.

Examples of the solvent for dissolving the epoxy resin composition of the present invention include glycols, monoether glycols, ketones, amides, aromatic hydrocarbons, esters, and nitriles. Specifically, diethylene glycol, triethylene glycol and the like as glycol solvents, ethylene glycol monomethyl ether and the like as monoether glycol solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like as ketone solvents are amide solvents. N-methylpyrrolidone, formaldehyde, N
-Methylformaldehyde, N, N-dimethylformamide and the like; aromatic hydrocarbon solvents such as toluene and xylene; and ester solvents such as methoxyethyl acetate, ethoxyethyl acetate and ethyl acetate. These solvents may be used alone or in combination of two or more.

In a normal epoxy resin, a highly polar hydroxyl group is by-produced as a result of ring opening of the epoxy group.
When a compound having two or more active ester groups reacts with the epoxy resin, it is considered that the compound having the active ester group reacts with the ring opening of the epoxy resin to form an ester having low polarity. Therefore, as a reason that the dielectric constant is lowered by using this compound as a curing agent,
It is presumed that unlike the ordinary epoxy resin curing reaction, a highly polar hydroxyl group is not generated, and even if a highly polar hydroxyl group is generated, the amount thereof is small and the polarizability of the cured resin can be suppressed low.

Further, by using the methine-bonded alkyl-substituted polyfunctional epoxy resin of the present invention as the main component in the epoxy resin, the crosslinking density is increased and the glass transition temperature (Tg) is increased as compared with the case where only the bifunctional epoxy resin is used. Can be improved. Further, this epoxy resin has a bulky skeleton as represented by Formula 1. It is said that a bulky skeleton is effective in reducing the dielectric constant, and it is considered that the dielectric constant can be reduced by introducing this skeleton into the cured product. Furthermore, a particle size of 0.1 to 100 μm with voids inside
By mixing the hollow particles of m with a phenolic antioxidant or a sulfur organic compound antioxidant, the dielectric constant and dielectric loss tangent can be reduced without impairing the mechanical properties and heat resistance, and the occurrence of metal migration is suppressed. An epoxy resin composition that provides electrical insulation can be obtained.

[0029]

EXAMPLES The present invention will now be described specifically with reference to specific examples, but the present invention is not limited to these examples.

(Synthesis Example 1: Condensation product of aromatic aldehyde (C
Synthesis of SA) 865 g of o-cresol was placed in a four-neck separable flask equipped with a thermometer, a cooling tube, and a stir bar.
1465 g of salicylaldehyde and 0.87 g of p-toluenesulfonic acid (monohydrate) were reacted at 180 ° C. with stirring for 6 hours. Then, after neutralizing with a 10% by weight sodium hydroxide solution, dissolving in 3 liters of toluene, washing twice with water, removing toluene and unreacted monomers by distillation, and aromatic condensate of alkyl-substituted phenol (CSA) ) 1571 g was obtained.

(Synthesis Example 2: Condensation product of aromatic aldehyde (T
Synthesis of BHA) 1202 g of t-butylphenol in place of o-cresol of Synthesis Example 1 and 1465 of p-hydroxybenzaldehyde in place of salicylaldehyde
g, p-toluenesulfonic acid 1.20 g, except that 1,840 g of an aromatic aldehyde condensate (TBHA) of an alkyl-substituted phenol was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 3: Condensation product of aromatic aldehyde (X
Synthesis of SA) In the same manner as in Synthesis Example 1 except that 977 g of 2,5-xylenol and 0.98 g of p-toluenesulfonic acid were used instead of o-cresol of Synthesis Example 1, an aromatic aldehyde condensate of an alkyl-substituted phenol ( XSA) 16
61 g were obtained.

(Synthesis Example 4: Condensation product of aromatic aldehyde (M
Synthesis of TB) 3) Instead of o-cresol of Synthesis Example 1
-Methyl-6-t-butylphenol 1320 g, p-
Except that 1.32 g of toluenesulfonic acid was used, 1935 g of an aromatic aldehyde condensate (MTB) of an alkyl-substituted phenol was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 5: Synthesis of Methine-Binding Alkyl-Substituted Polyfunctional Epoxy Resin (CSAE)) A thermometer, a dropping funnel, a stirring rod, and an azeotropic mixture of epichlorohydrin and water are condensed and separated to form a lower epichlorohydrin layer. Aromatic aldehyde condensate (CSA) 1 of alkyl-substituted phenol obtained in Synthesis Example 1 was placed in a flask equipped with a device to be returned to the reactor.
62 g was dissolved in 833 g of epichlorohydrin with stirring.
After the pressure in the reaction system was reduced to about 200 mmHg, epichlorohydrin and water were heated until azeotropic, and the reaction was carried out for 4 hours while water in the reaction system was continuously removed outside the reaction system. Then, the cooling tube was removed, the temperature of the flask was raised to 110 ° C. to remove water, excess epichlorohydrin was removed by evaporation under normal pressure, and further concentrated under reduced pressure. 1 liter of methyl isobutyl ketone and 51.6 g of a 10% by weight aqueous sodium hydroxide solution were added to the resulting mixture of the resin and sodium chloride, and the mixture was reacted at a temperature of 80 to 85 ° C. for 2 hours. After completion of the reaction, 1 liter of methyl isobutyl ketone and 0.5 liter of water were added, and the lower layer aqueous solution of sodium chloride was separated and removed. Next, 0.15 liter of water was added to the methyl isobutyl ketone solution layer for washing and neutralization with phosphoric acid. After separating the aqueous layer, the aqueous layer was further washed with 0.15 liter of water and separated. After removing most of the methyl isobutyl ketone by evaporation under normal pressure, the methyl isobutyl ketone resin solution is evaporated to dryness at a temperature of 140 ° C. under a reduced pressure of 5 mmHg, and 240 g of a methine bond type alkyl-substituted polyfunctional epoxy resin (CSAE) 240 g I got

(Synthesis Example 6: Synthesis of methine-bonded alkyl-substituted polyfunctional epoxy resin (TBHAE)) The aromatic aldehyde condensate of the alkyl-substituted phenol of Synthesis Example 5 (CS
265 g of methine-bonded alkyl-substituted polyfunctional epoxy resin (TBHAE) in the same manner as in Synthesis Example 5 except that A) was replaced with 192 g of an aromatic aldehyde condensate (TBHA) of an alkyl-substituted phenol obtained from Synthesis Example 2. I got

(Synthesis Example 7: Synthesis of methine-bonded alkyl-substituted polyfunctional epoxy resin (XSAE)) An aromatic aldehyde condensate of the alkyl-substituted phenol of Synthesis Example 5 (CS
249 g of methine-bonded alkyl-substituted polyfunctional epoxy resin (XSAE) except that A) was replaced with 172 g of an aromatic aldehyde condensate (XSA) of an alkyl-substituted phenol obtained from Synthesis Example 3. I got

(Synthesis Example 8: Synthesis of methine-bonded alkyl-substituted polyfunctional epoxy resin (MTBE)) The aromatic aldehyde condensate of the alkyl-substituted phenol of Synthesis Example 5 (CS
273 g of methine-bonded alkyl-substituted polyfunctional epoxy resin (MTBE) was prepared in the same manner as in Synthesis Example 5 except that A) was replaced with 203 g of an aromatic aldehyde condensate (MTB) of an alkyl-substituted phenol obtained from Synthesis Example 4. I got

(Synthesis Example 9: Synthesis of acetylated phenol novolak resin (NAc)) HP was placed in a 5-liter four-necked flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, and a stirring rod.
After adding 371 g of -850N (trade name of Hitachi Chemical Co., Ltd., phenol novolak resin, hydroxyl equivalent: 106), adding 2 liters of methyl isobutyl ketone, and stirring and dissolving under a nitrogen stream, 429 g of acetic anhydride and acetic anhydride were added. 5.7 g of sodium was added and dissolved. Thereafter, the temperature was raised in an oil bath, and the reaction was carried out at a reflux temperature for 4 hours. After cooling, 1 liter of a 5% by weight aqueous sodium hydrogen carbonate solution was added, and 370 g of sodium hydrogen carbonate was further added to neutralize the mixture. After sufficiently washing with distilled water and concentrating under reduced pressure, 470 g of acetylated phenol novolak resin (NAc) was obtained.

(Synthesis Example 10: Synthesis of arylesterified cresol novolak resin (NAR)) An o-cresol novolak resin (hydroxyl group) was placed in a 5-liter four-necked flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, and a stirring rod. Equivalent:
119) 238 g were added, 1 liter of methyl ethyl ketone was added, and the mixture was dissolved by stirring under a nitrogen stream, and then 240 g of triethylamine was added, and the mixture was cooled to an internal temperature of 10 ° C by an ice bath. 272 g of methyl benzoic acid was added dropwise over 2 hours while paying attention so that the internal temperature did not exceed 10 ° C. After completion of the addition, the mixture was further reacted at room temperature with stirring for 2 hours. After the reaction,
Triethylamine hydrochloride was removed by suction filtration, and methyl ethyl ketone was removed at 50 ° C. under reduced pressure to obtain a crude product. The obtained crude product was dissolved in 3 liters of toluene, washed sufficiently with a separating funnel, and dried over anhydrous magnesium sulfate. Toluene was removed at 50 ° C. under reduced pressure, and dried under reduced pressure at 100 ° C. for 6 hours to obtain an arylesterified cresol novolak resin (NA) as a target product.
R) 357 g were obtained.

(Synthesis Example 11: Synthesis of arylesterified phenol novolak resin (MNAR)) Instead of the o-cresol novolak resin of Synthesis Example 10, HP-850 was used.
Aryl esterified phenol novolak resin (MNAR) in the same manner as in Synthesis Example 10 except that 212 g of N (Hitachi Chemical Industries, Ltd., phenol novolak resin, hydroxyl equivalent: 106) was used, and 244 g of benzoic acid was used instead of methylbenzoic acid. 319 g were obtained.

(Synthesis Example 12: Synthesis of propionylated cresol novolak resin (PCN)) HP-8 of Synthesis Example 9
50N is converted to o-cresol novolak resin (hydroxyl equivalent:
119) 416 g, acetic anhydride was converted to propionic anhydride 296
498 g of propionylated cresol novolak resin (PCN) was obtained in the same manner as in Synthesis Example 9 except that the amount was changed to g.

Examples 1 to 8 Epoxy resins and curing agents were mixed in the amounts shown in Table 1 and dissolved in a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone at a weight ratio of 1: 1. Next, after the hollow particles were uniformly dispersed in the amounts shown in Table 1, an antioxidant was added. Finally, a curing accelerator is a resin 100 obtained by adding an epoxy resin component and a curing agent component.
A varnish having a concentration of 60% by weight was prepared by adding 0.5 parts by weight to the parts by weight.

Comparative Examples 1-4 Epoxy resins and curing agents were blended in the amounts shown in Table 1 and dissolved in a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone at a weight ratio of 1: 1.
0.5 parts by weight of a curing accelerator was added to 100 parts by weight of the total of the epoxy resin component and the curing agent component to prepare a varnish having a concentration of 60% by weight.

The varnishes of Examples 1 to 8 and Comparative Examples 1 to 4 were impregnated into a 0.2 mm thick glass cloth (basis weight: 210 g / m ² ) and dried at 160 ° C. for 5 minutes to obtain a prepreg. Four prepregs and 18 μm thick copper foil are laminated on top and bottom,
Press molding was performed for 1 hour at 70 ° C. and 2.45 MPa to produce a copper-clad laminate. Next, the glass transition temperature (Tg), dielectric constant, solder heat resistance and electric corrosion resistance of the laminate were evaluated. In addition, the evaluation method was performed as follows. Glass transition temperature (Tg): measured by TMA (thermomechanical analysis) method. Dielectric properties: evaluated by a broadband dielectric property measuring device (gap change method) manufactured by Japan E.M. Solder heat resistance: The test piece is 1 with a pressure cooker
After the moisture absorption treatment for 3 h at 21 ° C. and 0.22 MPa,
It was immersed in a 260 ° C. solder bath for 20 seconds, and the state of the test piece was visually evaluated. Bulging by visual observation, those without measling are marked with ○, those with measling are marked with △,
Those with blisters were evaluated as x. Electrolytic corrosion resistance: The insulation resistance of 400 holes was measured with time for each sample using a test pattern in which the wall spacing between through holes was 350 μm. Test conditions are 85 ° C, 90%
The measurement was performed by applying a voltage of 100 V in an RH atmosphere, and the time until the occurrence of conduction breakdown was measured. Table 1 shows the evaluation results.

[0045]

[Table 1]

From Table 1, it can be seen that the methine-bonded polyfunctional epoxy resin of the present invention, a compound having an active ester group in one molecule,
As apparent from Table 1, the epoxy resin composition using the hollow particles having voids therein and the antioxidant in a predetermined amount is excellent in high glass transition temperature (Tg), low dielectric constant, and corrosion resistance. You can see that.

[0047]

The epoxy resin composition of the present invention and the cured product using the same can achieve both a high glass transition temperature and a low dielectric constant, which have been difficult with conventional epoxy resin laminates. Further, since it is excellent in electric corrosion resistance, it is suitable as a printed wiring board resin for electronic devices requiring high-speed processing such as a computer and high heat resistance.

Continued on the front page (72) Inventor Tomio Fukuda 1500 Oji Ogawa, Shimodate City, Ibaraki Pref.Hitachi Kasei Kogyo Co., Ltd.Shimodate Research Laboratory (72) Inventor Michitoshi Arata 1500 Oji Ogawa Shimodate City Ibaraki Pref. Inside

Claims (14)

[Claims] 1. An epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent, (C) a curing accelerator, and (D) an inorganic or organic hollow having a void inside. In an epoxy resin composition containing particles and (E) an antioxidant, (A) an epoxy resin having two or more epoxy groups in one molecule is a methine-bonded alkyl-substituted polyfunctional epoxy resin represented by Formula 1. And (B) an epoxy resin composition wherein the curing agent is a compound represented by Formula 2 and having one or more active ester groups in one molecule. Embedded image Embedded image 2. (A) 100 to 100 parts by weight of an epoxy resin having two or more epoxy groups per molecule, (B) 50 to 150 parts by weight of a curing agent, and (A) and (B) a total of 100 parts by weight Parts by weight of (C) 0.1 to 5 parts by weight of a curing accelerator, (D) 1 to 50 parts by weight of inorganic or organic hollow particles having voids therein and (E) ) 0.1 to 20 parts by weight of an antioxidant per 100 parts by weight of the epoxy resin.
The epoxy resin composition according to claim 1, comprising parts by weight. 3. (A) A methine-bonded alkyl-substituted polyfunctional epoxy resin represented by the formula 1, an epoxy resin having two or more epoxy groups in one molecule, a bisphenol A epoxy resin, and a phenol novolak epoxy resin A mixture of at least one selected from a brominated phenol novolak epoxy resin, a cresol novolak epoxy resin, a brominated cresol novolak epoxy resin, a biphenyl epoxy resin and a phenol salicylaldehyde novolak epoxy resin.
Or the epoxy resin composition according to claim 2. 4. The method according to claim 1, wherein the methine-bonded alkyl-substituted polyfunctional epoxy resin represented by the formula 1 is an epoxy resin obtained by glycidyl etherification of a condensate of an alkyl-substituted phenol and an aromatic aldehyde. The epoxy resin composition according to any one of the above. 5. The method according to claim 1, wherein the alkyl-substituted phenol is cresols, t-butylphenol, 2,5-xylenol,
The epoxy resin composition according to claim 4, which is at least one or more selected from -methyl-6-t-butylphenol. 6. The epoxy resin composition according to claim 4, wherein the aromatic aldehyde is at least one selected from salicylaldehyde and p-hydroxybenzaldehyde. 7. The curing agent (B) is selected from a curing agent having one or more active ester groups in one molecule represented by the formula 2 and phenol novolak, bisphenol A novolak, cresol novolac, and tetrabromobisphenol A. The epoxy resin composition according to any one of claims 1 to 6, which is a mixture of at least one kind. 8. A compound having one or more active ester groups in one molecule represented by the formula 2 is obtained by esterifying a polyfunctional phenol compound with an acid anhydride or acid chloride of an aromatic or aliphatic carboxylic acid. 8. A compound having one or more active ester groups in one molecule.
The epoxy resin composition according to any one of the above. 9. The epoxy resin composition according to claim 8, wherein the polyfunctional phenol compound is phenol novolak or cresol novolak. 10. An aromatic or aliphatic carboxylic acid anhydride or acid chloride, wherein the acid anhydride or acid chloride is acetic anhydride, propionic anhydride,
The epoxy resin composition according to claim 8, wherein the epoxy resin composition is at least one selected from benzoic acid chlorides and methyl benzoic acid chlorides. 11. The epoxy resin according to claim 8, wherein the polyfunctional phenol compound is phenol novolak, and the acid anhydride or acid chloride of an aromatic or aliphatic carboxylic acid is acetic anhydride or benzoic acid chloride. Composition. 12. (C) The curing accelerator is 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-
The epoxy resin composition according to any one of claims 1 to 11, which is at least one or more selected from methylimidazole and N-dimethylaminopyridine. 13. The method according to claim 1, wherein (D) the inorganic or organic hollow particles having voids therein are hollow glass beads having a particle size of 0.1 μm to 100 μm or styrene hollow polymers. The epoxy resin composition according to the above. 14. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 13.