JPH08319337A - Epoxy resin mixture, epoxy resin composition, cured product and laminate - Google Patents

Abstract

PURPOSE: To obtain an epoxy resin mixture capable of giving cured products with low dielectric constant, low dielectric dissipation factor, low hygroscopicity and high heat resistance, useful for laminates, comprising a phenolated polybutadiene lower (co)polymer's glycidylated product and a specific epoxy resin. CONSTITUTION: This mixture comprises (A) a phenolated polybutadiene lower (co)polymer's glycidylated epoxy resin obtained by adding to (i) a butadiene lower (co)polymer (pref. with a number-average molecular weight of 500-2000) (ii) a phenolic compound at the molar ratio of the component (ii) to the double bond in the component (i) of pref. 0.27 to 0.45 and (B) an epoxy resin of formula I [A is of formula II (R is H, a halogen, etc. ; G is glycidyl; (l) is 1-2), X is of formula III ((m) is the same as (l); (n) is >=0] which is obtained, for example, by glycidylating a phenolic resin prepared by reaction between a phenolic compound and dicyclopentadiene in the presence of an acid catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention can provide a cured product having a low dielectric constant, a low dielectric loss tangent, a low hygroscopicity, and a high heat resistance, and is extremely useful in forming a laminate (printed wiring board). And an epoxy resin composition having excellent properties.

[0002]

2. Description of the Related Art In recent years, with the development in the electric / electronic fields, the performance of each electric / electronic component and the performance required for each raw material thereof have become more and more severe. In particular, in laminated boards (printed wiring boards), problems such as signal delay and transmission loss are accompanied by miniaturization of circuit patterns for high-density mounting of electric / electronic components, speeding up of signals, and higher frequencies. It has surfaced. For this reason, printed wiring boards used in computers and communication devices are required to have low permittivity and dielectric loss tangent.

[0003]

To meet these demands, a laminated board using polyethylene, fluororesin or the like has been developed, but there are problems such as a decrease in adhesive strength with a copper foil and heat resistance. . For this reason, mobile communication devices, etc., which have been rapidly becoming popular recently, are required to withstand all environments due to their characteristics, and in order to realize the physical properties that can withstand the current high-density mounting method, these resins cannot be used. Not enough.

[0004]

The present inventors have completed the present invention as a result of earnest research on a method for solving the above problems. That is, the present invention relates to (1) an epoxy resin (A) obtained by glycidylating a phenolized polybutadiene low (co) polymer obtained by adding a phenol to a butadiene low (co) polymer and a formula (1).

[0005]

Embedded image

(Where A is equation (2) and X is equation (3).

[0007]

[Chemical 4]

(In the formulas (2) and (3), a plurality of R's each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. G represents a glycidyl group. Represents an integer of 1 to 2),
l and m may be the same or different. Also, n
Represents an integer of 0 or more. ) An epoxy resin mixture containing the epoxy resin (B) represented by the formula (2), (2) an epoxy resin mixture according to the above (1), an epoxy resin composition containing a curing agent, (3) an epoxy according to the above (2). A cured product obtained by curing a resin mixture, and (4) a laminated board prepared by using the epoxy resin mixture as described in (2) above.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As a method for synthesizing a phenolized butadiene low (co) polymer which is a raw material of the epoxy resin (A) described in (1) above, for example, phenols are added to a butadiene low (co) polymer. There is a method of doing. The butadiene (co) polymer has a number average molecular weight of preferably 300 to 3000, more preferably 500 to 200.
No. 0 butadiene low polymer or a low copolymer of butadiene with a conjugated diolefin and / or an aromatic vinyl monomer or the like.

The butadiene low polymer can be produced by a known method. For example, it can be produced by a method of anionically polymerizing butadiene at a temperature of 0 to 100 ° C. using an alkali metal or organic alkali metal compound as a catalyst. In this case, in order to control the molecular weight to obtain a low polymer with less gel content, etc., an organic alkali metal compound such as benzyl sodium is used as a catalyst, and a compound having an alkylaryl group, for example, toluene is used as a chain transfer agent. Chain transfer polymerization method, living polymerization method using polycyclic aromatic compounds such as naphthalene as an activator in a tetrahydrofuran solvent and alkali metal such as sodium as a catalyst, aromatic hydrocarbons such as toluene and xylene as a solvent, sodium, etc. Method of controlling the molecular weight by adding ethers such as dioxane and the like with an alkali metal as a catalyst, or coordination using an acetylacenate compound of a Group 8 metal such as cobalt and nickel and an alkylaluminum halogenide as a catalyst A method such as an anionic polymerization method is preferable.

The butadiene low copolymer is, for example, preferably 3 to 40 mol%, more preferably 5 to 30 mol% isoprene, 2, or 2, based on butadiene.
A conjugated olefin such as 3-dimethylbutadiene or piperylene or a copolymer of aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene and vinylbenzene can be used.

The method for adding phenols to the butadiene low (co) polymer is not particularly limited, and the method described in, for example, JP-A-61-126162 can be used.

That is, a method of reacting a butadiene low (co) polymer with a phenol or the like in the presence of a Lewis acid catalyst can be used. Specific examples of phenols that can be used at this time include phenol, o-cresol, and m.
-Cresol, p-cresol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2-tertbutyl-5-methylphenol, brominated phenol, hydroquinone, 2-methylhydroquinone, resorcin,
Catechol, 1 naphthol, 2 naphthol, 2,7
-Dihydroxynaphthalene, 1,6-dihydroxynaphthalene and the like are included, but are not limited thereto.

The amount of the phenols used should be larger than the number of double bonds present in the butadiene low (co) polymer, preferably 1.2 times or more, and more preferably 1.2 times or more. Is 1.2 to 2 times the molar amount. Also,
The addition amount of phenols is preferably 0.25 to 0.5 mol, and more preferably 0.27 to 0.45 mol, based on 1 mol of the double bond present in the butadiene low (co) polymer. Is particularly preferable.

Specific examples of the Lewis acid catalyst that can be used include boron trifluoride complexes such as boron trifluoride / ether complex and boron trifluoride / phenol complex. The amount of the Lewis acid catalyst used is not particularly limited,
It can be appropriately selected depending on the type of catalyst used, and for example, when boron trifluoride is used, it is preferably 5 to 50 mmol, more preferably 10 to 20 mmol per 100 g of the butadiene low (co) polymer.

The reaction for adding phenols to the butadiene low (co) polymer can be carried out usually at 50 to 120 ° C, preferably 70 to 100 ° C.

In the above reaction, the cyclization reaction of the double bond existing in the butadiene (co) polymer simultaneously occurs at the same time as the addition reaction of the phenols, and heat is generated. Therefore, in order to control the reaction temperature, the catalyst is used. Is preferably used, and / or a method in which the butadiene low (co) polymer is sequentially added is preferably used, but particularly preferably.

In the above reaction, a small amount of an inert solvent such as toluene, for the purpose of decreasing the viscosity of the reaction mixture,
Xylene or the like can also be used. Further, the water content in the reaction mixture is usually 100 ppm by weight or less, preferably 60 ppm by weight or less.

The phenolized butadiene low (co) polymer obtained by the above reaction has a softening point of 90 to 200 ° C., preferably 100 to 160 ° C. and a hydroxyl equivalent of usually 250 to.
It is preferably 700 g / equivalent, preferably 280-600 g / equivalent. The phenolized polybutadiene low (co) polymer thus obtained will be referred to as a phenol resin (C) unless otherwise specified.

The epoxy resin (B) used in the present invention can be obtained by glycidylating a phenol resin represented by the following formula (4) by a known method.

[0021]

Embedded image

(Where B is the equation (5) and Y is the equation (6).

[0023]

[Chemical 6]

(In formulas (5) and (6), l, m and R have the same meanings as in formula (2)), and n represents an integer of 0 or more. )

The method for producing the phenolic resin represented by the above formula (4) is not particularly limited, and for example, it can be produced by the following method. That is, a method of reacting phenols with dicyclopentadiene in the presence of an acid catalyst can be adopted. Examples of the phenols that can be used at this time include the phenols specifically exemplified above, but are not particularly limited thereto.

Specific examples of the acid catalyst that can be used include boron trifluoride and its complexes, aluminum chloride, zinc chloride, sulfuric acid, Lewis acids such as titanium chloride, phosphoric acid, sulfuric acid, oxalic acid and other inorganic or organic acids. An acid etc. can be mentioned. These may be used alone or in combination of two or more.

As a method for reacting the above-mentioned phenols with dicyclopentadiene, for example, phenols are heated and melted, a catalyst is added thereto and uniformly dissolved, and then 50 to 180 ° C., preferably 80 to 150. Dicyclopentadiene is added dropwise at ° C. The addition amount of each is 0.001 to 1 mol of dicyclopentadiene,
0.1 mol, preferably 0.005 to 0.10 mol and phenols 0.1 to 10 mol, preferably 0.3 to 4 mol. Besides the above method, phenols may be added to the mixture of dicyclopentadiene and the catalyst, or the catalyst may be gradually added to the mixture of dicyclopentadiene and the phenol. The addition time of each raw material varies depending on the raw material blending method and the type of phenols as described above, but the reaction is carried out for 1 to 10 hours and then for several hours, and then the unreacted monomer is distilled off by heating under reduced pressure. Thus, the phenol resin represented by the above formula (4) is obtained.

In the above reaction, a small amount of an inert solvent such as toluene, for the purpose of decreasing the viscosity of the reaction mixture,
Xylene, nitrobenzene, etc. can also be used. Further, the amount of water in the reaction mixture is usually 100 weight pp.
m or less, preferably 60 ppm by weight or less. Hereinafter, the phenol resin thus obtained will be referred to as a phenol resin (D) unless otherwise specified.

The epoxy resin (A) and the epoxy resin (B) described in (1) used in the present invention are obtained by reacting a phenol resin (C) and a phenol resin (D) with epihalohydrin to form a glycidyl group. . Examples of the glycidylation method include the following methods. At a temperature between 20 and 120 ° C., a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the mixture of the phenol resin (C) or (D) and epihalohydrin all at once or gradually. React for 5 to 30 hours. At this time, an aqueous solution may be used as the alkali metal hydroxide. In that case, water and epihalohydrin are continuously added from the reaction mixture under reduced pressure or normal pressure while continuously adding the alkali metal hydroxide. A method may be used in which distilling is performed, liquid separation is performed, water is removed, and epihalohydrin is continuously returned to the reaction mixture. Examples of epihalohydrin include epichlorohydrin, epibromhydrin, epiiodohydrin, β-methylepichlorohydrin, and the like, with epichlorohydrin being most preferred.

Phenolic resin (C) in the above method
Alternatively, the amount of epihalohydrin used is usually 0.5 to 20 mol, preferably 0.7, relative to 1 equivalent of the hydroxyl group in (D).
The amount of alkali metal hydroxide used is usually 0.1.
It is 5 to 1.5 mol, preferably 0.7 to 1.2 mol. In addition, dimethyl sulfone, dimethyl sulfoxide,
By adding an aprotic polar solvent such as dimethylformamide or 1,3-dimethyl-2-imidazolidinone, a resin having a low amount of hydrolyzable halogen can be obtained, which is suitable for applications for encapsulating electronic materials. The amount of the aprotic polar solvent used is 5 to 200% by weight based on the weight of epihalohydrin,
It is preferably 10 to 100% by weight. The reaction is facilitated by adding alcohols such as methanol and ethanol or dioxane in addition to the above solvents. The amount of alcohol or dioxane used is usually 2 to 100% by weight, preferably 4 to 100% by weight based on the weight of epihalohydrin.
It is 50% by weight. When the amount of epihalohydrin used is small, the viscosity of the reaction mixture increases, but an inert solvent such as toluene or xylene can be used for the purpose of decreasing the viscosity.

Further, the phenol resin (C) or (D)
And a mixture of epihalohydrin (which may include the solvent shown above) tetramethylammonium chloride, tetramethylammonium bromide, quaternary ammonium salts such as trimethylbenzylammonium chloride as a catalyst, usually 30 ~ 150 ℃, Preferably, the reaction is carried out at 40 ° C to 120 ° C for 1 to 30 hours, and the resulting halohydrin ether of the phenol resin (C) or (D) is a solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. , Usually 20 ~
It is also possible to react at 120 ° C., preferably 30 to 100 ° C. for 1 to 30 hours to ring-close the halohydrin ether to obtain a glycidyl ether. In this case, the amount of the quaternary ammonium salt used is usually 0.001 to 0.2 with respect to 1 equivalent of the hydroxyl group of the phenol resin (C) or (D).
The molar amount is preferably 0.05 to 0.1 mol.

Usually, these reaction products are washed with water or after removing excess epihalohydrin under heating and reduced pressure without washing with water, and then dissolved in a solvent such as toluene, xylene or methyl isobutyl ketone to obtain sodium hydroxide or hydroxide. The reaction is carried out by adding an aqueous solution of an alkali metal hydroxide such as potassium. In this case, the amount of the alkali metal hydroxide used is 0.01 to 0.2 mol, preferably 0.05 to 0. 0, relative to 1 equivalent of the hydroxyl group of the phenol resin (C) or (D).
It is 1 mol. The reaction temperature is usually 40 to 120 ° C., preferably 50 to 100 ° C., the reaction time is usually 0.5 to 5 hours,
It is preferably 1 to 3 hours.

After completion of the reaction, the by-produced salt is removed by filtration, washing with water, etc., and the solvent such as toluene, xylene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain an epoxy resin having a small amount of hydrolyzable halogen. Obtainable. As described above, the epoxy resin (A)
Alternatively, the epoxy resin (B) can be obtained.

The epoxy resin mixture of the present invention contains the epoxy resin (A) and the epoxy resin (B) as essential components, and may be contained in combination with other epoxy resins if necessary. In the epoxy resin mixture of the present invention, the compounding ratio of the epoxy resin (A) and the epoxy resin (B) is usually such that the weight ratio of the epoxy resin (A) / epoxy resin (B) is 0.2.
The range is 5 to 4.0, preferably 0.32 to 3.1, and more preferably 0.42 to 2.4.

Specific examples of other epoxy resins which can be used in combination with the epoxy resin (A) and the epoxy resin (B) include novolac type epoxy resin, trisphenol methane type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, Condensates of phenols and various aldehydes, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, alicyclic epoxy resins, reactive diluents having a glycidyl group and the like are usually epoxy. There is no need to be limited to these as long as it can be used as a resin.
These may be used alone or in combination of two or more. The amount of the other epoxy resin that can be used together is usually 0.4 in the following formula L = (total weight of epoxy resin (A) and epoxy resin (B)) / (weight of other epoxy resin used in combination). The above conditions are satisfied, preferably 0.6 or more, and more preferably 0.65 or more.

Further, in order to cure the epoxy resin mixture of the present invention to obtain a cured product having flame retardancy, a glycidyl ether of tetrabromobisphenol A, a halogenated epoxy resin such as a brominated phenol novolac epoxy resin, or a , Commonly used flame retardants for polymers such as aluminum hydroxide and antimony trioxide.

The epoxy resin composition of the present invention contains the above epoxy resin mixture and a curing agent. Specific examples of the curing agent that can be used include aliphatic polyamines such as triethylenetetramine, diethylenetriamine, N-aminoethylpiperazine and isophoronediamine, aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone, amine curing agents such as polyamide polyamines. , Various phenol type novolac resins, trisphenolmethanes, phenolic curing agents such as phenolic resin (C) and phenolic resin (D) used in the present invention, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid, methylnaphthalenedicarboxylic acid anhydride, pyromellitic acid anhydride, trimellitic acid anhydride, acid anhydride curing agents such as dodecyl succinic anhydride, and curing agents such as dicyandiamide, but usually with a curing agent for epoxy resins There is no need to be limited to these as long as they are used Te. These may be used alone or in combination of two or more.

The amount of the curing agent used in the epoxy resin composition of the present invention is usually 0.5 to 1.5 equivalents, preferably 0.65 to 1 equivalent to 1 equivalent of epoxy groups of the epoxy resin used. .2 equivalents, more preferably 0.8-1.
It is used in an amount of 1 equivalent, more preferably 0.85 to 1.05 equivalent. However, when an acid anhydride is used as the curing agent in the above, the equivalent of the acid anhydride is multiplied by 0.9 to be the equivalent of the acid anhydride used. When dicyandiamide is used, the equivalent of dicyandiamide is multiplied by 0.65 to obtain the equivalent of dicyandiamide. This means that when one equivalent of the curing agent is used, 0.9 equivalent of the acid anhydride and 0.65 equivalent of the dicyandiamide should be used.

The epoxy resin composition of the present invention optionally contains a curing accelerator. Specific examples of the curing accelerator that can be used include imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, tertiary amine compounds such as tris- (dimethylaminomethyl) phenol,
Examples of known curing accelerators include triphenylphosphine compounds, Lewis acids such as boron trifluoride and salts thereof, and the like, but are not particularly limited. These may be used alone or in combination of two or more. The curing accelerator is 0.01 to 15 with respect to 100 parts by weight of the epoxy resin.
Parts by weight are used as needed.

The epoxy resin composition of the present invention may further contain known additives, if desired. Examples of the additive include polybutadiene and its modified products,
Modified product of acrylonitrile copolymer, silicone gel,
Silicone oil, silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride,
Inorganic fillers such as asbestos, mica, glass powder, glass fiber, glass non-woven fabric, carbon fiber, surface treatment agents for fillers such as silane coupling agents, release agents, carbon black, phthalocyanine blue, phthalocyanine green, etc. Agents.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components in a predetermined ratio, and the mixing at this time is usually a softening of each component constituting the epoxy resin composition of the present invention. It can be performed by heating and melting at a temperature about 20 to 100 ° C. higher than the point. Also, the respective components of the epoxy resin composition can be mixed by uniformly dispersing or dissolving them in a solvent or the like. The solvent is not particularly limited as long as each component can be uniformly mixed, and examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, methyl cellosolve, and dimethylformamide.

The epoxy resin composition of the present invention can be made into a cured product thereof by a generally known method. Eg 0
The cured product can be obtained in 0.5 minutes to 500 hours at 250 ° C.

Further, the epoxy resin composition of the present invention can be suitably used for a low dielectric constant laminate. When used as a laminate, flame retardancy is required, and therefore, in the cured product obtained by curing the epoxy resin composition of the present invention, usually 1
The halogenated epoxy resin or the curing agent containing halogen in the structure may be blended so as to contain 0 to 40% by weight, preferably 12 to 35% by weight, more preferably 15 to 27% of bromine. desirable. In this case, the epoxy resin composition of the present invention is dissolved in a solvent to form a varnish, and the varnish is impregnated and applied to a substrate such as glass cloth, glass non-woven fabric, synthetic fiber or paper, and heated and semi-dried to remove the solvent. Then, a prepreg is produced. Next, a required number of the prepregs are laminated to form a laminate, copper foil is laminated on one side or both sides of this laminate, and the laminate is produced by heating and pressing to cure the epoxy resin composition of the present invention. Can be done. Examples of the solvent at this time include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, and the like as specific examples, and the amount of these is usually relative to the total weight of the epoxy resin composition and the solvent. It is 10 to 70% by weight, preferably 15 to 65% by weight.

[0044]

EXAMPLES The present invention will be described more specifically with reference to synthesis examples and examples. The present invention is not limited to these examples.

Synthesis Example 1 A flask equipped with a stirrer, a reflux condenser, and a stirrer was placed in a phenolized butadiene low (co) polymer (manufactured by Nippon Petrochemical Co., Ltd., softening point 150 ° C., hydroxyl equivalent 317 g / e).
q, trade name "Nisseki Special Phenolic Resin PP-700-3
00 ") (hereinafter PP-700-300) 317 parts by weight,
925 parts by weight of epichlorohydrin and 93 parts by weight of methanol were charged, stirred, dissolved, and heated to 70 ° C., and 41 parts by weight of 41 parts of flaky sodium hydroxide (purity 99%) was added to 100 parts.
The mixture was added over a period of minutes and then reacted at 70 ° C. for 1 hour. Then, after repeatedly washing with water until the washing liquid became neutral, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 370 parts by weight of methyl isobutyl ketone (hereinafter MIBK) was added and dissolved. Furthermore, this MIB
The solution of K was heated to 70 ° C., 13 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour, and then repeatedly washed with water until the washing liquid became neutral. Then, MIBK is distilled off from the oil layer under heating and reduced pressure to obtain an epoxy resin (E1) (the above epoxy resin (A)) 3
50 parts by weight were obtained. The epoxy equivalent of the obtained epoxy resin (E1) was 540 g / eq and the softening point was 128 ° C.

Synthetic Example 2 In Synthetic Example 1, PP-700-300 was used as a phenolized butadiene low (co) polymer (manufactured by Nippon Petrochemical Co., Ltd.,
Softening point 112 ° C, hydroxyl equivalent 555g / eq, trade name "Nisseki special phenol resin PP-1000-180")
(The following PP-1000-180) 555 parts by weight, 1620 parts by weight of epichlorohydrin, 160 parts by weight of methanol, and 1200 parts by weight of MIBK were used. As a result, the epoxy resin (E
2) 500 parts by weight of (epoxy resin (A)) was obtained. The epoxy equivalent of the obtained epoxy resin (E2) was 740 g /
eq and softening point were 93 degreeC.

Synthesis Example 3 In Synthesis Example 1, PP-700-300 was mixed with phenol resin (D) (manufactured by Nippon Petrochemical Co., Ltd., softening point 112 ° C.,
Hydroxyl equivalent 180g / eq, trade name "Nisseki Special Phenolic Resin DPP-3H") (hereinafter DPP-3H) 180 parts by weight, epichlorohydrin 550 parts by weight, methanol 55 parts by weight, MIBK 470 parts by weight except Performed the same operation as in Synthesis Example 1. As a result, 223 parts by weight of the epoxy resin (E3) (above epoxy resin (B)) was obtained. The epoxy equivalent of the obtained epoxy resin (E3) was 290 g / eq and the softening point was 78 ° C.

The DPP-3H used as a raw material is a compound having a structure in which B in the formula (4) is represented by the following formula (7) and Y is represented by the following formula (8). Therefore, the obtained epoxy resin (E3) has a structure in which A in the formula (1) is represented by the formula (9) and X is represented by the formula (10). (G in the formulas (9) and (10) represents a glycidyl group.)

[0049]

[Chemical 7]

Synthesis Example 4 In Synthesis Example 1, PP-700-300 was used as a phenol resin (D) (manufactured by Nippon Petrochemical Co., Ltd., softening point 95 ° C.,
Hydroxyl equivalent 170 g / eq, trade name "Nisseki Special Phenolic Resin DPP-M") (hereinafter DPP-M) 170 parts by weight, epichlorohydrin 550 parts by weight, methanol 55 parts by weight, MIBK 470 parts by weight except Performed the same operation as in Synthesis Example 1. As a result, 220 parts by weight of the epoxy resin (E4) (the above epoxy resin (B)) was obtained. The epoxy equivalent of the obtained epoxy resin (E4) is 2
The softening point was 70 g / eq and 60 ° C. In the DPP-M used as the raw material, B in the formula (4) is represented by the above formula (7),
Y has a structure respectively represented by the above formula (8), and in the epoxy resin (E4), A in the formula (1) is represented by the above formula (9),
X has a structure represented by the above formula (10).

Examples 1 to 6 20 g of dimethylformamide prepared by dissolving dicyandiamide in the amounts shown in Tables 1 and 2 in a solution prepared by dissolving resins of the types and amounts shown in Tables 1 and 2 in 25 g of methyl ethyl ketone.
And 0.15 g of 2-ethyl-4-methylimidazole were added to prepare a varnish of the epoxy resin composition. Use this varnish with glass cloth (Nittobo Co., Ltd. WEA18W10)
5F-115) and dried at 150 ° C. for 5 minutes to obtain B
A stage-shaped prepreg was obtained. Eight sheets of this prepreg and one sheet of copper foil (Nikko Gould Co., Ltd.) were stacked, and 180 ° C
Then, it was heated under pressure for 2 hours to obtain a cured product (laminated plate). The results of measuring the physical properties of the cured product thus obtained are shown in Table 1
The physical properties of the cured product of No. 2 are shown.

The physical property values were measured by the following methods or conditions. -Glass transition temperature: measured by the TMA method. Moisture absorption rate: Test piece with copper foil peeled off at a temperature of 85 ° C and a humidity of 8
It was made to absorb moisture at 5% for 100 hours and calculated from the weight change before and after that. -Dielectric constant, dielectric loss tangent: It carried out based on the method described in JIS C-6481 (dielectric constant and dielectric loss tangent). -Copper foil peeling strength: Measured according to the method described in JIS C-6481 (peeling strength).

[0053]

[Table 1]

EH in Table 1 is Yuka Shell Epoxy Co., Ltd.
Manufactured by Epicoat 5050. (Same in Table 2)

[0055]

[Table 2]

In Table 2, EP is EPP manufactured by Nippon Kayaku Co., Ltd.
It represents N-501.

[0057]

The epoxy resin composition of the present invention has excellent low dielectric constant and low dielectric loss tangent, suppresses deterioration of heat resistance and adhesiveness, and exhibits low hygroscopicity (water resistance). It is extremely useful when a cured product is given and it is used as a material for laminated boards (printed wiring boards, etc.).

Claims (4)

[Claims] 1. An epoxy resin (A) obtained by glycidylation of a phenolized polybutadiene low (co) polymer obtained by adding phenols to a butadiene low (co) polymer, and a compound of formula (1): (Where A is the formula (2) and X is the formula (3) (A plurality of Rs in formulas (2) and (3) each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. G represents a glycidyl group. Represents an integer of 2), and l and m may be the same or different. In addition, n represents an integer of 0 or more. ) An epoxy resin mixture containing an epoxy resin (B) represented by 2. An epoxy resin composition comprising the epoxy resin mixture according to claim 1 and a curing agent. 3. A cured product obtained by curing the epoxy resin composition according to claim 2. 4. A laminated board prepared by using the epoxy resin composition according to claim 2.