TWI639628B - Epoxy resin composition and cured article thereof - Google Patents

Abstract

The present invention provides an epoxy resin composition and a hardened product thereof. The epoxy resin composition has the properties of low dielectric properties and high heat resistance, and is an epoxy resin composition which is effective for lamination, molding, injection molding, and adhesion. And its hardened.

An epoxy resin composition and a cured product thereof include an epoxy resin (A) and a curing agent (B) represented by the general formula (1).

(In the formula, m is the number of repeated units, the average value is 0 <m <10. N is the number of repeated units, the average value is 0 ≦ n <10. X and Y systems may have a hydrocarbon group of 1 to 10 carbon atoms, or The halogen atom as a substituent is at least one selected from the group consisting of a phenylene group, a naphthyl group, or a group represented by the general formula (2), which may be the same or different. G is a glycidyl group.)

Description

Epoxy resin composition and hardened material thereof

The present invention relates to an epoxy resin composition and a cured product thereof, which are those which provide a cured product excellent in low dielectric properties, high heat resistance, and low hygroscopicity.

In recent years, the signal bandwidth of information communication equipment such as mobile phones and the computer's CPU clock time have reached the GHz frequency range.

The dielectric loss of an electrical signal is proportional to the product of the square root of the specific permittivity of the insulator forming the loop, the dissipation factor, and the frequency of the signal used. Therefore, the higher the frequency of the signal used, the larger the dissipation factor.

Dielectric loss weakens the signal and impairs the credibility of the signal. In order to suppress this, in the insulator, a material with a small dielectric constant and a small dissipation factor must be selected (Patent Document 1).

It is known to provide a material of a thermosetting resin composition having such a characteristic, and then, it is known to aryl esterify a phenolic hydroxyl group in a novolac resin, and use the obtained active ester compound as a resin A technique using a hardening agent has insufficient heat resistance (Patent Documents 2 and 3).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-221968

[Patent Document 2] Japanese Patent Laid-Open No. 11-130939

[Patent Document 3] Japanese Unexamined Patent Publication No. 7-82348

Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition and a cured product thereof, which have the properties of low dielectric properties and high heat resistance, and are effective for applications such as lamination, molding, injection molding, and bonding. Epoxy resin composition and its cured product.

That is, this invention is an epoxy resin composition containing the epoxy resin (A) and hardening | curing agent (B) represented by General formula (1).

(In the formula, m is the number of repeated units, the average value is 0 <m <10. N is the number of repeated units, the average value is 0 ≦ n <10. X and Y systems may have a hydrocarbon group of 1 to 10 carbon atoms, or The halogen atom as a substituent is at least one selected from the group consisting of a phenylene group, a naphthyl group, or a group represented by the general formula (2), which may be the same or different. G is a glycidyl group.)

(In the formula, R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, which may be the same or different from each other. R ₂ is a single bond or a divalent group.)

The epoxy resin (A) in the aforementioned epoxy resin composition of the present invention is based on 1 mole of the dihydroxy compound (a) represented by the following general formula (3). The halogenated methyl compound (b) represented by (4) is reacted at 0.001 to 1.0 mole to obtain a dihydroxy compound (c), and then the dihydroxy compound (c) is reacted with epichlorohydrin (Epichlorohydrin), preferably An epoxy resin obtained by glycidizing a hydroxyl group of a dihydroxy compound (c).

HO-Y-OH (3) (In the formula, Y is synonymous with the aforementioned general formula (1).)

Z-CH ₂ -X-CH ₂ -Z (4) (wherein X is synonymous with X of the aforementioned general formula (1)), and Z represents a halogen atom. )

(In the formula, m, X, and Y are each synonymous with m, X, and Y of the aforementioned general formula (1).)

The epoxy resin composition of the present invention is preferably 0.4 to 1.2 moles of the active hydrogen group of the hardener (B) relative to 1 mole of the epoxy group of the epoxy resin (A). Ear range.

The present invention is a prepreg obtained from the epoxy resin composition described above, an adhesive sheet, an epoxy laminate, an epoxy sealing material, or an epoxy injection molding material. The present invention is a cured product obtained by curing the aforementioned epoxy resin composition.

The epoxy resin composition of the present invention provides a hardened product having low dielectric characteristics and high heat resistance, and is suitable for use in applications such as lamination, molding, injection molding, and adhesion.

The epoxy resin composition of the present invention includes the epoxy resin (A) and the hardener (B) represented by the general formula (1) as essential components.

In the epoxy resin (A) represented by the general formula (1), m is the number of repeated units, and the average value must be 0 <m <10, preferably 0.01 <m <8, and more preferably 0.05 <m. <5. When m is 0, the amount of hydroxyl groups is not sufficiently reduced without low intermediation The effect of electrical characteristics, when m is 10 or more, there is a concern of increasing the viscosity. In addition, n is the number of repeated units, and the average value is not particularly specified, but it is more preferably 0 <n <5, and still more preferably 0 <n <3. The epoxy equivalent is not particularly limited, but is preferably less than 2000 g / eq, and more preferably less than 1000 g / eq. When the epoxy equivalent is larger than 2000g / eq, the molecular weight also becomes large, so there is a concern that the viscosity becomes high. Here, the average value is an average number.

In addition, X and Y in the general formula (1) may have at least one selected from the group consisting of a phenylene group, a naphthyl group, or a group represented by the general formula (2), and may have the same or phase boundary. When having a substituent, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom that can be used as a substituent, and specific examples of such a hydrocarbon group and a halogen atom may be the same as those of R ₁ in the general formula (2) described later.

In the general formula (2), R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and their systems may be the same or different from each other. Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, Linear or branched alkyl groups having 1 to 10 carbons such as n-hexyl, or cyclic alkyl groups having 4 to 10 carbons such as cyclohexyl, or may have phenyl, naphthyl, tolyl, xylyl Aryl groups having 6 to 10 carbon substituents such as dihydroindenyl, or may have benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,6 -Substituents such as aralkyl having 7 to 10 carbon substituents such as dimethylbenzyl, 3,5-dimethylbenzyl, α-methylbenzyl, etc., preferred substituents are methyl, ethyl, Tributyl, cyclohexyl, phenyl, α-methylbenzyl.

R ₂ is a single bond or a divalent group, and may contain a halogen atom, a hetero element such as a sulfur element, a nitrogen element, and an oxygen element. Specific examples of the divalent group include -CH _2- , -C (CH ₃ ) _2- , -CH (CH ₃ )-, -C (CF ₃ ) _2- , -CO-, -O-,- S-, -SO _2- , benzylidene, α-methylbenzylidene, cyclohexylene, cyclopentylene, 9H-fluorene-9-ylidene, or cyclohexenyl, etc., these groups are aromatic The family main chain may further have a substituent having the same meaning as R ₁ . Preferred divalent groups are -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -S-, -SO _2- , 9H-fluorene-9-subunit.

In addition, in the general formulae (1) to (5), the same symbols have the same meaning unless otherwise specifically prohibited.

In the aforementioned epoxy resin (A) system, the aforementioned dihydroxy compound (a) is first reacted with the aforementioned halogenated methyl compound (b) to obtain the aforementioned dihydroxy compound (c), and the dihydroxy compound ( c) Reaction with epichlorohydrin by glycidyl esterification of a hydroxyl group. In addition, when the dihydroxy compound (c) is reacted with epichlorohydrin to form an epoxy resin, there are components having a structure in which an epoxy group is ring-opened and a small amount is polymerized, but such components have no effect even if they are mixed.

Conventionally, polyether synthesis has been known by reacting a salt of a hydroxy alkali metal with a halide to obtain a dihydroxy compound (c). In the reaction of a dihydroxy compound (a) with a halogenated methyl compound (b), This polyether synthesis method can be used. In addition, m in the general formulae (1) and (5) is synonymous, but m can be roughly calculated from the molar ratios of the dihydroxy compound (a) and the halogenated methyl compound (b). The closer the Morse ratio is to 1, the larger m is. However, from the viewpoint that both ends need to be dihydroxy groups, the value of (a) / (b) is larger than one.

Specific examples of the dihydroxy compound (a) include diphenyl compounds containing diphenyl groups such as hydroquinone, resorcinol, and catechol, 1,4-dihydroxynaphthalene, and 1,6 -Naphthyl glycols such as dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol Z, 4,4 ' Divalent phenols such as -oxybisphenol, 4,4'-carbonylbisphenol, bisphenol hydrazone, 4,4'-biphenol, 2,2'-biphenol, bisphenolacetophenone, and the like are further exemplified Examples thereof include compounds having a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms, which are synonymous with R _{1 in the} above-mentioned general formula (2), and the like. Preferred examples include 4-hexaresorcinol, 1,6-dihydroxynaphthalene, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol, 4,4'-oxybisphenol, 4,4'-carbonylbisphenol, bisphenol hydrazone, and tetrabromobisphenol A. More preferable examples include tetramethylbisphenol S, bisphenol hydrazone, and tetrabromobis. Phenol A.

Specific examples of the halogenated methyl compound (b) include dichlorotoluene, dichloromethylene naphthalene, dichloromethylbiphenyl, dichloromethane, and the like. 2) R _{1 is a} synonym and a compound having a hydrocarbon group of 1 to 10 or a halogen atom or the like.

The epoxy resin (A) is a dihydroxy compound (c) obtained by reacting a dihydroxy compound (a) with a halogenated methyl compound (b), and further reacts with an epoxy ring to open the ring by reacting the dihydroxy compound (c ) Is obtained by glycidylation of a hydroxyl group. At this time, it is necessary to react the halogenated methyl compound (b) in the range of 0.001 to 1.0 mol with respect to 1.0 mol of the dihydroxy compound (a), preferably in the range of 0.01 to 0.9 mol, more preferably It is 0.05 to 0.8 mol, and a still more preferable range is 0.1 to 0.7 mol. When the halogenated methyl compound (b) is 1 mole or more, the terminal group of the dihydroxy compound (c) becomes a halogen, and therefore the epoxy resin (A) represented by the general formula (1) cannot be obtained.

The reaction system of the dihydroxy compound (a) and the halogenated methyl compound (b) can be performed in the presence of alkali metal hydroxides such as potassium carbonate, sodium hydroxide, and potassium hydroxide. The amount of alkali metal hydroxide used Relative to two The hydroxy compound (a) is preferably 1.0 mol, preferably 1.8 to 2.5 mol, and more preferably 2.0 to 2.2 mol. The reaction temperature is 20 to 100 ° C, preferably 50 to 60 ° C, and the reaction time is 1 to 10 hours. When the temperature is lower than 20 ° C, the reaction does not proceed, and when the temperature is higher than 100 ° C, there is a concern that an electrophilic substitution reaction may occur.

By reacting the dihydroxy compound (c) with epichlorohydrin, an epoxy resin (A) represented by the general formula (1) can be obtained. For example, after dissolving the dihydroxy compound (c) in an excessive amount of epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, the temperature is 20 to 150 ° C, preferably 30 to A method for reacting in the range of 80 ° C for 1 to 10 hours. The amount of the alkali metal hydroxide used at this time is 0.8 to 2.5 mol, preferably 0.85 to 2.0 mol, and more preferably 0.9 to 1.5 mol relative to 1 mol of the hydroxyl group of the dihydroxy compound (c). range. As a more preferable method, a method of directly reacting epichlorohydrin after synthesizing the dihydroxy compound (c) and subjecting the dihydroxy compound (c) to a form without taking it out of the reaction system can be mentioned. At this time, the alkali metal hydroxide remaining in the synthesis of the dihydroxy compound (c) is also added to the alkali metal hydroxide used in the epoxidation reaction. In addition, epichlorohydrin is used excessively with respect to the hydroxyl group in the dihydroxy compound (c), and it is usually 1.5 to 15 moles, preferably 2 to 10 moles, with respect to 1 mole of the hydroxyl group. After the epoxidation reaction is completed, the excess epichlorohydrin is distilled, and the remaining part is dissolved in solvents such as toluene and methyl isobutyl ketone, and then filtered, washed with water, and removed the inorganic salts. Then, the target epoxy resin can be obtained by distillation of the solvent . The average value of n in the general formula (1) is calculated from the epoxy equivalent of the epoxy resin (A).

Hardness used as the epoxy resin composition of the present invention Chemical agent (B) can be used for various epoxy resin hardeners such as phenol resins or acid oxides, amines, hydrazines, active esters, etc. These hardeners are only used 1 One type or two or more types may be used. Specific examples of the type of hardener include tris- (4-hydroxybenzene) methane, 1,1,2,2- (4-hydroxybenzene) ethane, novolac resin, and o-methylbenzene. The trivalent or higher compounds represented by o-cresol novolac resin, Naphthol novolac resin, dicyclopentadiene-type phenol resin, phenol aralkyl resin, etc., are further combined with phenols and naphthol Or bisphenol A, bisphenol F, bisphenol S, bisphenol hydrazone, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, catechol, Divalent phenols such as naphthalene glycol, and formaldehyde, acetaldehyde, benzaldehyde, p-o-hydroxybenzaldehyde, p-o-diol, p-o-diol, dimethyl ether, divinylbenzene, diisopropene Polyvalent phenol compounds synthesized by the reaction of cross-linking agents such as phenylbenzene, dimethoxymethylbiphenyls, diethylene, diisopropenylbiphenyls, etc., obtained from phenols and dichloromethylbiphenyls Biphenylaralkyl resins, naphthol aralkyl resins synthesized from naphthols and p-Xylenedichloride, etc., and methyl tetrahydro is exemplified as the acidic oxide. Phthalic anhydride Hexahydrophthalic anhydride, Pyromellitic anhydride, Methylnadic Anhydride and the like can be exemplified by diethylenetriamine, Isophoronediamine, Diamine diphenylmethane, diaminodiphenyl sulfone, dicyandiamine, and the like. Examples of the hydrazine include hydrazine adipate, hydrazine sebacate, and isobenzoylhydrazine. Examples of the active esters include EPICLON HPC-8000-65T (manufactured by DIC Corporation). In addition, the functional group concentration after hardening can be lowered in the low electromotive forward connection. A hardener is preferred, and a high hydroxyl equivalent phenol resin or an active ester is preferred. In the epoxy resin composition of the present invention, the active hydrogen group of the hardener (B) is preferably in the range of 0.4 to 1.2 moles relative to 1 mole of the epoxy group in the epoxy resin (A), and 0.5 to 1.1. Morse is more preferable, and 0.7 to 1.0 mole is further more preferable.

A hardening accelerator can be used in the epoxy resin composition of this invention as needed. Specific examples of hardening accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2- (dimethylaminomethyl). ) Tertiary amines such as phenol, 1,8-diazabicyclo (5,4,0) undec-7-ene, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenyl Phosphines such as borane, and metal compounds such as caprylic acid. The hardening accelerator may be used alone or in combination of two or more kinds. The hardening accelerator is used in an amount of 0.02 to 5.0 parts by mass based on 100 parts by mass of the epoxy resin (A) in the epoxy resin composition of the present invention. The use of a hardening accelerator can reduce the hardening temperature and shorten the hardening time.

The epoxy resin composition of the present invention is composed of the epoxy resin (A) represented by the aforementioned general formula (1) as an essential epoxy resin component, but may be used in combination as long as the object of the present invention is not impaired. Epoxy.

Specific examples of other epoxy resins that can be used in combination include bisphenol A, bisphenol F, bisphenol S, bisphenol hydrazone, 4,4'-bisphenol, 3,3 ', 5,5 '-Tetramethyl-4,4'-dihydroxybiphenyl, resorcinol, naphthalene and other divalent phenolic epoxides, tri- (4-hydroxybenzene) methane, 1,1, Epoxy of trivalent or higher phenols such as 2,2-tetrakis (4-hydroxybenzene), phenol Novolak, o-cresol Novolak, epoxide of co-condensation resin obtained from dicyclopentadiene and phenols , Co-polymers obtained from cresols and formaldehyde and alkoxy substituted naphthalenes Epoxides of condensation resins, epoxides of phenol aralkyl resins obtained from phenols and p-Xylenedichloride, etc., obtained from phenols and dichloromethyl biphenyls, etc. Epoxides of biphenylaralkyl phenol resins, naphthol aralkyl resins synthesized from naphthols and p-xylene dichloride, etc. These epoxy resins may be used alone or in combination of two or more kinds. These blending amounts may be within a range that does not impair the object of the present invention, but are preferably relative to the total amount of the epoxy resin (A) represented by the general formula (1) and other epoxy resins. It is less than 50% by mass, more preferably less than 40% by mass, and even more preferably less than 25% by mass.

In the epoxy resin composition of the present invention, an organic solvent can also be used for viscosity adjustment. If specific examples of the organic solvent that can be used include amines such as N, N-dimethylformamide, and ethylene dioxane Ethers such as monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, and aromatic hydrocarbons such as benzene and toluene. These solvents may be used alone or in combination of two or more kinds.

The epoxy resin composition of the present invention may be blended with a curable resin or a thermoplastic resin other than the epoxy resin within a range that does not impair its characteristics. Specific examples include phenol resins, acrylic resins, petroleum resins, indene resins, indene-coumarone resins, and phenoxyesin resins. , Cyanate resins, Epoxy acrylate resin, Vinyl compounds, Polyurethane, Polyester, Polyamide, Polyimide , Polyamideimide, Polyetherimide, B-triazine resin (Bismaleimide-triazine resin), Polyethersulfone, Polysulfone, Polyetheretherketone, Polyphenylenesulfide, Polyvinyl formal, but Not limited to these.

A filler (Filler) can be used in the epoxy resin composition of this invention as needed. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, fired talc, clay, kaolin, titanium hydroxide, glass powder, and silica balloon. However, it is also possible to blend organic or inorganic moisture-resistant pigments, scaly pigments, and the like. The reason for using a general inorganic filler is to improve impact resistance. Fibrous fillers such as glass fibers, wood pulp fibers, synthetic fibers, and ceramic fibers, or organic fillers such as particulate rubber and thermoplastic elastomers can be blended.

Further, additives such as a flame retardant, a shading material, and a fluidity promoter may be blended in the epoxy resin composition of the present invention as necessary. Examples of the shake-modifying material include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite. Further, as needed, a release agent such as Carnauba-wax and OP wax, a coloring agent such as carbon black, a flame retardant such as antimony trioxide, a low stress agent such as silicone oil may be blended in the resin composition of the present invention, Lubricants such as calcium stearate.

Next, a prepreg obtained using the epoxy resin composition of the present invention will be described. As the sheet-like substrate, woven or non-woven fabrics of inorganic fibers such as glass or polyester, organic fibers such as polyamine, polyacrylate, polyimide, and Kevlar can be used, but it is not limited thereto. . Epoxy resin composition of the present invention and method for making prepreg from base material There is no particular limitation in the method. For example, the aforementioned substrate is immersed in a resin varnish (Varnish) whose viscosity is adjusted by using the solvent of the aforementioned epoxy resin composition, and the resin component is semi-hardened after being impregnated and dried. For example, the obtained product can be dried by heating at 100 to 200 ° C for 1 to 40 minutes. Here, the amount of the resin in the prepreg is preferably 30 to 80% by mass of the resin component.

Next, the adhesive sheet obtained using the epoxy resin composition of this invention is demonstrated. The method for manufacturing the adhesive sheet is not particularly limited, but if the carrier film is not dissolved in a resin film such as a polyester film or a polyimide film, the epoxy resin composition of the present invention is preferably used. After coating to a thickness of 5 to 100 μm, it is heated and dried at 100 to 200 ° C. for 1 to 40 minutes to form a sheet. A resin sheet is formed by a method generally called a casting method. If the sheet coated with the epoxy resin composition is surface-treated with a release agent beforehand, the formed adhesive sheet can be easily peeled off. Here, the thickness of the adhesive sheet is desirably formed to 5 to 80 μm. The adhesive sheet obtained in this way is usually an insulating adhesive sheet. However, by mixing fine particles of a conductive metal or metal coating in an epoxy resin composition, a conductive adhesive sheet can be obtained. .

Next, a method for manufacturing a laminated board using the prepreg or insulating adhesive sheet of the present invention will be described. When a prepreg is used to form a laminate, the prepreg is laminated in one or more layers, and metal foils are arranged on one or both sides to form a laminate, and the laminate is laminated and integrated after heating and pressing. The metal foil used here may be a single, alloy, or composite metal foil such as copper, aluminum, brass, or nickel. The heating and pressing conditions of the laminate are appropriately adjusted under the condition that the epoxy resin composition is hardened, and then heating and pressing, but if the amount of pressure is too low, air bubbles remain inside the laminate and the electrical characteristics are reduced. Therefore, it is desirable to pressurize under the condition of satisfying moldability. For example, the temperature can be set to 160 to 220 ° C, the pressure can be set to 49.0 to 490.3 N / cm ² (5 to 50 kgf / cm ² ), and the heating time can be set to 40 to 240 minutes. Further, a single-layer laminated board obtained by such a method can be used as an inner layer material to produce a multilayer board. At this time, firstly, a circuit is formed on the laminated board by an additive method or a subtractive method, and the surface of the formed circuit is treated with an acid solution and then blackened to obtain an inner layer material. A multi-layer board is formed by forming an insulating layer with a prepreg material or an insulating adhesive sheet on one or both sides of the inner layer material, and a conductor layer is formed on the surface of the insulating layer. When forming an insulating layer with an insulating adhesive sheet, an insulating adhesive sheet is arranged on a line formation surface of a plurality of layers of inner layers to form a laminate. Alternatively, an insulating adhesive sheet is disposed between the circuit-forming surface of the inner layer material and the metal foil to form a laminate. Then, the laminated body is integrally molded by applying heat and pressure to the laminated body. As the hardened material of the insulating and bonding sheet is formed into an insulating layer, a multilayered inner layer material is formed. Alternatively, the hardened material of the insulating adhesive sheet is used as an insulating layer to form an inner layer material and a metal foil of a conductor layer. Here, the same can be used for the metal foil as the laminated board used for the inner layer material. The heating and press forming can be performed under the same conditions as in the case of forming the inner layer material. When the laminated board is coated with an epoxy resin composition to form an insulating layer, the aforementioned epoxy resin composition is coated with a resin at a thickness of preferably 5 to 100 μm to the outermost line forming surface of the inner layer material, and then 100 to 100 μm. Heated at 200 ° C for 1 to 90 minutes to form a flake. Formed by a method commonly known as Casting. A thickness of 5 to 80 μm after drying is desirable. On the surface of the multi-layer laminated board formed by such a method, a via hole formation or a circuit formation can be applied by addition or subtraction to form a printed wiring board. Furthermore, by using the printed wiring board as an inner layer material and repeating the aforementioned method, a multi-layer laminated board can be formed. In the case of forming an insulator with a prepreg, one or more layers of the prepreg after lamination are arranged on the circuit formation surface of the inner layer, and a metal foil is arranged on the outside to form a laminate. Then, the laminate is integrally formed by applying heat and pressure to the laminate, and forming the cured product of the prepreg as an insulating layer and the outer metal foil as a conductor layer. Here, the same can be used for the metal foil as the laminated board used for the inner layer board. The heating and press forming can be performed under the same conditions as in the case of forming the inner layer material. On the surface of the multi-layer laminated board formed by such a method, a via hole formation or a circuit formation can be applied by addition or subtraction to form a printed wiring board. Furthermore, by using the printed wiring board as an inner layer material and repeating the aforementioned method, a multi-layered multilayer board can be formed.

In addition, if the epoxy resin composition of the present invention is heat-hardened, it can be regarded as an epoxy resin hardened material, and this hardened material system has excellent properties such as low dielectric properties, heat resistance, and low hygroscopicity. This hardened material can be obtained by remolding processing such as injection molding, compression forming, and transfer forming of the epoxy resin composition. The temperature at this time is usually in the range of 120 to 250 ° C.

The epoxy resin composition of the present invention and a prepreg, an adhesive sheet, a laminate, a sealant, a molding, and a hardened material obtained by using the composition have excellent low dielectric properties, heat resistance, and low absorption. Those who exhibit excellent wettability and adhesion.

(Example)

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited thereto. As long as there is no special prohibition, "part" in the examples means mass parts, and "%" means mass%.

(1) Determination of epoxy equivalent

Measured in accordance with JIS K 7236. Specifically, a potentiometric titration device was used, copper butyl was used as a solvent, a tetraethylammonium bromide acetic acid solution was added, and a 0.1 mol / L perchloric acid-acetic acid solution was used.

(2) Measurement of softening point

Measured in accordance with JIS K 7234 standard and ring and ball method. Specifically, an automatic softening point device (Meitec, Inc., ASP-MG4) was used.

(3) Measurement of glass transition temperature

Measured in accordance with JIS K 7121 and differential scanning calorimetry. The glass transition start temperature (Tig) was extrapolated from the DSC chart obtained in the second cycle by measuring using a EXII DSC6200 manufactured by SII Corporation at a heating rate of 20 ° C / min from 20 ° C.

(4) Determination of specific permittivity and dissipation factor

The value of 1 GHz was measured by a cavity resonance method (Vector network analyzer (VNA) E8363B (manufactured by Agilent Technologies) and a resonance cavity perturbation method dielectric permittivity measuring device (manufactured by Kanto Electronics Application Development)).

(5) Measurement of adhesive force

According to JIS K 6854-1, an autograph manufactured by Shimadzu Corporation was measured under a 25 ° C environment at 50 mm / min.

(6) Measurement of water resistance

The heat resistance of the solder after PCT was measured as an index of water resistance. A test piece made in accordance with JIS C 6481 was treated in an autoclave at 121 ° C and 0.2 MPa for 3 hours, and then immersed in a solder bath at 260 ° C. 20 Those who did not swell or fall off for more than one minute were rated as ○, those who swelled or fell off within 10 were rated as ×, and others were rated as △.

(7) Tensile strength

According to JIS K 7113.

Synthesis example 1 (synthesis of epoxy resin (A1))

A glass separable flask with four openings including a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device was charged with 806 parts of methanol and 201.5 parts of potassium hydroxide and stirred. To this was added the dihydroxy compound (a). 550 parts of bis (4-hydroxy-3,5-dimethylphenyl) fluorene (hereinafter, TMBPS) was used as an alkali metal salt. Thereafter, 4.5 parts of 4,4'-dichloromethylbiphenyl (hereinafter, BCMB) as a halogenated methyl compound (b) and 488 parts of bis (2-methoxy) ether as a solvent were added, and the other side Heat to 75 ° C with stirring for 2 hours.

After completion of the reaction, the mixture was heated to 100 ° C. under a reduced pressure of 50 mmHg, and after all the methanol was distilled off, 1644 parts of epichlorohydrin was added thereto to stir and dissolve. After uniformly dissolving, maintaining a reduced pressure of 180 mmHg at 75 ° C, 148 parts of a 48% sodium hydroxide aqueous solution was dropped over 2 hours, and the refluxing distillate and epichlorohydrin in the dropping were separated by a separation layer to separate Epichlorohydrin is returned to the reaction vessel, and water is removed from the system for the reaction. After the dropping was completed, the reaction was continued for another hour under the same conditions. After the reaction was completed, the produced salt was removed by filtration, and the epichlorohydrin after washing with water was distilled off to obtain 600 parts of a pale yellow solid epoxy resin. The epoxy equivalent of the obtained epoxy resin was 212 / eq. The softening point was 60 ° C.

Synthesis example 2 (synthesis of epoxy resin (A2))

A glass separable flask with four openings, including a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device, was added with 366 parts of methanol and 91.6 parts of potassium hydroxide, and the mixture was stirred. 250 parts of TMBPS as an alkali metal salt. Thereafter, 61.5 parts of BCMB as a halogenated methyl compound (b) and 360 parts of bis (2-methoxy) ether as a solvent were added, and the mixture was heated to 75 ° C. for 2 hours while stirring and reacted for 2 hours.

After completion of the reaction, it was heated to 100 ° C. under a reduced pressure of 50 mmHg, and 43 parts of all methanol and bis (2-methoxy) ether were distilled. Then, 528 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining a reduced pressure of 180 mmHg at 75 ° C, 48 parts of a 48% sodium hydroxide aqueous solution was dropped for 1 hour, and the refluxing distillate and epichlorohydrin in the dropping were separated by a separation layer to separate Epichlorohydrin is returned to the reaction vessel, and water is removed from the system for the reaction. After the dropping was completed, the reaction was continued for another hour under the same conditions. After the reaction was completed, the produced salt was filtered off, and after further washing with water, epichlorohydrin was distilled off to obtain 286 parts of a pale yellow solid epoxy resin. The equivalent weight of the obtained epoxy resin was 313 g / eq, and the softening point was 94 ° C.

Synthesis example 3 (synthesis of epoxy resin (A3))

A detachable glass-made separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device was charged with 293 parts of methanol and 73.3 parts of potassium hydroxide, and the mixture was stirred. Then, as a dihydroxy compound (a), 200 parts of TMBPS as an alkali metal salt. Thereafter, 114.8 parts of BCMB as a halogenated methyl compound (b) and bis (2-methoxy) as a solvent were added. 440 parts of ether was heated to 75 ° C. for 2 hours while stirring.

After completion of the reaction, it was heated to 100 ° C. under a reduced pressure of 50 mmHg, and 333 parts of all methanol and bis (2-methoxy) ether were distilled. Then, 182 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining at a reduced pressure of 180 mmHg at 75 ° C, 10 parts of a 48% sodium hydroxide aqueous solution was dropped for 30 minutes, and the refluxing distillate and epichlorohydrin in the dropping were separated by a separation layer to separate Epichlorohydrin is returned to the reaction vessel, and water is removed from the system for the reaction. After the dropping was completed, the reaction was continued for another 90 minutes under the same conditions. After completion of the reaction, the produced salt was removed by filtration, and epichlorohydrin was further distilled off to obtain 247 parts of a pale yellow solid epoxy resin. The equivalent weight of the obtained epoxy resin was 776 g / eq, and the softening point was 135 ° C.

Synthesis example 4 (synthesis of epoxy resin (A4))

A glass separable flask with four openings including a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device was added with 366 parts of methanol and 99 parts of potassium hydroxide, and the mixture was stirred. Then, a dihydroxy compound (a) was added thereto. 250 parts of 4,4'-methylenebis (2,6-dimethylphenol) (hereinafter, referred to as TMBPF) was used as an alkali metal salt. Thereafter, 51.2 parts of 1,4-bis (chloromethyl) benzene (hereinafter, referred to as PXDC) as a halogenated methyl compound (b) and 265 parts of bis (2-methoxy) ether as a solvent were added. The mixture was heated to 75 ° C for 2 hours while stirring.

After completion of the reaction, the mixture was heated to 100 ° C. under a reduced pressure of 50 mmHg, and after all the methanol was distilled off, 632 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining a reduced pressure of 180 mmHg at 75 ° C, 27 parts of a 48% sodium hydroxide aqueous solution was dropped for 1 hour, and the refluxing distillate and epichlorohydrin in the dropping were separated by a separation layer to separate Epichlorohydrin is returned to the reaction vessel, and water is Remove the system for reaction. After the dropping was completed, the reaction was continued for another hour under the same conditions. After the reaction was completed, the produced salt was filtered off, and the epichlorohydrin after water washing was distilled off to obtain 285 parts of a pale yellow solid epoxy resin. The equivalent weight of the obtained epoxy resin was 261 g / eq, and the softening point was 62 ° C.

Synthesis example 5 (synthesis of epoxy resin (A5))

A glass separable flask with 4 openings including a stirring device, a thermometer, a cooling pipe, and a nitrogen introduction device was charged with 256 parts of methanol and 66 parts of potassium hydroxide and stirred. To this was added the dihydroxy compound (a). 200 parts of 9,9'-bis (4-dihydroxybenzene) fluorene (hereinafter, BPFL) was used as an alkali metal salt. Thereafter, 71.7 parts of BCMB as a halogenated methyl compound (b) and 378 parts of bis (2-methoxy) ether as a solvent were added, and the mixture was heated to 75 ° C. for 2 hours while stirring and reacted for 2 hours.

After completion of the reaction, it was heated to 100 ° C. under a reduced pressure of 50 mmHg, and after all the methanol was distilled off, 264 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining a reduced pressure of 180 mmHg at 75 ° C, 27 parts of a 48% sodium hydroxide aqueous solution was dropped for 1 hour, and the refluxing distillate and epichlorohydrin in the dropping were separated by a separation layer to separate Epichlorohydrin is returned to the reaction vessel, and water is removed from the system for the reaction. After the dropping was completed, the reaction was continued for another hour under the same conditions. After the reaction was completed, the produced salt was filtered off, and epichlorohydrin was further distilled off to obtain 226 parts of a pale yellow solid epoxy resin. The equivalent weight of the obtained epoxy resin was 497 g / eq, and the softening point was 147 ° C.

Synthesis example 6 (synthesis of epoxy resin (A6))

A glass separable flask with a stirring device, thermometer, cooling tube, and nitrogen introduction device was added to 185 parts of methanol and 62 parts of potassium hydroxide, and the mixture was stirred. To this was added the dihydroxy compound (a). 125 parts of TMBPF, used as alkali metal salt. Thereafter, 55 parts of BCMN (a mixture of 1,4-bis (chloromethyl) naphthalene and 1,5-bis (chloromethyl) naphthalene) as a halogenated methyl compound (b) and bis ( 220 parts of 2-methoxy) ether was heated to 75 ° C while stirring for 2 hours to react.

After completion of the reaction, it was heated to 100 ° C. under a reduced pressure of 50 mmHg, and 180 parts of all methanol and bis (2-methoxy) ether were distilled off. Then 310 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining a reduced pressure of 180 mmHg at 75 ° C, 29 parts of a 48% sodium hydroxide aqueous solution was dropped for 1 hour, and the refluxing distillate and epichlorohydrin in the dropping were separated by a separation layer to make the surface The chlorohydrin is returned to the reaction vessel, and water is removed from the system for the reaction. After the dropping was completed, the reaction was continued for another hour under the same conditions. After completion of the reaction, the produced salt was filtered off, and epichlorohydrin was further distilled off to obtain 115 parts of a pale yellow solid epoxy resin. The equivalent weight of the obtained epoxy resin was 396 g / eq, and the softening point was 71 ° C.

The epoxy resins, hardeners, and hardening accelerators used in the examples and comparative examples are as follows.

Epoxy resin (A)

(A1): Epoxy resin of Synthesis Example 1

(A2): Epoxy resin of Synthesis Example 2

(A3): Epoxy resin of Synthesis Example 3

(A4): Epoxy resin of Synthesis Example 4

(A5): Epoxy resin of Synthesis Example 5

(A6): Epoxy resin of Synthesis Example 6

(A7): TX-0902 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., TMPBS type solid epoxy resin, epoxy equivalent = 212g / eq, softening point = 56 ° C)

(A8): EpotohtoYD-011 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., bisphenol A type solid epoxy resin, epoxy equivalent = 475g / eq, softening point = 68 ° C)

(A9): EpotohtoYD-903N (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., bisphenol A type solid epoxy resin, epoxy equivalent = 812g / eq, softening point = 96 ° C)

Hardener (B)

(B1): ShonolBRG-557 (manufactured by Showa Denko, novolac, phenolic hydroxyl equivalent = 105g / eq, softening point = 86 ° C)

(B2): Dicyandiamide (DICY, active hydrogen equivalent = 21g / eq)

(B3): RIKACIDMH-700 (manufactured by Shin Nippon Physico Chemical Co., Ltd., a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, active equivalent = 164g / eq)

(B4): KayahardAA (manufactured by Nippon Kayaku Co., Ltd., diethyldiamine biphenylmethane, active hydrogen equivalent = 63g / eq, viscosity = 2500mPa · s)

Hardening accelerator

(C1): 2E4MZ (manufactured by Shikoku Chemical Co., Ltd., 2-ethyl-4methylimidazole)

(C2): DCMU (manufactured by Hodogaya Chemical Industry Co., Ltd., 3,4-dichlorophenyl-1,1-dimethylurea)

Examples 1 to 5 and Comparative Examples 1 to 2

The epoxy resin (A), the hardener (B), the hardening accelerator, and the solvent having the formula shown in Table 1 were blended to obtain an epoxy resin composition varnish having a nonvolatile content of 50%. The epoxy resin (A), the hardener (B), and the hardening accelerator are dissolved in methyl ethyl ketone (MEK) before use. The glass fiber cloth (Nittobo Co., Ltd., IPC specification 2116) was impregnated with the obtained epoxy resin composition varnish, and the impregnated cloth was dried in a hot air circulation oven at 150 ° C. for 8 minutes to obtain a B-stage. Prepreg. Furthermore, the obtained 4 layers of prepreg and copper foil (manufactured by Mitsui Metals Mining Co., Ltd., 3EC-III, thickness: 35 μm) were laminated, and a vacuum of 2 MPa was performed at a temperature of 130 ° C. for 15 minutes + 190 ° C. for 80 minutes. Compression to obtain a laminated board having a thickness of 0.5 mm. The evaluation results of the obtained laminated board are shown in Table 1.

Examples 6 to 8 and Comparative Examples 3 to 4

The epoxy resin (A), the hardener (B), and the hardening accelerator with the formula shown in Table 2 were blended and added to a heating kneader to heat and mix to obtain a resin composition. Next, high-strength carbon fiber (T700, manufactured by TORAY Co., Ltd., tensile strength 4.8 GPa, tensile modulus 235 GPa) is woven in one direction, and the obtained resin composition is heated and melted, and then impregnated with pressure to obtain a resin. Unidirectional carbon fiber prepreg with a content of 35%. The obtained prepreg was cut to a length of 30 cm and a width of 30 cm, and was laminated 17 times in the direction of the fiber to form a laminate. After releasing the release cloth, the laminate was further laminated. A layered cloth (bleeder cloth) is covered with a nylon sheet (Nylon pack) to form a stack for formation. This laminate for forming was formed in an autoclave under conditions of 130 ° C and 1 hour to obtain a carbon fiber composite material having a fiber volume content of 60%. The method for measuring the resin content in the prepreg is measured in accordance with JIS K 7071, and the fiber volume content is measured in accordance with JIS H 7401. The evaluation results of the obtained carbon fiber composite material are shown in Table 2.

Examples 9 to 12 and Comparative Examples 5 to 7

The epoxy resin (A), the hardener (B), and the hardening accelerator having the formula shown in Table 3 were blended, and heated to 120 ° C. with stirring to homogenize to obtain an epoxy resin composition. The obtained epoxy resin composition was defoamed under reduced pressure, and then it was injection-molded into a mold, and was heated in a hot air circulation oven at 150 ° C for 2 hours. To harden, and then hardened at 180 ° C. for 3 hours to obtain a cured product. The evaluation results of the obtained cast-hardened materials are shown in Table 3.

Claims (9)

An epoxy resin composition containing an epoxy resin (A) and a hardener (B) represented by the general formula (1), (Where m is the number of repeating units, the average value is 0 <m <10, n is the number of repeating units, the average value is 0 ≦ n <10, and X and Y systems may have a hydrocarbon group of 1 to 10 carbon atoms or The halogen atom as a substituent is a group selected from at least one of a phenylene group, a naphthyl group, or a group represented by the general formula (2), which may be the same or different, and G is a glycidyl group.) (Wherein R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, which may be the same or different, and R ₂ is a single bond or a divalent group). The epoxy resin composition according to item 1 of the scope of patent application, wherein the aforementioned epoxy resin (A) is 1 mole to the dihydroxy compound (a) represented by the following general formula (3), By reacting the halogenated methyl compound (b) represented by the general formula (4) in a range of 0.001 mol or more and less than 1.0 mol, the dihydroxy compound (c) represented by the general formula (5) is obtained. ) Further reacted with epichlorohydrin, and the epoxy resin obtained by glycidizing the hydroxyl group of a dihydroxy compound, HO-Y-OH (3) (where Y may have 1 to 10 carbon atoms) A hydrocarbon group or a halogen atom as a substituent is a group selected from at least one of a phenylene group, a naphthyl group, or a group represented by the general formula (2), which may be the same or different,) (In the formula, R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, which may be the same or different from each other, and R ₂ is a single bond or a divalent group.) Z-CH ₂ -X- CH ₂ -Z (4) (wherein X is a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom as a substituent selected from at least phenyl, naphthyl or a group represented by the general formula (2) A kind of radical, which can be the same or different, Z represents a halogen atom,) (Wherein R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, which may be the same or different from each other, and R ₂ is a single bond or a divalent group) (In the formula, m is the number of repeated units, and the average value is 0 <m <10. X, Y may have a hydrocarbon group of 1 to 10 or a halogen atom as a substituent selected from the group consisting of phenylene, naphthyl or (A group of at least one of the groups represented by the general formula (2) may be the same or different,) (In the formula, R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, which may be the same or different from each other, and R ₂ is a single bond or a divalent group). The epoxy resin composition according to item 1 or 2 of the scope of the patent application, wherein the active hydrogen group of the hardener (B) is 1 mole relative to the epoxy group of the epoxy resin (A). The range is from 0.4 to 1.2 moles. A prepreg is an epoxy resin composition as described in any one of claims 1 to 3. An adhesive sheet uses the epoxy resin composition described in any one of claims 1 to 3. An epoxy resin laminated board uses the epoxy resin composition described in any one of claims 1 to 3 of the patent application scope. An epoxy resin sealing material is the epoxy resin composition described in any one of claims 1 to 3 of the scope of patent application. An epoxy resin injection molding material uses the epoxy resin composition described in any one of claims 1 to 3 of the scope of patent application. A hardened product is obtained by hardening the epoxy resin composition described in any one of claims 1 to 3 of the scope of patent application.