JP3537549B2 - Epoxy resin composition, cured product and laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a cured product having a low dielectric constant, a low dielectric loss tangent, a low hygroscopic property, and a high heat resistance, and is very useful for a laminate (printed wiring board). The present invention relates to an epoxy resin composition having excellent heat resistance.

[0002]

2. Description of the Related Art In recent years, with the development in the electric and electronic fields, the performance of each electric and electronic component and the required performance for each raw material have become increasingly severe. In particular, in the case of laminated boards (printed wiring boards), problems such as signal delays and transmission losses are accompanied by the miniaturization of circuit patterns for high-density mounting of electric and electronic components, the increase in signal speed, and the increase in frequency. Has emerged. For this reason, printed wiring boards used in computers and communication devices are required to have a low dielectric constant and a low dielectric loss tangent.

[0003]

To meet these demands, laminates using polyethylene, fluororesin or the like have been developed, but have problems such as a decrease in adhesive strength to copper foil and heat resistance. For this reason, mobile communication devices and the like that are rapidly spreading in recent years are required to withstand all kinds of environments due to their characteristics, and in order to realize physical properties that can withstand the current high-density mounting method, these resins must be used. Not enough.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on a method for solving the above-mentioned problems, and as a result, completed the present invention. That is, the present invention relates to (1) an epoxy resin (A) obtained by glycidylating a phenolized polybutadiene low (co) polymer (D) obtained by adding a phenol to a low butadiene (co) polymer, and (1)

[0005]

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(Where A is the formula (2) and X is the formula (3)

[0007]

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(A plurality of Rs in the 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 1 to 2).
l and m may be the same or different. Also, n
Represents an integer of 0 or more. (2) (a) a mixture of the following phenolic resin (D) and phenolic resin (E), or (2) (a) a mixture of the following phenolic resin (D) and phenolic resin (E): b) an epoxy resin composition containing a phenolic resin (D), a phenolic resin (E), an epoxy resin (F) obtained by reacting a mixture of polyhydric phenols with epihalohydrin, and a compound (C) having a cyanate group; Phenol resin (D): Phenolic resin obtained by adding phenol to butadiene low (co) polymer Phenol resin (E): Phenolic resin represented by formula (4)

[0009]

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

[0011]

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(In the formulas (5) and (6), l, m and R represent the same meanings as in the formulas (2) and (3).), And n represents an integer of 0 or more. (3) a cured product obtained by curing the epoxy resin composition according to the above (1) and / or (2); (4) using the epoxy resin composition according to the above (1) and / or (2) The present invention relates to a prepared laminate.

As a method for synthesizing the phenolated low-butadiene (co) polymer (the phenolic resin (D) according to (2)) as a raw material of the epoxy resin (A) according to (1), for example, A method of adding a phenol to the (co) polymer. The butadiene low (co) polymer preferably has a number average molecular weight of 300 to 30.
00, more preferably 500 to 2000 butadiene low polymer or butadiene and conjugated diolefin and / or
Alternatively, a low copolymer with an aromatic vinyl monomer or the like can be used.

The butadiene low polymer can be produced by a known method. For example, it can be produced by a method in which butadiene is anionically polymerized 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 obtain a low polymer having a low gel content by controlling the molecular weight, an organic alkali metal compound such as benzyl sodium is used as a catalyst, and an aromatic compound having an alkyl group such as toluene is used as a chain transfer agent. A chain transfer polymerization method, a living polymerization method using a polycyclic aromatic compound such as naphthalene as an activator in a tetrahydrofuran solvent, an alkali metal catalyst such as sodium as a catalyst, an aromatic hydrocarbon such as toluene, xylene as a solvent, sodium A polymerization method in which an alkali metal such as dioxane is used as a catalyst and an ether such as dioxane is added to control the molecular weight, or a polymerization method using an acetylacenate compound of a Group VIII metal such as cobalt or nickel and an alkylaluminum halide as a catalyst. A method such as a coordination anion polymerization method is preferred.

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

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

That is, a method of reacting a phenol with a butadiene low (co) polymer 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, m-cresol, p-cresol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2-tertbutyl-4-methylphenol, bromine Phenol, 2-methylhydroquinone, resorcin, catechol, 1 naphthol, 2 naphthol, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and the like, but are not limited thereto.

The amount of the phenol used must be greater than the number of moles of the double bond present in the butadiene low (co) polymer, preferably at least 1.2 times the mole, more preferably at least 1.2 moles. Is 1.2 to 2 times mol. Also,
The addition amount of phenols is preferably 0.25 to 0.5 mol, more preferably 0.27 to 0.45 mol, per 1 mol of double bond present in the butadiene low (co) polymer. Is particularly preferred.

Specific examples of the usable Lewis acid catalyst include boron trifluoride / ether complex and boron trifluoride / ether complex.
And boron trifluoride complexes such as phenol complexes. The amount of the Lewis acid catalyst used is not particularly limited, and can be appropriately selected depending on the type of the catalyst used. For example, when boron trifluoride is used, 100 g of a butadiene low (co) polymer is used.
Preferably 5 to 50 mmol, more preferably 1
0-20 mmol.

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

In the above reaction, a cyclization reaction of the double bond present in the butadiene (co) polymer is generated simultaneously with the addition reaction of the phenol, and heat is generated. Is preferably employed, and / or a method of sequentially adding a low-butadiene (co) polymer is preferably employed. Particularly, it is most preferable to sequentially add the low-butadiene (co) polymer little by little.

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

The phenolated 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 200 ° C.
It is preferably 700 g / equivalent, preferably 280-600 g / equivalent. As described above, the phenolated butadiene low (co) polymer (phenol resin (D) is obtained.

The method for producing the phenolic resin (E) represented by the above formula (4), which is a raw material of the epoxy resin (B) used in the present invention, is not particularly limited, and can be produced, for example, by the following method. That is, a method of reacting phenols with dicyclopentadiene in the presence of an acid catalyst can be used. The phenols that can be used at this time include, but are not limited to, the phenols specifically exemplified above.

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

As a method of reacting the above-mentioned phenols with dicyclopentadiene, for example, the phenols are heated and melted, a catalyst is added thereto, and the mixture is uniformly dissolved, and then heated at 50 to 180 ° C., preferably 80 to 150 ° C. At 0 ° C., dicyclopentadiene is added dropwise. The amount of each is 0.001 to 1 mole of dicyclopentadiene,
It is 0.1 mol, preferably 0.005 to 0.10 mol, and 0.1 to 10 mol, preferably 0.3 to 4 mol of phenols. In addition to the above method, a phenol may be added to a mixture of dicyclopentadiene and a catalyst, or a catalyst may be gradually added to a mixture of dicyclopentadiene and a phenol. The addition time of each raw material varies depending on the method of blending the raw materials as described above and the type of the phenol, but is allowed to react for 1 to 10 hours, and then for several hours, and then the unreacted monomer is distilled off by distillation under reduced pressure while heating. As a result, a phenol resin (E) represented by the above formula (4) is obtained.

In the above reaction, a small amount of an inert solvent such as toluene is used for the purpose of lowering the viscosity of the reaction mixture.
Xylene, nitrobenzene and the like can also be used. Further, the amount of water in the reaction mixture is usually 10% by weight.
It is preferably at most 0 ppm, more preferably at most 60 ppm.

The epoxy resin (A) and the epoxy resin (B) described in the above (1) used in the present invention are obtained by reacting the phenolic resin (D) and the phenolic resin (E) obtained as described above with epihalohydrin, respectively. And glycidylation. The specific method of glycidylation will be described later.

The epoxy resin (F) according to the above (2) is
(A) an epoxy resin obtained by reacting a mixture obtained by mixing the phenol resin (D) and the phenol resin (E) obtained above with epihalohydrin, or (b) a phenol resin (D) and a phenol resin ( E) and an epoxy resin obtained by reacting a mixture obtained by mixing one or more polyhydric phenols with epihalohydrin. The epoxy resin (F) is a component in which molecules of the phenol resin (D) and a part of the molecules of the phenol resin (E) (and polyhydric phenols) are respectively bonded by -CH ₂ CH (OH) CH _2- groups. Therefore, compared with the case of mixing after glycidylation (the epoxy resin composition described in the above (1)), the components of each epoxy resin are more familiar, and the resin composition using this resin has an adhesive property with a copper foil. In some cases, a cured product excellent in toughness, toughness, blister resistance and the like may be given. The above epoxy resin is thus phenol resin (D), phenol resin (E)
The OH groups of (and polyhydric phenols) are glycidylated, but some of the molecules of these glycidylated products are
As described above, some are bonded by the above groups, but some are not bonded and glycidylated phenol resin (D) (epoxy resin (A)) or glycidylated phenol resin (E) (epoxy resin (B )).

In the case of the above (a), the phenol resin (D)
The mixing ratio of phenol resin (E) and phenol resin (E) is represented by the following formula R = (hydroxyl equivalent of phenol resin (D) +56) /
R defined by (hydroxyl equivalent of phenolic resin (E) +56) is usually in the range of 0.25 to 4.0, preferably 0.32 to 3.1, more preferably 0.42 to 2.4. To do.

In the case of the above (b), the polyhydric phenol mixed as the third component is not particularly limited as long as it is a known polyhydric phenol. Specific examples of polyhydric phenols that can be used include phenol novolaks, cresol novolaks, bisphenols, biphenols, trisphenolmethanes, tetraphenolethanes, condensates of various aldehydes and ketones with phenols, and These bromides are exemplified. In addition, the amount of each used is the same as in the case of the above (a), the mixing ratio of the phenol resin (D) and the phenol resin (E), and the polyhydric phenol is represented by the following formula M = [phenol resin (D) Used amount × (1 + 56 / hydroxyl equivalent of phenolic resin (D)) + used amount of phenolic resin (E) × (1 + 56 / hydroxyl equivalent of phenolic resin (E)) / [used amount of polyhydric phenols × ( 1+
56 / hydroxyl equivalent of polyhydric phenol) + used amount of phenol resin (D) × (1 + 56 / phenol resin (D)
Of the phenolic resin (E) × (1)
+ 56 / hydroxyl equivalent of phenolic resin (E))] is usually 0.30 or more, preferably 0.3
The amount is 5 or more, more preferably 0.40 or more. In the above, the unit of the amount used is g, and the unit of the hydroxyl equivalent is g / eq. When two or more polyhydric phenols are used as a mixture, the hydroxyl equivalent is a weighted average of the hydroxyl equivalents of the respective polyhydric phenols in the mixture.

A mixture of a phenol resin (D) and a phenol resin (E) (and a polyhydric phenol) satisfying such conditions (hereinafter referred to as a phenol mixture) is glycidylated to obtain an epoxy resin (F). Examples of the glycidylation method include the following methods. An alkali metal hydroxide solid such as sodium hydroxide, potassium hydroxide or the like is added to the mixture of the phenol mixture and the epihalohydrin, or the mixture is reacted at a temperature between 20 and 120 ° C. In this case, an aqueous solution of the alkali metal hydroxide may be used.In this case, the alkali metal hydroxide is continuously added, and water and epihalohydrin are continuously removed from the reaction mixture under reduced pressure or normal pressure. A method may be employed in which the water is removed by distilling, the water is removed, and the epihalohydrin is continuously returned to the reaction mixture. Examples of the epihalohydrin include epichlorohydrin, epibromhydrin, epiiodohydrin and the like, and epichlorohydrin is most preferable.

In the above method, the amount of epihalohydrin used is generally 0.5 to 20 mol, preferably 0.7 to 10 mol, per equivalent of hydroxyl group in the phenol mixture, and the amount of alkali metal hydroxide used is Usually 0.5-1.
It is in the range of 5 moles, preferably 0.7-1.2 moles.
Further, by adding an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, and 1,3-dimethyl-2-imidazolidinone, a resin having a low hydrolyzable halogen content can be obtained, and electronic material sealing is performed. Suitable for use. The amount of the aprotic polar solvent used is 5 to 200% by weight, preferably 10
-100% by weight. The reaction can be facilitated by adding alcohols such as methanol and ethanol and dioxane in addition to the above solvents. The amount of the alcohol or dioxane to be used is usually 2 to 100% by weight, preferably 4 to 50% by weight, based on the weight of epihalohydrin. 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 reducing the viscosity.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is used as a catalyst in a mixture of a phenol mixture and an epihalohydrin (which may contain the solvent described above), Usually 30 to 150 ° C, preferably 40 to 120 ° C.
The reaction is carried out at 0 ° C., and a solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the resulting halohydrin ether of the phenol mixture, usually at 20 to 120 ° C., preferably at 30 to 100 ° C. The reaction can be carried out at an intermediate temperature to ring-close the halohydrin ether to give the glycidyl ether. The amount of the quaternary ammonium salt used in this case is usually in the range of 0.001 to 0.2 mol, preferably 0.05 to 0.1 mol, per equivalent of the hydroxyl group of the phenol mixture.

Usually, these reaction products are washed with water, or after removing excess epihalohydrin under heating and reduced pressure without washing with water, dissolved again in a solvent such as toluene, xylene, methyl isobutyl ketone, and the like. An aqueous solution of an alkali metal hydroxide such as potassium oxide is added to react again. In this case, the amount of the alkali metal hydroxide used is 0.1 to 1 equivalent of the hydroxyl group of the phenol mixture.
The amount is from 01 to 0.2 mol, preferably from 0.05 to 0.1 mol. The reaction temperature is usually 40 to 120 ° C, preferably 50
The reaction is carried out at a temperature of usually 0.5 to 5 hours, preferably 1 to 3 hours.

After the completion of the reaction, salts produced as by-products are removed by filtration, washing with water, and the like. Further, by distilling off solvents such as toluene, xylene and methyl isobutyl ketone under reduced pressure under heating, an epoxy resin having a small amount of hydrolyzable halogen is obtained. Obtainable. As described above, the epoxy resin (F) described in the above (2) can be obtained. In the above, when the phenol resin (D) or the phenol resin (E) is used instead of the phenol mixture, the epoxy resin (A) and the epoxy resin (B) in the epoxy resin composition described in the above (1) are obtained. Can be

The epoxy resin composition of the present invention (the epoxy resin composition described in the above (1) and (2) is hereinafter referred to as the epoxy resin composition of the present invention) unless otherwise specified. C) and an epoxy resin (A) and an epoxy resin (B) or an epoxy resin containing (F) as an essential component, and further containing another epoxy resin if necessary. The mixing ratio of the epoxy resin (A) and the epoxy resin (B) is such that the weight ratio of the epoxy resin (A) / epoxy resin (B) is usually 0.25 to 4.0,
Preferably 0.32 to 3.1, more preferably 0.42
~ 2.4.

The compound (C) may be any compound having a cyanate group. Specific examples that can be used include dicyanatobenzene, tricyanatobenzene,
Dicyanatonaphthalene, dicyanatobiphenyl,
2,2'-bis (4-cyanatophenyl) propane,
Bis (4-cyanatophenyl) methane, bis (3,5
-Dimethyl-4-cyanatophenyl) methane, 2,
2′-bis (3,5-dimethyl-4-cyanatophenyl) propane, 2,2′-bis (4-cyanatophenyl) ethane, 2,2′-bis (4-cyanatophenyl) hexafluoropropane, bis (4 -Cyanatophenyl) sulfone, bis (4-cyanatophenyl) thioether, phenol novolak cyanate, phenol-dicyclopentadiene cocondensate obtained by converting a hydroxyl group to a cyanate group, and the like, but are not limited thereto. is not. When the amount of the epoxy resin used is X, the amount of the following curing agent (optional component) is Y, and the amount of the compound (C) is Z, the compound (C) is (X + Y) / Z on a weight basis. = 0.3-3, preferably 0.5-2.

Specific examples of the above-mentioned other epoxy resin which the epoxy resin composition of the present invention optionally contains include novolak 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, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, alicyclic epoxy resins, reactive diluents having a glycidyl group, and the like. There is no need to be limited. These may be used alone or as a mixture of two or more. The amount of other epoxy resin used is
The following formula L = (total weight of epoxy resin (A) and epoxy resin (B)) / (weight of other epoxy resin used together) or L = (weight of epoxy resin (F)) / (other weight used together) (Weight of epoxy resin) is generally 0.4 or more, preferably 0.6 or more, and more preferably 0.65 or more.

In order to obtain a cured product having flame retardancy by curing the epoxy resin composition of the present invention, a glycidyl ether of tetrabromobisphenol A or a brominated phenol novolak epoxy resin may be used in combination. Usually, 10 to 40% by weight, preferably 1% by weight in the cured product
The above epoxy resin may be blended so as to contain 2 to 35% by weight, more preferably 15 to 27% by weight of bromine.

In the epoxy resin composition of the present invention, if necessary, the cyanate group of compound (C) is trimerized to form
zinc naphthenate to form an m-triazine ring,
Catalysts such as cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, dibutyltin maleate and the like can also be used. The catalyst is usually used in an amount of 0.0001 to 0.5% based on 100 parts by weight of the total weight of the epoxy resin, the curing agent and the compound (C).
10, preferably 0.00015 to 0.0015 parts by weight.

If necessary, the epoxy resin composition of the present invention may contain a compound generally used as a curing accelerator for epoxy resin. For example, imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, boron trifluoride complexes, and the like are used, and the amount of use is 0.01 to 15 parts by weight, preferably 0 to 100 parts by weight of the epoxy resin. 0.1 to 10 parts by weight.

The epoxy resin composition of the present invention may contain a compound generally used as a curing agent for an epoxy resin, if necessary. Specific examples of the curing agent that can be used include triethylenetetramine, diethylenetriamine,
Mensendiamine, N-aminoethylpiperazine, aliphatic polyamines such as isophoronediamine, diaminodiphenylmethane, aromatic polyamines such as diaminodiphenylsulfone, amine-based curing agents such as polyamide polyamines,
Acid anhydride-based curing agents having an acid anhydride group such as phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnaphthalenedicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, dodecylsuccinic anhydride, etc. And dicyandiamide, phenol type novolak resin, trisphenolmethanes, and curing agents such as phenolic resin (D) and phenolic resin (E) in the present invention, but need not be limited thereto. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.
The curing agent is usually 500 per 100 parts by weight of the epoxy resin.
Not more than 400 parts by weight, preferably not more than 400 parts by weight is used.

The epoxy resin composition of the present invention may further contain known additives, if necessary. Specific examples of additives that can be used include polybutadiene and modified products thereof, modified acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, silica, alumina, calcium carbonate, Inorganic filler such as quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, glass fiber, glass non-woven fabric or carbon fiber, silane coupling agent Examples of the filler include a surface treating agent for a filler, a release agent, and a coloring agent such as carbon black, phthalocyanine blue, and phthalocyanine green.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at a predetermined ratio.
Mixing may be carried out, if necessary, from 20 to 100 from the softening point of
It can be performed by heating and melting at a temperature as high as about ° C. Also, the components can be mixed by uniformly dispersing or dissolving the components of the epoxy resin composition in a solvent or the like. Although the solvent is not particularly limited, specific examples that can be used include toluene, xylene, methyl ethyl ketone,
Examples thereof include methyl isobutyl ketone, dioxane, methyl cellosolve, and dimethylformamide. These solvents are usually 5 to 300 parts by weight based on 100 parts by weight of the resin component,
Preferably, 10 to 150 parts by weight is used.

Since the cured product of the epoxy resin composition of the present invention thus obtained has excellent low dielectric constant and low dielectric loss tangent, it can be suitably used for a low dielectric constant sealing material, a low dielectric constant paint, and the like. Can be done.

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, so that the cured product usually contains 10 to 40% by weight, preferably 12 to 35% by weight, more preferably 15 to 27% by weight of bromine. As described above, it is desirable to blend a halogenated epoxy resin or a compound containing a halogen in the molecule as a curing agent. The laminate of the present invention is, for example, a resin composition of the present invention is dissolved in a solvent to form a varnish, and the varnish is impregnated and applied to a base material such as glass cloth, glass nonwoven fabric, synthetic fiber, and paper, and dried by heating. To remove the solvent to produce a prepreg. Next, a required number of the prepregs are laminated to form a laminate, and a copper foil is laminated on one side or both sides of the laminate, and the composition of the present invention is cured by heating and pressurizing. As the solvent at this time, specific examples in which toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide and the like can be used, and these solvents are usually 10 to 70% by weight in the mixture of the epoxy resin composition and the solvent , Preferably 15 to
An amount occupying 65% by weight is used.

[0048]

EXAMPLES The present invention will be described more specifically with reference to synthesis examples and examples. Note that the present invention is not limited to these examples. In addition, the unit of the epoxy equivalent in a synthesis example is g / eq.

Synthesis Example 1 A phenolated butadiene low polymer (Nippon Petrochemical Co., Ltd.) was placed in a flask equipped with a stirrer, a reflux condenser, and a stirrer.
, Softening point 150 ° C, hydroxyl equivalent 317 g / eq, trade name “Nisseki special phenolic resin PP-700-300”)
317 parts by weight (hereinafter referred to as PP-700-300), 925 parts by weight of epichlorohydrin, 93 parts by weight of methanol were charged, stirred, dissolved, and heated to 70 ° C. to give 41 parts by weight of flake sodium hydroxide (99% pure). Was added over 100 minutes, and then reacted at 70 ° C. for 1 hour. Then, after repeating washing with water until the washing solution became neutral, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure,
370 parts by weight of methyl isobutyl keto (hereinafter referred to as M
IBK) was added and dissolved. Further, the MIBK solution was heated to 70 ° C., and 13 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. The mixture was reacted for 1 hour, and then repeatedly washed with water until the washing solution became neutral. Then, MIBK was distilled off from the oil layer under heating and reduced pressure to obtain 350 parts by weight of the epoxy resin (E1) (the epoxy resin (A)). The epoxy equivalent of the obtained epoxy resin (E1) is 5
40, softening point was 128 ° C.

Synthesis Example 2 In Synthesis Example 1, PP-700-300 was converted to a phenolated butadiene low polymer (manufactured by Nippon Petrochemical Co., Ltd., softening point 112 ° C., hydroxyl equivalent 555 g / eq, trade name “Nisseki Special Phenol Resin PP-1000-180 ”) (hereinafter P
P-1000-180) 555 parts by weight, 1620 parts by weight of epichlorohydrin, 160 parts by weight of methanol, M
The same operation was performed except that the weight was changed to 1200 parts by weight of IBK. As a result, 500 parts by weight of the epoxy resin (E2) (the epoxy resin (A)) was obtained. The obtained epoxy resin (E1) had an epoxy equivalent of 740 and a softening point of 93 ° C.

Synthesis Example 3 In Synthesis Example 1, PP-700-300 was converted to a phenol resin (E) (manufactured by Nippon Petrochemical Co., Ltd., having a softening point of 112 ° C.).
Hydroxyl equivalent 180 g / 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 same Was performed. As a result, the epoxy resin (E3)
(The above epoxy resin (B)) 223 parts by weight was obtained. The obtained epoxy resin (E3) had an epoxy equivalent of 290 and a softening point of 78 ° C.

Synthesis Example 4 In Synthesis Example 1, PP-700-300 was converted to a phenol resin (E) (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,
550 parts by weight of epichlorohydrin and 55 parts by weight of methanol
The same operation was performed except that the parts by weight and MIBK were changed to 470 parts by weight. As a result, 220 parts by weight of the epoxy resin (E4) (the epoxy resin (B)) was obtained. The obtained epoxy resin (E4) had an epoxy equivalent of 270 and a softening point of 60 ° C.

The following Synthesis Examples 5 to 13 show synthesis examples of the epoxy resin (F).

Synthesis Example 5 In Synthesis Example 1, PP-700-300 was changed to 53 parts by weight, DPP-3H was further added at 144 parts by weight, epichlorohydrin was at 620 parts by weight, methanol was at 60 parts by weight, and MIBK was at 500 parts by weight. The same operation was performed except for changing to. As a result, 236 parts by weight of the epoxy resin (E5) was obtained. The obtained epoxy resin (E5) had an epoxy equivalent of 325 and a softening point of 85 ° C.

Synthesis Example 6 In Synthesis Example 1, PP-700-300 was changed to 106 parts by weight, DPP-3H was further added at 96 parts by weight, epichlorohydrin was at 620 parts by weight, methanol was at 60 parts by weight, and MIBK was at 500 parts by weight. The same operation was performed except for changing to. As a result, 240 parts by weight of an epoxy resin (E6) was obtained. The epoxy equivalent of the obtained epoxy resin (E6) was 362, and the softening point was 95 ° C.

Synthesis Example 7 In Synthesis Example 1, PP-700-300 was changed to 160 parts by weight, DPP-3H was further added by 48 parts by weight, epichlorohydrin was 640 parts by weight, methanol was 65 parts by weight, and MIBK was 500 parts by weight. The same operation was performed except for changing to. As a result, 236 parts by weight of the epoxy resin (E7) was obtained. The obtained epoxy resin (E7) had an epoxy equivalent of 434 and a softening point of 110 ° C.

Synthesis Example 8 In Synthesis Example 1, PP-700-300 was changed to 106 parts by weight, DPP-M was added at 94 parts by weight, epichlorohydrin was 620 parts by weight, methanol was 60 parts by weight,
The same operation was performed except that MIBK was changed to 500 parts by weight. As a result, 239 parts by weight of the epoxy resin (E8) was obtained. The obtained epoxy resin (E8) had an epoxy equivalent of 350 and a softening point of 90 ° C.

Synthesis Example 9 In Synthesis Example 1, PP-700-300 was replaced with PP-10.
00-180 114 parts by weight, DPP-3H
Was added, and the same operation was performed except that epichlorohydrin was changed to 650 parts by weight, methanol was changed to 65 parts by weight, and MIBK was changed to 500 parts by weight. As a result, 226 parts by weight of the epoxy resin (E9) was obtained. The obtained epoxy resin (E9) has an epoxy equivalent of 595 and a softening point of 89 ° C.
Met.

Synthesis Example 10 In Synthesis Example 1, PP-700-300 was changed to 64 parts by weight, 57 parts by weight of DPP-3H and 83 parts by weight of tetrabisphenol A were added, and epichlorohydrin was added to 6 parts by weight.
30 parts by weight, 63 parts by weight of methanol, 50 parts of MIBK
The same operation was performed except that the amount was changed to 0 parts by weight. As a result, 242 parts by weight of the epoxy resin (E10) was obtained. The epoxy equivalent of the obtained epoxy resin (E10) was 365,
The softening point was 85 ° C.

Synthesis Example 11 In Synthesis Example 1, PP-700-300 was changed to 96 parts by weight, 29 parts by weight of DPP-3H and 83 parts by weight of tetrabisphenol A were added, and epichlorohydrin was added to 6 parts by weight.
30 parts by weight, 63 parts by weight of methanol, 50 parts of MIBK
The same operation was performed except that the amount was changed to 0 parts by weight. As a result, 238 parts by weight of the epoxy resin (E11) was obtained. The epoxy equivalent of the obtained epoxy resin (E11) was 377,
The softening point was 92 ° C.

Synthesis Example 12 In Synthesis Example 1, PP-700-300 was changed to 32 parts by weight, DPP-3H (86 parts by weight) and tetrabisphenol A (83 parts by weight) were added, and epichlorohydrin was added to 6 parts by weight.
30 parts by weight, 63 parts by weight of methanol, 50 parts of MIBK
The same operation was performed except that the amount was changed to 0 parts by weight. As a result, 245 parts by weight of the epoxy resin (E12) was obtained. The epoxy equivalent of the obtained epoxy resin (E12) was 360,
The softening point was 98 ° C.

Synthesis Example 13 In Synthesis Example 1, PP-700-300 was changed to 53 parts by weight, and 48 parts by weight of DPP-3H, 83 parts by weight of tetrabisphenol A and 16 parts by weight of trisphenolmethane were added, and 630 parts of epichlorohydrin was added. The same operation was performed except that the parts by weight, methanol were changed to 63 parts by weight, and MIBK was changed to 500 parts by weight. As a result, 244 parts by weight of the epoxy resin (E13) was obtained. The epoxy resin (E13) obtained had an epoxy equivalent of 344 and a softening point of 79 ° C.

Examples 1 to 16 In a solution prepared by dissolving the resin and the compound (C) of the kind and amount shown in the column of varnish composition in Tables 1 to 4 in 50 g of a 1: 1 mixed solvent of methyl ethyl ketone / toluene, 0.1 part by weight of zinc naphthenate was added per minute to prepare an epoxy resin composition (varnish). The varnish was impregnated in a glass cloth (WEA18W105F-115, manufactured by Nitto Boseki Co., Ltd.) and dried at 150 ° C. for 5 minutes to obtain a B-stage prepreg. Eight sheets of this prepreg and one sheet of copper foil (JTC foil 70 μm manufactured by Nikko Gould Co., Ltd.)
The laminate was heated at 0 ° C. for 2 hours under pressure to form a laminate having a thickness of 1.6 mm.

The cured product thus obtained (laminate)
Are shown in Tables 1 to 4.

The physical properties of the cured product were measured by the following methods. -Glass transition temperature: Measured by TMA method. Water absorption: 100 at 85 ° C. and 85% relative humidity
Weight increase rate when tested for time. -Dielectric constant and dielectric tangent: Measured according to the method described in JIS C-6481 (dielectric constant and dielectric tangent). -Copper foil peel strength: Measured according to the method described in JIS C-6481 (peel strength).

[0066]

[Table 1]                                   Table 1 Example 1 2 3 4 5 Varnish composition   Resin / weight (g) E1 / 18 E1 / 18 E2 / 18 E5 / 36 E6 / 36   Resin / weight (g) E3 / 18 E4 / 18 E3 / 18 EH / 35 EH / 35   Resin / weight (g) EH / 35 EH / 35 EH / 35   Compound (C) / weight (g) C1 / 29 C1 / 29 C1 / 29 C1 / 29 C1 / 29 Physical properties of cured product   Glass transition temperature (° C) 170 167 163 175 172   Water absorption (%) 0.47 0.48 0.42 0.48 0.46   Dielectric constant 3.7 3.8 3.6 3.9 3.7   Dielectric tangent 0.006 0.006 0.005 0.007 0.006   Peel strength (Kg / cm) 1.7 1.8 1.7 1.7 1.8 1.8

[0067]

[Table 2]                                   Table 2 Example 6 7 8 9 10 Varnish composition   Resin / weight (g) E7 / 36 E8 / 36 E9 / 36 E10 / 40 E11 / 40   Resin / weight (g) EH / 35 EH / 35 EH / 35 EH / 20 EH / 20   Compound (C) / weight (g) C1 / 29 C1 / 29 C1 / 29 C1 / 40 C1 / 40 Physical properties of cured product   Glass transition temperature (° C) 169 168 162 173 169   Water absorption (%) 0.44 0.44 0.43 0.45 0.43   Dielectric constant 3.6 3.7 3.6 3.6 3.7 3.6   Dielectric tangent 0.005 0.006 0.005 0.006 0.005   Peel strength (Kg / cm) 1.8 1.7 1.8 1.8 1.7

[0068]

[Table 3]                                   Table 3 Example 11 12 13 14 15 Varnish composition   Resin / weight (g) E12 / 40 E13 / 40 E10 / 40 E10 / 40 E10 / 30   Resin / Weight (g) EH / 20 EH / 20 EH / 20 EH / 20 P1 / 20   Resin / weight (g) EH / 20   Compound (C) / weight (g) C1 / 40 C1 / 40 C2 / 40 C3 / 40 C1 / 30 Physical properties of cured product   Glass transition temperature (° C) 177 182 165 173 162   Water absorption (%) 0.49 0.51 0.42 0.43 0.49   Dielectric constant 3.9 4.0 3.5 3.5 3.7   Dielectric tangent 0.008 0.008 0.005 0.005 0.007   Peel strength (Kg / cm) 1.7 1.6 1.7 1.7 1.7 1.6

[0069]

Table 4 Example 16 Composition of Varnish Resin / Weight (g) E10 / 30 Resin / Weight (g) P2 / 20 Resin / Weight (g) EH / 20 Compound (C) / Weight (g) C1 / 30 Physical properties of cured product Glass transition temperature (℃) 159 Water absorption (%) 0.48 Dielectric constant 3.6 Dielectric tangent 0.008 Peel strength (Kg / cm) 1.6 EH: Yuka Shell Epoxy Co., Ltd. Epicoat 505
0 EP: Nippon Kayaku Co., Ltd. EPPN-501 P1: Nippon Petrochemical Co., Ltd. special phenolic resin PP
-700-300 P2: Nippon Petrochemical Co., Ltd. special phenolic resin PP
-1000-180 C1: 2,2'-di (4-cyanatophenyl) propane C2: 2,2'-di (4-cyanatophenyl) hexafluoropropane C3: cyanate of phenol-dicyclopentadiene copolymer monster

[0070]

The epoxy resin composition of the present invention has excellent low dielectric properties and low dielectric loss tangent properties, suppresses a decrease in heat resistance and adhesiveness, and exhibits high moisture resistance (water resistance). This is extremely useful when an object is provided, particularly when used as a material for a laminated board (such as a printed wiring board).

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-8-319338 (JP, A) JP-A-8-319337 (JP, A) JP-A-7-10963 (JP, A) JP-A-6-319338 345846 (JP, A) JP-A-5-339473 (JP, A) JP-A-5-214072 (JP, A) JP-A 5-1129 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/20-59/32 C08L 63/00-63/10 C08L 79/04-79/06 C08J 5/24 CFC

Claims (4)

(57) [Claims] 1. An epoxy resin (A) obtained by glycidylation of a phenolized polybutadiene low (co) polymer (D) obtained by adding a phenol to a butadiene low (co) polymer, and a compound represented by the formula (1): Formula 1 (Where A is the formula (2) and X is the formula (3) (In formulas (2) and (3), a plurality of Rs each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. G represents a glycidyl group. L and m represent 1
Represents an integer of ２2. ), And l and m may be the same or different. N represents an integer of 0 or more. An epoxy resin composition containing the epoxy resin (B) represented by the formula (I) and a compound (C) having a cyanate group. 2. An epihalohydrin is reacted with (a) a mixture of the following phenolic resin (D) and phenolic resin (E) or (b) a mixture of phenolic resin (D), phenolic resin (E) and polyhydric phenols. An epoxy resin composition comprising an epoxy resin (F) obtained by the above method and a compound (C) having a cyanate group. Phenol resin (D): A phenol resin obtained by adding phenols to a butadiene low (co) polymer. Phenol resin (E): A phenol resin represented by formula (4). (Where B is the formula (5), and Y is the formula (6)) (In the formulas (5) and (6), l, m and R represent the same meanings as in the formulas (2) and (3).), And n represents an integer of 0 or more. ) 3. A cured product obtained by curing the epoxy resin composition according to claim 1. 4. A laminate prepared by using the epoxy resin composition according to claim 1 and / or 2.