JP2002012650A - Epoxy resin composition for low-dielectric material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition for low-dielectric materials having excellent adhesion, solder resistance and curability and assuming a low permittivity and/or a low dielectric dissipation factor and a cured product obtained therefrom. SOLUTION: This epoxy resin composition for the low-dielectric materials consists essentially of (A) an epoxy resin having >=2 epoxy groups in one molecule, (B) an aromatic compound obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group and having >=2 active ester groups in one molecule and (C) a reaction accelerator.

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 and a cured product thereof, and more particularly, it is useful as a resin for printed circuit boards, a resin for laminated boards, a resin for electrical insulation, and a resin for various adhesives. Epoxy resin composition having excellent dielectric properties, especially low dielectric constant, low dielectric loss tangent, and also excellent in adhesiveness, solder resistance and curability, and a cured product thereof, and a low dielectric material using the composition, For example, the present invention relates to a substrate and a laminate.

[0002]

2. Description of the Related Art Conventionally, epoxy resins excellent in electrical properties, mechanical properties, adhesiveness and the like have been widely used for laminated boards, printed boards and the like. In recent years, with the advent of an information-oriented society and an enormous amount of information, there has been a growing need for higher-density and higher-layer printed wiring boards and higher heat-resistant materials. High-speed signal transmission and high-frequency communication in equipment are indispensable, and transmission characteristics are required to be improved, and an insulating material having a low dielectric constant and a low dielectric loss tangent is desired. Particularly for communication, it is important to reduce the dielectric loss tangent.

However, in a normal epoxy resin, the ring opening of the epoxy group occurs in the reaction with the curing agent.
Accordingly, a hydroxyl group having a high polarity was generated, and the dielectric constant and the dielectric loss tangent could not be reduced due to the hydroxyl group.

In recent years, JP-A-11-71499 and JP-A-11-7
As disclosed in Japanese Patent Publication No. 1500 and Japanese Patent Application Laid-Open No. H11-130939, a cured epoxy resin using a compound containing an active ester group as a curing agent for an epoxy resin has been proposed as a low dielectric constant material. Japanese Patent Application Laid-Open No. 7-292067 describes a modified epoxy resin using an aromatic compound having an active ester group as a modifying agent, and a method for producing the modified epoxy resin, which is proposed as a low dielectric constant material.

[0005] However, among these, the compound containing an active ester group as a curing agent or the compound containing an active ester as a modifier used in a modified epoxy resin is a phenolic hydroxyl group of a polyhydric phenol compound. Are esterified with a monocarboxylic acid, and an aromatic compound having two or more active ester groups in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group according to the present invention. The configuration is completely different. In addition, the invention according to JP-A-7-292067,
The present invention differs from the present invention because it contains a hardener not present in the present invention as an essential component. Furthermore, an active ester group-containing aromatic compound obtained by esterifying a phenolic hydroxyl group of a polyhydric phenol compound with a monocarboxylic acid has a low insulating property because the phenol component is generated as a free acid when the ester portion is cleaved. Not only that, the dielectric constant and dielectric tangent also increase.

Further, Japanese Patent Application Laid-Open Nos. 5-51517 and 5-263
No. 058, and Japanese Patent Application Laid-Open No. 5-271637 disclose nothing about dielectric properties, and heat-cured a thermosetting resin composition containing an epoxy resin and a polyester as essential components shown in the publication. The polyester in the cured resin does not show low dielectric properties.

[0007] Also, JP-A-11-349666, JP-A-6-2
No. 93823, JP-A-63-57614, JP-A-63-30451
JP, JP-A-62-212416, and JP-A-8-120057
In the active ester shown in the publication, active esters composed of polyhydric carboxylic acids are used, but none of them mentions the dielectric properties of the epoxy resin and has low dielectric properties. I didn't know at all.

[0008]

The problems to be solved by the present invention are excellent in adhesiveness, solder resistance and curability,
Another object of the present invention is to provide an epoxy resin composition which gives a cured epoxy resin having a low dielectric constant and / or a low dielectric loss tangent.

[0009]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the use of an aromatic compound containing an active ester group as a curing agent for an epoxy resin produces free acid. Without, and at the time of curing does not produce a highly polar hydroxyl group,
It has been found that an epoxy resin composition having excellent dielectric properties, that is, an epoxy resin cured product having a low dielectric constant and / or a low dielectric loss tangent can be obtained, and the present invention has been completed.

That is, the present invention provides

(1) Epoxy resin having two or more epoxy groups in one molecule (A), two or more in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group An epoxy resin composition for a low dielectric material, comprising an aromatic compound having an active ester group (B) and a reaction accelerator (C) as essential components;

(2) The epoxy resin composition for a low dielectric material according to (1), wherein the low dielectric property is a dielectric constant of 3.5 or less.

(3) The epoxy resin composition for a low dielectric material according to (1) or (2), wherein the low dielectric property is a dielectric loss tangent of 0.01 or less.

(4) The ratio of the active ester group-containing aromatic compound (B) to the epoxy resin (A) having two or more epoxy groups in one molecule is based on the epoxy equivalent of the epoxy resin (A). The ester equivalent of the aromatic compound (B) is 0.3 to 1.5 equivalents,

When the reaction accelerator (C) is an epoxy resin (A)
And the active ester group-containing aromatic compound (B) in a total of 10
The epoxy resin composition for a low dielectric material according to any one of (1) to (3), wherein the amount is 0.005 to 10.0 parts by weight with respect to 0 parts by weight.

(5) An aromatic compound (B) having two or more active ester groups in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group,

An aromatic compound having a polycarboxylic acid;
(1) to (4), which are all aromatic compounds (B ') having two or more active ester groups in one molecule obtained from an aromatic compound having a phenolic hydroxyl group.
An epoxy resin composition for a low dielectric material according to any one of the above,

(6) An aromatic compound (B) having two or more active ester groups in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group has the general formula (1) The epoxy resin composition for a low dielectric material according to any one of (1) to (4), which is an aromatic compound represented by the following formula:

General formula (1)

[0020]

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Wherein k is an integer of 2 to 4, and R ¹ is the following three formulas

[0022]

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(Wherein A and B are the same or different and each represents a halogen atom or an alkyl group, m ₁ is 0-5,
m ₂ is 0 to 4, and m ₃ represents a 0-3. Any one of)
Is an aromatic ring represented by

R ² is the following nine formulas

[0025]

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(Wherein, D, E and G each independently represent the same or different and represent a halogen atom or an alkyl group, X represents a sulfur atom, an oxygen atom, SO ₂ or CO, n ₁ , n ₂ and n ₃ are each independently 0 to 4, n ₄ and n ₅ each independently 0
To 3, n ₆ represents 0-2. ) Is an aromatic ring represented by any one of the above. ]

(7) The epoxy resin (A) having two or more epoxy groups in one molecule has an epoxy equivalent of 100 to 1
The epoxy resin composition for a low dielectric material according to any one of (1) to (6), wherein

(8) The reaction accelerator (C) is selected from the group consisting of imidazole compounds, organic phosphine compounds, organic phosphite compounds, phosphonium salts, amines and salts thereof, urea compounds, bases, and salts of crown ethers. The epoxy resin composition for a low dielectric material according to any one of (1) to (7), which is a mixture of at least one selected from the group consisting of:

(9) A low dielectric material obtained by curing the epoxy resin composition for a low dielectric material according to any one of (1) to (8),

(10) A low-dielectric substrate comprising a film or sheet comprising the low-dielectric material according to (9), which has a metal foil on one or both sides of the film or sheet.

Is provided.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin composition for a low dielectric material of the present invention has not only excellent adhesiveness, solder resistance and curability, but also excellent low dielectric properties, that is, low dielectric constant, It is important to exhibit a low dielectric loss tangent. In order to satisfy these required properties, a specific composition component, that is, an epoxy resin (A) having two or more epoxy groups in one molecule (the above) Hereinafter, this may be referred to as “epoxy resin (A)” as necessary.), An aromatic compound having two or more active ester groups in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group. Group compound (B) (hereinafter referred to as "active ester group-containing aromatic compound (B)" as necessary), reaction accelerator (C)
It is necessary to use an epoxy resin composition for a low dielectric material, which contains as an essential component.

However, in the present invention, "low dielectric property" means a low dielectric constant and / or a low dielectric loss tangent.
Dielectric constant at 100 kHz to 10 GHz at room temperature is 3.5
Or less, preferably 3.2 or less, more preferably 2.0 to
3.2 and a dielectric loss tangent of 0.01 or less, preferably 0.009 or less, and more preferably 0.001 to 0.00.
9 means.

In the present invention, the term “low-dielectric material” means a material used for applications requiring low-dielectric properties, and the term “epoxy resin composition for low-dielectric materials” refers to low-dielectric materials. It means an epoxy resin composition used for the material.

In general, when the heat resistance of an epoxy resin cured product increases, the adhesiveness typified by the peel strength of copper foil decreases. However, the epoxy resin cured product has a good balance having strong adhesiveness while maintaining the heat resistance. A cured product is required, and the epoxy resin composition of the present invention has a glass transition temperature of 130 ° C. or more as an index of heat resistance and a copper foil peel strength of 1.2 kN / m as an index of adhesiveness. An epoxy resin cured product satisfying the above is provided.

The epoxy resin (A) having two or more epoxy groups in one molecule of the present invention has an epoxy equivalent of 10
0-1000, low to medium molecular weight (300-500
0) an epoxy resin;

Specifically, for example, cresol novolak, phenol novolak, naphthol-modified novolak, bisphenol-A, bisphenol-F, tetrabromobisphenol-A, biphenyl type epoxy resin, triphenyl type epoxy resin, tetraphenyl type epoxy resin, etc. Phenol glycidyl ether type epoxy resin, polypropylene glycol, alcohol type glycidyl ether type epoxy resin such as hydrogenated bisphenol-A, dicyclopentadiene skeleton-containing dicyclopentadiene type epoxy resin, naphthalene type containing naphthalene skeleton Epoxy resin, glycidyl ester type epoxy resin using hexahydrophthalic anhydride or dimer acid as raw material, polyamine such as diaminodiphenylmethane as raw material Glycidyl amine type epoxy resin, alicyclic epoxy resin,

[0038] Brominated epoxy resins and mixtures thereof are mentioned. Among them, in order to obtain good heat resistance, cresol novolak epoxy resin, phenol novolak epoxy resin, naphthol-modified novolak epoxy resin, bisphenol Epoxy resin, biphenyl epoxy resin, triphenyl epoxy resin,
A mixture of one or more epoxy resins selected from a tetraphenyl epoxy resin, a dicyclopentadiene epoxy resin, a naphthalene epoxy resin, and a brominated epoxy resin is preferred.

The aromatic compound (B) having two or more active ester groups in one molecule obtained from the compound having a polyvalent carboxylic acid and the aromatic compound having a phenolic hydroxyl group according to the present invention has at least 2 More than one carboxylic acid
An aromatic compound obtained from a compound (I) having in the molecule and an aromatic compound (II) having a phenolic hydroxyl group, and having two or more ester groups in the molecule of the aromatic compound. Group compound. Further, a linear or dendritic polymer may be included. When the compound (I) is a compound containing an aliphatic chain, the compatibility with the epoxy resin (A) can be increased. When the compound has an aromatic ring, the heat resistance can be increased.

Further, in the present invention, in order to impart heat resistance, the active ester group-containing aromatic compound (B) is obtained from an aromatic compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group. A wholly aromatic compound (B ′) having two or more active ester groups in one molecule (hereinafter referred to as “active ester group-containing wholly aromatic compound (B ′)” as necessary) as a curing agent. Preferably, it is used.

However, in the present invention, a wholly aromatic compound means that the aromatic ring contained in the compound is one of the molecules obtained from an aromatic compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group. An aromatic compound that is directly bonded to one or more ester groups and / or other aromatic rings in the molecule and has no aliphatic chains connecting them, said compound having high heat resistance and low heat resistance. It can exhibit dielectric properties, that is, a low dielectric constant and / or a low dielectric loss tangent.
Also, in the case of the wholly aromatic compound, a linear or dendritic polymer may be used.

For example, a highly heat-resistant wholly aromatic polyester derived from tetramethylbiphenol and iso- and / or terephthalic acid is also preferably used as the active ester group-containing aromatic compound (B) of the present invention.

Here, the above-mentioned wholly aromatic compound (B ')
The structural skeleton of the aromatic ring in the following three formulas

[0044]

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(A and B are the same or different and each represents a halogen atom or an alkyl group, m ₁ is from 0 to 5, and m ₂ is from 0 to
4, and m ₃ represents a 0-3. ) (Hereinafter referred to as “R ¹ ”).

Alternatively, the following nine formulas

[0047]

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(Wherein D, E and G are each independently the same or different and represent a halogen atom or an alkyl group, X represents a sulfur atom, an oxygen atom, SO ₂ or CO, n ₁ , n ₂ and n ₃ are each independently 0 to 4, n ₄ and n ₅ each independently 0
To 3, n ₆ represents 0-2. ) (Hereinafter referred to as “R ² ”).

The halogen atom of A, B, D, E or G includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom, a chlorine atom and a bromine atom.

The alkyl group of A, B, D, E or G is not particularly limited in the number of carbon atoms, but is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
-Butyl group, sec-butyl group, tert-butyl group,
n-pentyl group, isopentyl group, neopentyl group, t
ert-pentyl group, n-hexyl group, 4-methyl-2
-A pentyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and the like, preferably an alkyl group having 1 to 3 carbon atoms. X represents a sulfur atom, an oxygen atom, SO ₂ or CO.

M ₁ is 0-5, m ₂ is 0-4, and m ₃ is 0
3 are shown. n ₁ , n ₂ and n ₃ are each independently 0 to 4, n ₄
And n ₅ are each independently 0 to 3, n ₆ represents 0-2.

Further, the active ester group-containing wholly aromatic compound (B ') of the present invention comprises two or more R ¹ components and one or more R ² components.
An ester compound in which the components are directly linked by an ester bond is preferable.

More specifically, as the active ester group-containing wholly aromatic compound (B '), a wholly aromatic compound represented by the general formula (1) is more preferably mentioned.

General formula (1)

[0055]

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Wherein k is an integer of 2 to 4;
¹ and R ² are as previously defined.

According to the present invention, an active ester group-containing aromatic compound (B), more preferably an active ester group-containing wholly aromatic compound (B ') is used as a curing agent, so that the epoxy resin cured product can be hydrolyzed. Since the free acid generated by this can be suppressed as much as possible, it exhibits low dielectric properties.

The active ester group-containing aromatic compound (B) of the present invention may have a molecular weight of 3 if it requires liquid formability.
It is 00-5000, preferably 300-1000.

Examples of the method for synthesizing the active ester group-containing wholly aromatic compound (B) of the present invention include an acetic anhydride method, an interface method,
A conventionally known synthesis method such as a direct method may be used.

For example, in the acetic anhydride method, an aromatic compound having a phenolic hydroxyl group is acetylated with, for example, an excess of acetic anhydride, and then subjected to a deacetic acid reaction with a compound having a polyvalent carboxylic acid to form an active ester group. A method for obtaining a contained aromatic compound is exemplified. The amount of acetic anhydride is desirably at least equimolar to the phenolic hydroxyl group in order to perform sufficient acetylation.

In the interfacial method, an organic phase containing an acid chloride of a polycarboxylic acid and an aqueous phase containing an aromatic compound containing a phenolic hydroxyl group are brought into contact with each other to obtain an active ester group-containing aromatic compound. Can be. The solvent used for the organic phase is a water-insoluble solvent that dissolves the acid chloride of the polycarboxylic acid, and for example, toluene, hexane, and the like are preferable.

Specifically, as a compound used as a raw material of the active ester group-containing aromatic compound (B), malonic acid, an aliphatic carboxylic acid mainly used for the purpose of increasing compatibility with an epoxy resin, Succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid,
Itaconic acid, aconitic acid, tricarballylic acid, 1,
2,3,4-butanetetracarboxylic acid, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid, 1,2,3,4-
Saturated or unsaturated aliphatic polycarboxylic acids such as cyclopentanetetracarboxylic acid, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2-dicarboxylic anhydride, or And anhydrides and acid chlorides thereof. The aromatic carboxylic acids mainly used for increasing the heat resistance include benzoic acids such as benzoic acid, methylbenzoic acid, dimethylbenzoic acid and trimethylbenzoic acid, and naphthoic acids such as 1-naphthoic acid and 2-naphthoic acid. Acids, phthalic acid, isophthalic acid, benzenedicarboxylic acid such as terephthalic acid or its acid anhydride and acid chloride, trimellitic acid,

Tricarboxylic acids such as trimesic acid or acid anhydrides and acid chlorides thereof, pyromellitic acid and 3,3
A tetracarboxylic acid such as 3 ′, 4,4′-bienylenetetracarboxylic acid or an acid anhydride thereof, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
Examples thereof include naphthalenedicarboxylic acids such as 2,3-naphthalenedicarboxylic acid and acid anhydrides thereof, and 3,3 ′, 4,4′-benzophenonetetracarboxylic acid and acid anhydrides thereof. Examples of the aromatic compound having a phenolic hydroxyl group include phenols such as phenol, cresol and xylenol, hydroquinone, resorcinol,
Catechol, benzenediols such as methylhydroquinone, benzenetriols such as phloroglucin,

Naphthols such as α-naphthol and β-naphthol, naphthalene diols, o-phenylphenol, 2,2′-dihydroxybiphenyl and 2,2 ′,
Biphenols such as 4,4'-tetramethylbiphenol; and 2,2 ', 4,4'-tetrahydroxybenzophenone.

The amount of the active ester group-containing aromatic compound (B) is preferably from 0.3 to 1.5 equivalents, more preferably from 0.5 to 1.5 equivalents, based on the epoxy equivalent of the epoxy resin (A). 1.0 equivalent, more preferably 0.8 to
1.0 equivalent is used.

When the amount of the active ester group-containing aromatic compound (B) is less than 0.3 equivalent as the ester equivalent to the epoxy equivalent of the epoxy resin (A), the epoxy resin is completely cured. If the amount exceeds 1.5 equivalents, it is difficult to obtain a cured epoxy resin having sufficiently low dielectric properties, which is not preferable.

In the present invention, a reaction accelerator (C) is used together with the active ester group-containing aromatic compound (B) which is an epoxy resin curing agent.

As the reaction accelerator (C), a general epoxy resin curing accelerator can be mainly used. Examples of the curing accelerator include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole and 2-undecylimidazole, triphenylphosphine, tributyl Organic phosphine compounds such as phosphine,

Organic phosphite compounds such as trimethyl phosphite and triethyl phosphite, phosphonium salts such as ethyltriphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, trialkylamines such as triethylamine and tributylamine, and 1,8 diazabicyclo (5 , 4,0) -undecene-7 (hereinafter abbreviated as DBU) and salts derived from DBU and terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc., tetraethylammonium chloride, tetrapropylammonium chloride, Butylammonium chloride, tetrabutylammonium bromide,

Quaternary ammonium salts such as tetrahexylammonium bromide and benzyltrimethylammonium chloride, 3-phenyl-1,1-dimethylurea,
3- (4-methylphenyl) -1,1-dimethylurea,
Chlorophenylurea, 3- (4-chlorophenyl)-
Urea compounds such as 1,1-dimethylurea and 3- (3,4-dichlorophenyl) -1,1-dimethylurea; bases such as sodium hydroxide and potassium hydroxide; crown ethers such as potassium phenoxide and potassium acetate. And the like, and these can be used alone or as a mixture of two or more.

The compounding amount of the reaction accelerator (C) is 0.005 to 1 with respect to 100 parts by weight of the epoxy resin (A) and the active ester group-containing aromatic compound (B) in total.
0.0 parts by weight. If the amount is less than 0.005 parts by weight, the curing reaction is slow, and if it exceeds 10.0 parts by weight, storage stability may be reduced, and the self-polymerization of the epoxy resin may be prioritized.

The method for obtaining a cured product using the epoxy resin composition of the present invention is not particularly limited, and includes a known and commonly used method. For example, a method of uniformly mixing the epoxy resin composition of the present invention, heating and melting, and then molding to obtain a cured product, or dissolving the epoxy resin composition in a solvent to form a varnish, and applying, pouring, or glass. Impregnate the cloth base material,
There is a method in which the resin is preliminarily cured and the solvent is removed, and then pressurized and heated again.

As a specific method, as a method for producing an epoxy resin laminate, a solvent is added to an epoxy resin (A), an aromatic compound (B) containing an active ester group as a curing agent, and a reaction accelerator (C). A varnish is prepared and then impregnated into a glass cloth and dried at 160 ° C. for 5 minutes to produce a B-stage prepreg. A metal foil such as gold, copper, or aluminum is attached to one or both surfaces of the prepreg,
By molding under pressure at 3 ° C for 1 hour,
There is a method of obtaining an epoxy resin substrate or a laminate.

As the solvent for dissolving the epoxy resin composition of the present invention, various organic solvents capable of uniformly dissolving the epoxy resin, the active ester group-containing aromatic compound and the reaction accelerator together are used. Although it cannot be specified unconditionally depending on the type of the epoxy resin used, generally, amide solvents such as N-methylpyrrolidone, N-methylformaldehyde, N, N′-dimethylformamide, N, N′-dimethylacetamide, acetone, methyl ethyl ketone, Examples thereof include ketone solvents such as methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbon solvents such as toluene and xylene, and monoether glycol solvents such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether. These solvents may be used alone or as a mixture of two or more.

Usually, in the reaction between an epoxy resin and a curing agent, a hydroxyl group having a high polarity is often generated along with the ring opening of the epoxy group. For example, an amine-based or phenol-based curing agent gives a hydroxyl group, and an acid anhydride-based curing agent easily becomes a carboxylic acid by absorbing moisture, and consequently gives a hydroxyl group. However, when an active ester group-containing aromatic compound is used as a curing agent for an epoxy resin, the active ester group reacts with ring opening of the epoxy group, and an ester group having a low polarity is formed, and a hydroxyl group is not formed. That is, the water absorption properties of the cured epoxy resin are improved, and the epoxy resin has a low dielectric property, that is, a low dielectric constant and a low dielectric loss tangent. Further, when the present active ester group-containing wholly aromatic compound is used, it has high heat resistance and flame retardancy because it contains many aromatic rings.

The epoxy resin composition of the present invention can provide a cured product having better dielectric properties, especially a dielectric loss tangent than conventional epoxy resins. It can be effectively used for applications such as board resins, electrical insulation resins, sealant resins, and various adhesive resins.If necessary, cloth such as glass, aramid, polyester, etc. Effective for use in printed wiring boards, flexible printed wiring boards, fusion films for interlayer insulation materials for build-up, coating materials, resin-coated copper foil, etc. in a form that contains materials or fillers such as silica and mica Can be used.

[0077]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these ranges. <Synthesis Example 1> (Synthesis of active ester (TAAN)) Terephthalic acid (manufactured by Mitsubishi Aroma Co., Ltd.) was placed in a four-neck separable flask equipped with a stirring rod, a cooling tube, and a nitrogen inlet tube.
0.2 mol (33.23 g), α-naphthol (manufactured by Sugai Chemical Co., Ltd.) 0.4 mol (57.67 g) and acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 0.48 mol (4
9.00 g) was added, and nitrogen was passed for 30 minutes to replace the inside of the system with nitrogen.

Then, the temperature was increased with stirring while flowing nitrogen, and the mixture was kept at 145 ° C. for 3 hours to acetylate the hydroxyl group of α-naphthol. 1H-NMR confirmed that the hydroxyl groups were almost acetylated. Then raise the temperature 2
When the temperature reaches 30 ° C., the temperature is maintained for 1 hour.
The temperature was raised to 50 ° C. over 3 hours to carry out a deacetic acid reaction to carry out an esterification reaction.

Thereafter, the product was taken out, ground and washed twice with boiling methanol to remove unreacted monomers and acetic acid. Vacuum drying was performed at 60 ° C. for 10 hours to obtain 67.0 g of an active ester group-containing aromatic compound (TAAN). The obtained active ester group-containing aromatic compound (TAA
GPC measurement was performed on N) to determine an esterification ratio (ester ratio), which was 97.4%.

<Synthesis Example 2> (Active ester (TABN)
Synthesis of Synthesis Example 1 except that β-naphthol (manufactured by Ueno Pharmaceutical Co., Ltd.) was changed to 0.4 mol (57.67 g) and acetic anhydride 1.00 mol (102.09 g) in place of α-naphthol in Synthesis Example 1. In the same manner as in Example 1, 69.2 g of an active ester group-containing aromatic compound (TABN) was obtained. Esterification rate is 9
It was 3.5%.

<Synthesis Example 3> (Active ester (IAAN)
Synthesis of Isophthalic acid (manufactured by AG International Chemical Co., Ltd.) instead of terephthalic acid in Synthesis Example 1 0.2
Mol (33.23 g), 0.80 mol of acetic anhydride (81.
63.1 g of an active ester group-containing aromatic compound (IAAN) was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 67 g).
The esterification rate was 91.8%.

<Synthesis Example 4> (Active ester (IABN)
Synthesis of terephthalic acid in Synthesis Example 1 instead of isophthalic acid 0.2
Mol (33.23 g), β- instead of α-naphthol
0.4 mol of naphthol (manufactured by Ueno Pharmaceutical Co., Ltd.) (57.
62.5 g of an active ester group-containing aromatic compound (IABN) was obtained in the same manner as in Synthesis Example 1 except that the amount was 67 g) and 0.80 mol (81.67 g) of acetic anhydride. The esterification rate was 96.9%.

<Synthesis Example 5> (Active ester (26NDC)
Synthesis of AAN) 0.2 mol (43.24 g) of 2,6-naphthalenedicarboxylic acid (manufactured by Sumikin Chemical Co., Ltd.) and 0.80 mol of acetic anhydride (81.67) instead of terephthalic acid in Synthesis Example 1
63.3 g of an active ester group-containing aromatic compound (26NDCAAN) was obtained in the same manner as in Synthesis Example 1 except that g) was used. The esterification rate was 98.2%.

<Synthesis Example 6> (Active ester (26NDC)
Synthesis of ABN) 0.2 mol (43.24 g) of 2,6-naphthalenedicarboxylic acid (manufactured by Sumikin Chemical Co., Ltd.) instead of terephthalic acid in Synthesis Example 1, and β-naphthol (Ueno Pharmaceutical Co., Ltd.) instead of α-naphthol 0.4 mol (57.67)
g) and 0.80 mol (81.67 g) of acetic anhydride, and 79.2 g of an active ester group-containing aromatic compound (26NDCABN) was obtained in the same manner as in Synthesis Example 1. The esterification rate was 95.8%.

<Synthesis Example 7> (Active ester (14NDC
Synthesis of ABN) 0.2 mol (43.24 g) of 1,4-naphthalenedicarboxylic acid (manufactured by Sumikin Chemical Co., Ltd.) instead of terephthalic acid in Synthesis Example 1, and β-naphthol (Ueno Pharmaceutical Co., Ltd.) instead of α-naphthol 0.4 mol (57.67)
g) and 0.80 mol (81.67 g) of acetic anhydride, and 84.7 g of an active ester group-containing aromatic compound (14NDCABN) was obtained in the same manner as in Synthesis Example 1. The esterification rate was 78.4%.

<Synthesis Example 8> (Active ester (PyroA
Synthesis of AN)) Instead of terephthalic acid in Synthesis Example 1, 0.12 mol (30.50) of pyromellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
g), α-naphthol 0.48 mol (69.20 g) and acetic anhydride 1.20 mol (122.51 g), except that the active ester group-containing aromatic compound (PyroAAN) was used in the same manner as in Synthesis Example 1. 0.4 g was obtained. The esterification rate was 63.2%.

<Synthesis Example 9> (Active ester (TriAB
Synthesis of N)) Instead of terephthalic acid in Synthesis Example 1, 0.15 mol (31.52) of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
g), active ester group-containing aromatic compound (TriABN) 63. in the same manner as in Synthesis Example 1 except that 0.45 mol (64.88 g) of β-naphthol and 0.90 mol (91.88 g) of acetic anhydride were used. 6 g were obtained. Esterification rate is 7
2.6%.

<Synthesis Example 10> (Active ester (TAAN
/ I)) 100 ml of distilled water was placed in a 300 ml flask equipped with a nitrogen inlet tube.
0.0204 mol of sodium hydroxide (0.816
g) and dissolve. Nitrogen was sufficiently bubbled through the nitrogen inlet tube to remove oxygen in distilled water and in the reaction system.
There, 0.02 mol of α-naphthol (2.883 g)
Is dissolved.

In another flask, 100 ml of hexane is put, and 0.01 mol (2.030 g) of terephthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved. Both were added to a high-speed stirrer together with 0.1 g of trioctylmethylammonium chloride as a phase transfer catalyst,
The reaction was performed at room temperature at 2,000 rpm for 20 minutes.

After filtering the product precipitated in the organic phase,
Washed twice with hot water. By vacuum drying at 80 ° C. for 15 hours, an aromatic compound having an active ester group (T
(AAN / I) 3.82 g. When the esterification ratio was measured in the same manner as in Synthesis Example 1, it was 100.0%.

<Synthesis Example 11> (Active ester (TABN)
/ I)) Using 150 ml of distilled water of Synthesis Example 10, 0.306 mol (1.224 g) of sodium hydroxide, and 0.03 mol (4.325 g) of β-naphthol instead of α-naphthol.
Using 150m of toluene instead of hexane in the organic phase
1, 0.015 mol of terephthalic acid chloride (3.04
In the same manner as in Synthesis Example 10 except that the amount was changed to 5 g), 5.88 g of an active ester group-containing aromatic compound (TABN / I) was obtained. The esterification rate was 97.4%.

<Synthesis Example 12> (Active ester (IABN)
/ I)) Using 150 ml of distilled water of Synthesis Example 10, 0.306 mol (1.224 g) of sodium hydroxide, and 0.03 mol (4.325 g) of β-naphthol instead of α-naphthol.
Using 150m of toluene instead of hexane in the organic phase
1, Active ester group-containing aromatic compound (IABN / I) in the same manner as in Synthesis Example 10 except that phthalic acid chloride was replaced by isophthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in an amount of 0.015 mol (3.045 g). ) 4.
51 g were obtained. The esterification rate was 98.9%.

<Synthesis Example 13> (Active ester (AdAB)
N / I)) Using 150 ml of distilled water of Synthesis Example 10, 0.306 mol (1.224 g) of sodium hydroxide, and 0.03 mol (4.325 g) of β-naphthol instead of α-naphthol.
Using 150m of toluene instead of hexane in the organic phase
1, an active ester group-containing aromatic compound (AdABN /) was prepared in the same manner as in Synthesis Example 10 except that adipoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in place of 0.015 mol (2.745 g) instead of terephthalic acid chloride. I)
4.67 g were obtained. The esterification rate was 97.9%.

Examples 1 to 9 Epoxy resins, active ester group-containing wholly aromatic compounds, reaction accelerators (curing accelerators) and solvents were blended in the amounts shown in Tables 1 to 3 to prepare varnishes. Here, DMF is used instead of THF as a solvent.
The composition shown in Example 3 was used except that
The gel time was measured on a hot plate of
30 seconds.

The varnish prepared according to Tables 1 to 3 was applied in an aluminum container, kept at 70 ° C. for 18 hours to remove the solvent and pre-cured, and then kept at 170 ° C. for 2 hours to cure the epoxy resin. Was done. Then, it was peeled off from the aluminum container to obtain a cured epoxy resin.

<Comparative Examples 1 to 3> Epoxy resin, curing agent,
A reaction accelerator (curing accelerator) and a solvent were mixed in the amounts shown in Tables 1 to 3 to prepare a varnish. Then, the composition is applied in an aluminum container, kept at 70 ° C. for 18 hours to perform solvent removal and preliminary curing, and then kept at 170 ° C. for 2 hours to perform a curing reaction of the epoxy resin, and then peeled off from the aluminum container. An epoxy resin cured product was obtained.

In the epoxy resin cured products obtained in Examples 1 to 9 and Comparative Examples 1 to 3, the glass transition temperature (T
g), dielectric properties and coefficient of linear thermal expansion were evaluated.

Glass transition temperature (Tg): DMS (DMS200 manufactured by Seiko Instruments Inc .: Dynamic viscoelasticity measurement)
Measured as a peak of tan δ at 1 Hz.

Dielectric properties: The dielectric constant and the dielectric loss tangent at 1 MHz, 30 MHz and 1 GHz were evaluated with an HP4291B RF impedance / material analyzer (manufactured by Agilent Technologies) in accordance with JIS-C-6481.

Linear thermal expansion coefficient: Evaluated from TMA (TMA / SS120C manufactured by Seiko Denshi Kogyo Co., Ltd .: thermomechanical analysis measurement) based on the expansion of the cured product in the range from around room temperature to around 50 ° C.

Solder heat resistance: In accordance with JIS-C-6481, the test piece was immersed in a solder bath at 300 ° C. for 120 seconds, and the state of the test piece was visually evaluated. When there was no swelling or cracking by visual observation, it was evaluated as ○, and when swelling or cracking occurred, ×.
And

Copper foil peel strength: Autograph (manufactured by Shimadzu Corporation, AG) according to JIS-C-6481.
SH), the epoxy resin composition and copper foil (18 μm
Using Furukawa Circuit Wheel Co., Ltd.)
The evaluation was performed using a 60 × 40 × 2 mm copper-clad laminate that was heat-cured at 2 ° C. for 2 hours.

The evaluation results are shown in Tables 1 to 3.

[0104]

[Table 1]

[0105]

[Table 2]

[0106]

[Table 3]

N-660: Cresol novolak type epoxy resin (Dainippon Ink and Chemicals, Inc., epoxy equivalent 210)

N-770: phenol novolak type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 190)

TD-2090: Novolak type phenolic resin (manufactured by Dainippon Ink and Chemicals, Inc., OH equivalent: 10)
5)

B-650: Acid anhydride type epoxy resin curing agent (manufactured by Dainippon Ink and Chemicals, Inc., acid anhydride equivalent: 1)
68)

2E4MZ: 2-ethyl-4-methylimidazole

Bu ₄ NBr: tetra-n-butylammonium bromide

(C ₆ H ₅ ) ₃ P: triphenylphosphine

From Table 1, it can be seen that the epoxy resin composition using the active ester group-containing aromatic compound of the present invention as a curing agent for an epoxy resin and the cured product obtained therefrom have an adhesive property,
It was found that low dielectric constant and low dielectric loss tangent could be achieved as well as solder resistance and curability.

Also, from Example 6 and Comparative Example 1, the system using a trifunctional curing agent (Example 6) is a system using a novolak type phenol resin having a larger number of functional groups as a curing agent (Comparative Example 1). ), It was found that the copper foil peel strength was greatly improved while maintaining the same heat resistance.

[0116]

The epoxy resin composition comprising the active ester group-containing aromatic compound (B) of the present invention as a curing agent and a cured product comprising the same have excellent adhesiveness, solder resistance and curability. Low dielectric constant and / or low dielectric loss tangent,
It can provide low dielectric materials, insulating materials, etc. in a wide range of fields such as the electric / electronics industry and the communication equipment industry.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J036 AA01 AD07 AD08 AD09 AD12 AF06 AF07 AF08 AJ09 DB23 DC02 DC14 DC25 DC41 DD07 JA08

Claims (10)

[Claims] 1. An epoxy resin (A) having two or more epoxy groups in one molecule, a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group, two or more in one molecule. An epoxy resin composition for a low dielectric material comprising an aromatic compound having an active ester group (B) and a reaction accelerator (C) as essential components. 2. The epoxy resin composition for a low dielectric material according to claim 1, wherein the low dielectric property is a dielectric constant of 3.5 or less. 3. The epoxy resin composition for a low dielectric material according to claim 1, wherein the low dielectric property is a dielectric loss tangent of 0.01 or less. 4. The ratio of the active ester group-containing aromatic compound (B) to the epoxy resin (A) having two or more epoxy groups in one molecule is based on the epoxy equivalent of the epoxy resin (A). The ester equivalent of the aromatic compound (B) is 0.3 to 1.5 equivalents, and the reaction accelerator (C) is a total of 100% by weight of the epoxy resin (A) and the active ester group-containing aromatic compound (B). The epoxy resin composition for a low dielectric material according to any one of claims 1 to 3, wherein the amount is 0.005 to 10.0 parts by weight based on parts. 5. A compound obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group.
An aromatic compound (B) having two or more active ester groups in a molecule is obtained from an aromatic compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group.
The epoxy resin composition for a low dielectric material according to any one of claims 1 to 4, which is a wholly aromatic compound (B ') having two or more active ester groups in a molecule. . 6. An aromatic compound (B) having two or more active ester groups in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group has a general formula (1) The epoxy resin composition for a low dielectric material according to any one of claims 1 to 4, wherein the epoxy resin composition is a wholly aromatic compound represented by the following formula: General formula (1) [Wherein, k is an integer of 2 to 4, and R ¹ is the following three formulas: (Wherein, A and B are each the same or different, a halogen atom, an alkyl group, m ₁ is 0 to 5, m ₂ is 0 to 4, and m ₃ represents a 0-3.) Either R ² is an aromatic ring represented by one of the following nine formulas: (Wherein D, E and G are each independently the same or different,
X represents a sulfur atom, an oxygen atom, SO ₂ or CO, n ₁ , n ₂ and n ₃ are each independently 0 to 4, n ₄ and n ₅ are each independently 0 to 3, n ₆ is 0
2 are shown. ) Is an aromatic ring represented by any one of the above. ] 7. The epoxy resin (A) having two or more epoxy groups in one molecule has an epoxy equivalent of 100 to 1,000.
The epoxy resin composition for a low dielectric material according to any one of claims 1 to 6, wherein 8. The reaction accelerator (C) comprises an imidazole compound, an organic phosphine compound, an organic phosphite compound,
It is a mixture of at least one selected from the group consisting of phosphonium salts, amines and salts thereof, urea compounds, bases, and crown ether salts.
8. The epoxy resin composition for a low dielectric material according to any one of items 7 to 7. 9. A low dielectric material obtained by curing the epoxy resin composition for a low dielectric material according to claim 1. 10. A low dielectric substrate comprising a metal foil on one or both sides of the film or sheet made of the low dielectric material according to claim 9.