KR102366352B1 - Oxazolidone ring-containing epoxy resin, method for producing the thereof, epoxy resin composition and cured product - Google Patents

Abstract

(Project) To provide an epoxy resin having improved heat resistance while maintaining conventional adhesive strength.
(Solution) An oxazolidone ring-containing epoxy resin obtained from an epoxy resin (a) and an isocyanate compound (b), wherein the epoxy resin (a) has a dinuclear content of 20 area% as measured by gel permeation chromatography It is characterized in that it is a novolak-type epoxy resin having a molecular weight distribution having a trinuclear content of 15 area% or more and 60 area% or less, a pentanuclear content content of 45 area% or less, and a number average molecular weight of 350 or more and 700 or less. Epoxy resin containing an oxazolidone ring.

Description

Oxazolidone ring-containing epoxy resin, manufacturing method thereof, epoxy resin composition and cured product

The present invention relates to an oxazolidone ring-containing epoxy resin that gives a cured product excellent in low dielectric properties, high heat resistance, low moisture absorption, high adhesion, etc., an epoxy resin composition comprising the resin as an essential component, and an epoxy resin obtained from the composition It relates to hardened|cured material, a prepreg, a laminated board, and a printed wiring board.

Epoxy resins are excellent in adhesiveness, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity, so they are used in various fields such as paints, civil bonding, molds, electrical and electronic materials, and film materials. In particular, it is widely used by providing flame retardance to an epoxy resin in the printed wiring board use which is one of electrical and electronic materials.

BACKGROUND ART [0002] A portable device, which is one of the uses for printed wiring boards, and infrastructure devices such as a base station connecting them, are required to be highly functionalized with the recent rapid increase in the amount of information. In portable devices, high multilayering and fine wiring are progressing for the purpose of miniaturization. In order to make the substrate thinner, a material with a lower dielectric constant is required, and since the adhesive surface is reduced by fine wiring, a more highly adhesive material is is being demanded For base station substrates, materials with a lower dielectric loss tangent are required in order to suppress the attenuation of signals due to high frequencies.

Characteristics such as low dielectric constant, low dielectric loss tangent, and high adhesive strength are largely derived from the structure of the epoxy resin, which is the matrix resin of a printed wiring board, and a new epoxy resin or its modification technology is required.

Regarding the low dielectric constant of the epoxy resin, Patent Document 1 discloses 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[2,6-dimethyl]phenol diglycidyl ether Cargo is starting. Further, Patent Document 2 discloses an epoxy resin obtained by reacting an epoxy resin having an alcoholic hydroxyl equivalent weight of 1.0 meq/g or less with an isocyanate compound having two or more isocyanate groups in the molecule, and an epoxy resin polymerized by an oxazolidone ring. has a low dielectric constant, a low dielectric loss tangent, and a high glass transition temperature is disclosed.

Patent Document 3 also discloses an oxazolidone ring-containing epoxy resin by reaction of an epoxy resin and an isocyanate, and as a raw material epoxy resin, a compound obtained by glycidylation of dihydric phenols such as bisphenol A, tris(glycidyloxyphenyl) ) There are examples of compounds obtained by glycidylation of alkanes, aminophenols, and the like, and compounds obtained by glycidylation of novolacs such as phenol novolac.

However, neither the epoxy resins disclosed in any of the literatures satisfactorily satisfies the demand for dielectric properties based on recent high functionalization, and the adhesiveness was also insufficient.

Japanese Laid-Open Patent Publication No. 5-293929 Japanese Patent Laid-Open No. 9-278867 Japanese Laid-Open Patent Publication No. 5-43655

Therefore, the problem to be solved by the present invention is an epoxy resin that has excellent performance in low dielectric properties, high heat resistance, and high adhesion, and is useful for lamination, molding, casting, bonding, etc., and an epoxy containing the epoxy resin as an essential component To provide a resin composition and a cured product thereof.

In order to solve the above problems, the present inventors have intensively studied low-dielectric constant and low-dielectric dissipation tangent materials. Among epoxy resins, oxazolidone ring-containing epoxy resins obtained by using an epoxy resin having a specific molecular weight distribution and an isocyanate compound have been conventionally used. The present invention was completed by finding that the low dielectric constant, low dielectric dissipation tangent and high glass transition temperature that are not found in the present invention are compatible, and furthermore, the adhesive strength is also good.

That is, the present invention is an oxazolidone ring-containing epoxy resin obtained from an epoxy resin (a) and an isocyanate compound (b), wherein the epoxy resin (a) is a dinuclear in gel permeation chromatography (GPC) measurement. Novolac-type epoxy resin having a molecular weight distribution having a content rate of 20 area% or less, a trinuclear content of 15 area% or more and 60 area% or less, a content of pentanuclear or more of 45 area% or less, and a number average molecular weight of 350 or more and 700 or less It is an oxazolidone ring-containing epoxy resin, characterized in that

Here, the GPC measurement conditions are as follows.

Tosoh Corporation GPC measuring apparatus and HLC-8220GPC were used. The column temperature was 40 degreeC using the thing equipped with the Tosoh Corporation column, TSKgelG4000HXL, TSKgelG3000HXL, and TSKgelG2000HXL in series. In addition, as the eluent, tetrahydrofuran (THF) was used at a flow rate of 1 ml/min, and an RI (differential refractometer) detector was used as the detector. For data processing, GPC-8020 Model II version 4.10 manufactured by Tosoh Corporation was used. As the measurement sample, 100 µL of a sample obtained by dissolving 0.1 g of a sample in 10 ml of THF and filtering with a microfilter was used. The dinuclear content and trinuclear content were calculated from the obtained chromatogram, and standard monodisperse polystyrenes (manufactured by Tosoh Corporation, A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40, F-80, F-128), the number average molecular weight was measured by the calibration curve.

As for the said novolak-type epoxy resin, the epoxy resin represented by following formula (1) is preferable.

[Formula 1]

(Wherein, Ar is an aromatic group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic groups may have an alkyl group having 1 to 6 carbon atoms substituted with an aromatic ring. X is a divalent aliphatic hydrocarbon group or any of the crosslinking groups represented by the following formula (1a) or the following formula (1b), G represents a glycidyl group, m represents 1 or 2, and n represents an integer of 0 or more as a repeating unit.)

[Formula 2]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and B represents any of an aromatic group consisting of a benzene ring, a biphenyl ring or a naphthalene ring, and these The aromatic group may have an alkyl group having 1 to 6 carbon atoms substituted with an aromatic ring)

It is preferable that the said isocyanate compound (b) has 1.8 or more isocyanate groups on average in a molecule|numerator.

It is preferable to make the isocyanate group of the said isocyanate compound (b) react in 0.02 mol or more and 0.6 mol or less with respect to 1 mol of the epoxy groups of the said epoxy resin (a).

The epoxy equivalent of the oxazolidone ring-containing epoxy resin is 200 to 500 g/eq. It is preferable that it is, and it is preferable that a softening point is 50-150 degreeC.

Further, in the present invention, the oxazolidone ring-containing epoxy resin and the curing agent are essential components, and the active hydrogen groups of the curing agent are 0.2 mol or more with respect to 1 mol of the epoxy groups of all epoxy resins containing the oxazolidone ring-containing epoxy resin. It is an epoxy resin composition which mix|blends in the range of 1.5 mol or less, characterized by the above-mentioned. Moreover, this invention is the epoxy resin hardened|cured material formed by hardening|curing the said epoxy resin composition. Moreover, this invention uses the said epoxy resin composition, The prepreg, laminated board, and electronic circuit board characterized by the above-mentioned.

Further, the present invention is a method for producing an oxazolidone ring-containing epoxy resin obtained from an epoxy resin (a) and an isocyanate compound (b), wherein the epoxy resin (a) has a dinuclear content in the GPC measurement under the GPC measurement conditions. A novolac-type epoxy resin having a molecular weight distribution of 15 area% or less, a trinuclear content of 15 area% or more and 60 area% or less, a pentanuclear content content of 45 area% or less, and a number average molecular weight of 350 or more and 700 or less, It is the manufacturing method of the said oxazolidone ring containing epoxy resin characterized by the range of 0.02 mol or more and 0.6 mol or less of the isocyanate group of an isocyanate compound (b) with respect to 1 mol of the epoxy groups of an epoxy resin (a).

It is preferable that the said novolak-type epoxy resin is an epoxy resin represented by the said Formula (1), It is preferable that the said isocyanate compound (b) has 1.8 or more isocyanate groups on average in a molecule|numerator.

While maintaining the adhesive strength of the present invention, it exhibits physical properties of a cured product having a high glass transition temperature. In addition, the cured epoxy resin product has excellent dielectric properties and exhibits good properties in laminates and electronic circuit boards requiring low dielectric constant and low dielectric loss tangent.

BRIEF DESCRIPTION OF THE DRAWINGS The GPC chart of the phenol novolak-type epoxy resin of Synthesis Example 2 is shown.
2 shows a GPC chart of YDPN-638, which is a general-purpose phenol novolak-type epoxy resin.
3 shows a GPC chart of the oxazolidone ring-containing epoxy resin of Example 1. FIG.
Fig. 4 shows an IR chart of the epoxy resin containing an oxazolidone ring of Example 1.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

The epoxy resin (a) used for the oxazolidone ring-containing epoxy resin of the present invention is preferably a polyfunctional furnace represented by the following formula (2) obtained by condensing a crosslinking agent such as phenols and aldehydes in the presence of an acidic catalyst It is a polyfunctional novolak-type epoxy resin which is obtained by making rock resin and epihalohydrin react, and has a specific molecular weight distribution represented by Formula (1).

[Formula 3]

(Wherein, Ar, X, m, and n have the same meaning as Ar, X, m, and n in Formula (1), respectively)

In Formulas (1) and (2), Ar is an aromatic group selected from any group consisting of a benzene ring, a naphthalene ring, or a biphenyl ring which may have a substituent. When these aromatic groups have a substituent, they are a C1-C6 alkyl group, for example, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Although a hexyl group, a cyclohexyl group, etc. are mentioned, It is not limited to these, When there exist two or more, each may be same or different. As a preferable substituent, there exists a methyl group from a viewpoint of physical properties, such as easy availability and adhesiveness in a laminated board.

X is either a divalent aliphatic hydrocarbon group or a crosslinking group represented by formula (1a) or formula (1b). 5-15 are preferable and, as for carbon number of a divalent aliphatic cyclic hydrocarbon group, 5-10 are more preferable. R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and B represents an aromatic group comprising a benzene ring, a biphenyl ring or a naphthalene ring. In addition, these rings constituting B may be substituted with an alkyl group having 1 to 6 carbon atoms.

m is 1 or 2, and represents the number of hydroxyl groups of raw material phenols. n represents an integer of 0 or more as a repeating unit, and, as for the average value, 0.5-4 are preferable ranges, 1-3.5 are more preferable ranges, and 1.5-3 are still more preferable ranges.

As phenols used in order to obtain the novolak resin represented by Formula (2), phenol, cresol, ethylphenol, butylphenol, styrenated phenol, cumylphenol, naphthol, catechol, resorcinol, naphthalenediol, etc. are mentioned. However, it is not limited to these, These phenols may be used independently and may use 2 or more types together. Among these phenols, monophenols such as phenol and alkylphenol are preferable. As an alkyl group in the case of an alkylphenol, a C1-C6 alkyl group is suitable.

As a crosslinking agent for obtaining a novolak resin, aldehydes, such as formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, amylaldehyde, benzaldehyde, which are represented by following formula (3), and acetone and methyl ethyl ketone represented by following formula (4) , methyl isobutyl ketone, ketones such as acetophenone, p-xylylene glycol, p-xylylene glycol dimethyl ether, p-xylylene dichloride, 4,4'-dimethoxymethyl Crosslinking agents such as phenyl, 4,4'-dichloromethylbiphenyl, dimethoxymethylnaphthalene and dichloromethylnaphthalene, divinylbenzenes, divinylbiphenyls, divinylnaphthalenes represented by the following formula (6), and the like and cycloalkyl dienes such as cyclopentadiene and dicyclopentadiene, but are not limited thereto, and these crosslinking agents may be used alone or in combination of two or more. X in formulas (1) and (2) is a divalent aliphatic cyclic hydrocarbon group when cycloalkyldiene is used, and when a crosslinking agent of formula (3) or (4) is used, it is represented by formula (1a) It becomes a crosslinking group shown, and when the crosslinking agent of Formula (5) or Formula (6) is used, it becomes a crosslinking group represented by Formula (1b). Among these crosslinking agents, formaldehyde, acetaldehyde, benzaldehyde, acetone, p-xylylene dichloride, and 4,4'-dichloromethylbiphenyl are preferable, and formaldehyde is particularly preferable. As a preferable form when formaldehyde is used for reaction, formalin aqueous solution, paraformaldehyde, trioxane, etc. are mentioned.

[Formula 4]

(Wherein, R ₁ and R ₂ are R ₁ and R ₂ of Formula (1a), and R ₃ , R ₄ and B have the same meaning as R ₃ , R ₄ and B of Formula (1a), respectively, and Y is independently represents a hydroxyl group, an alkoxy group, or a halogen atom)

Examples of the acidic catalyst used to obtain the novolak resin include protonic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid and toluenesulfonic acid, boron trifluoride, aluminum chloride, tin chloride, zinc chloride, and Lewis acids such as iron chloride, oxalic acid, mono Although chloroacetic acid etc. are mentioned, It is not limited to these, These acidic catalysts may be used independently and may use 2 or more types together. Among these acidic catalysts, phosphoric acid, toluenesulfonic acid, and oxalic acid are preferable.

Moreover, as a novolak-type epoxy resin commonly used, a phenol novolak-type epoxy resin, for example, Epottot (trademark) YDPN-638 (made by Shin-Nitetsu Sumikin Chemical Co., Ltd.), Epicoat (registered trademark) 152 , Epicoat 154 (manufactured by Mitsubishi Chemical Co., Ltd.), Epicron (registered trademark) N-740, Epicron N-770, Epicron N-775 (manufactured by DIC Corporation), cresol novolac-type epoxy resins, such as Epicron T YDCN-700 series (manufactured by Nippon-Sumikin Chemical Co., Ltd.), Epichron N-660, Epichron N-665, Epichron N-670, Epichron N-673, Epichron N-695 (manufactured by DIC Corporation), EOCN-1020, EOCN-102S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), alkyl novolak-type epoxy resins such as EPOTOT ZX-1071T, ZX-1270, ZX-1342 (manufactured by Nippon Chemicals Co., Ltd.) ), a styrenated phenol novolak-type epoxy resin, such as Epototte ZX-1247, GK-5855, TX-1210 (manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd.), a naphthol novolak-type epoxy resin such as Epoto toe ZX-1142L (manufactured by Nippon-Sumikin Chemical Co., Ltd.), β-naphthol aralkyl type epoxy resin, such as ESN-155, ESN-185V, ESN-175 (manufactured by Nippon-Nippon Sumikin Chemical Co., Ltd.), dinaphthol aralkyl A type epoxy resin, for example, ESN-355 of ESN-300 series, ESN-375 (made by Shin-Nippon Sumikin Chemical Co., Ltd.), alpha naphthol aralkyl type epoxy resin, for example, ESN-475V of ESN-400 series, ESN -485 (manufactured by Nippon Chemicals Co., Ltd.) and biphenyl aralkylphenol-type epoxy resins such as NC-3000 and NC-3000H (manufactured by Nippon Kayaku Co., Ltd.) The resin does not have a specific molecular weight distribution as in the novolak-type epoxy resin used in the present invention.

As the novolac resin used in the present invention, it is preferable to use a novolac resin having a specific molecular weight distribution as the raw material, and the novolak resin is obtained by adjusting the molar ratio of phenols and aldehydes, and It can be obtained by the method of removing a low molecular weight component from rock rock resin. Moreover, you may obtain such a novolak resin using the manufacturing method as shown in Unexamined-Japanese-Patent No. 2002-194041 and Unexamined-Japanese-Patent No. 2007-126683. Here, the specific molecular weight distribution means that the dinuclear content is 20 area% or less, the trinuclear content is 15 area% or more and 60 area% or less, and the pentanuclear or more content is 45 area% or less in the measurement in GPC. Moreover, it is preferable that number average molecular weights are 350-700.

The molar ratio of phenols and crosslinking agent is expressed by the molar ratio of phenols to 1 mole of crosslinking agent (phenols/crosslinking agent), and the molar ratio is prepared in a ratio of 1 or more. When is small, many high molecular weight substances of pentanuclear or higher are produced, and the number of dinuclear and trinuclear is decreased. Here, in the novolac resin represented by Formula (2) or the novolac-type epoxy resin represented by Formula (1), nuclei, such as a dinuclear body and a trinuclear body, mean the number of Ar present in a molecule|numerator. That is, the i-nuclear body is a compound of the structural formula of n=i-2 in Formulas (1) and (2). The ratio of the dinuclear body, the trinuclear body, etc. is related to the ratio in the novolac resins before epoxidation, but also changes depending on the conditions of the epoxidation, so it should be within the above range for the novolac-type epoxy resin. Therefore, the molar ratio of phenols and crosslinking agent (phenols/crosslinking agent) becomes like this. Preferably it is 3 or more and 6 or less, More preferably, it is 4 or more and 5 or less.

As described above, by adjusting the molar ratio of the phenols and the crosslinking agent to the novolac resins obtained by reducing or removing low molecular weight components, a novolac resin having a specific molecular weight distribution can be obtained. In this case, as a method of reducing or removing a low molecular weight component, especially a dinuclear body, the method of using the solubility difference of various solvent, the method of dissolving in aqueous alkali solution, other well-known separation methods, etc. are mentioned.

A novolac-type epoxy resin having a specific molecular weight distribution used in the present invention can be obtained by using a known epoxidation method for a novolac resin having a specific molecular weight distribution. Alternatively, a novolak-type epoxy resin having a specific molecular weight distribution can be obtained by reducing or removing a low molecular weight component, particularly a dinuclear component, by various methods from a commercially available novolak-type epoxy resin.

The novolac-type epoxy resin used in the present invention has a dinuclear content of 15 area% or less in GPC measurement, a trinuclear content of 15 area% or more and 60 area% or less, and a pentanuclear content of 45 area% or less, , having a molecular weight distribution having a number average molecular weight of 350 or more and 700 or less. Thereby, a desired oxazolidone ring-containing epoxy resin excellent in dielectric properties, heat resistance and adhesiveness can be obtained. In addition, the total area is the sum total of the areas of a dinuclear body or more.

A dinuclear body content rate is 20 area% or less, 15 area% or less is preferable, and 5 area% or more and 12 area% or less are more preferable. When the dinuclear content exceeds 20 area %, heat resistance will fall gradually. When there are too few dinuclear bodies, there exists a possibility that the resin viscosity as an oxazolidone ring containing epoxy resin may become high. The trinuclear content is 15 area% or more and 60 area% or less, more preferably 15 area% or more and 50 area% or less, and still more preferably 15 area% or more and 35 area% or less. If the trinuclear content is less than 15 area%, the oxazolidone ring content cannot be made high, and there is a fear that the heat resistance may be inferior. The content rate of pentanuclear or more is 45 area% or less, 40 area% or less is more preferable, 30 area% or less is still more preferable. If the content rate of pentanuclear or more is 45 area% or less, the hardened|cured material with higher heat resistance can be obtained without reducing adhesiveness. If the content of the pentanuclear body is too large, the content of the oxazolidone ring cannot be increased, the effect of improving the dielectric properties is not exhibited, and gelation during manufacture proceeds, so that the target epoxy resin containing an oxazolidone ring cannot be obtained. there is a fear that it will not In addition, although the content rate of a tetranuclear body is not specifically prescribed|regulated, it is preferable that the total content of a trinuclear body and a tetranuclear body is 15 area% or more and 85 area% or less, It is more preferable that it is 30 area% or more and 70 area% or less, 40 area% or more and 60 area% are more preferable. By setting it as this range, since molecular weight increase at the time of making it isocyanate modification|denaturation can be suppressed, it becomes possible to improve the oxazolidone ring content rate. Comparing the effects of the trinuclear body and the tetranuclear body, the trinuclear body improves adhesion more, and the tetranuclear body improves heat resistance more. As a result, the physical properties of the resin such as dielectric properties, heat resistance, and adhesion are improved.

They are 350 or more and 700 or less, and, as for a number average molecular weight, 380 or more and 600 or less are more preferable. When the number average molecular weight exceeds 700, the viscosity of the obtained oxazolidone ring-containing epoxy resin becomes high, and there is a risk of adversely affecting workability and impregnating properties of the substrate. On the other hand, when a number average molecular weight will be less than 350, there exists a possibility that heat resistance may be remarkably inferior.

In order to manufacture the oxazolidone ring containing epoxy resin of this invention, an isocyanate compound (b) is used with an epoxy resin (a). A desired oxazolidone ring containing epoxy resin can be obtained by reaction of this epoxy resin (a) and an isocyanate compound (b). As this isocyanate compound (b), what is necessary is just an isocyanate compound which has two or more isocyanate groups (-N=C=O) in a molecule|numerator, and a well-known and usual isocyanate compound can be used.

Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, hexamethylene Diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, transcyclohexane-1,4-diisocyanate, 4,4-dicyclohexylmethane diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, lysine ester triisocyanate, undecane triisocyanate, 1,8-di Isocyanate-4-isocyanatemethyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, methane diisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, butane-1 ,2-diisocyanate, transvinylene diisocyanate, propane-1,3-diisocyanate, butane-1,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutene-1,4-di Isocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1, 7-diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω,ω'-1, 3-dimethylbenzene diisocyanate, ω,ω′-1,4-dimethylbenzenediisocyanate, ω,ω′-1,3-dimethylcyclohexanediisocyanate, ω,ω′-1,4-dimethylcyclohexanediisocyanate , ω,ω'-1,4-dimethylnaphthalene diisocyanate, ω,ω'-1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, dish Chlohexylmethane-4,4'-diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediiso Cyanate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate , diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-4,4' -diisocyanate, 3,3'-dimethylbisphenyl-4,4'-diisocyanate, 2,3'-dimethoxybisphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate , 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfite-4,4'-di Bifunctional isocyanate compounds such as isocyanate and diphenylsulfone-4,4'-diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, tris(4-phenylisocyanatethiophosphate)-3,3',4; Polyfunctional isocyanate compounds such as 4'-diphenylmethane tetraisocyanate, polymers such as dimers and trimers of the isocyanate compound, block-type isocyanates masked with a blocking agent such as alcohol or phenol, bisurethane compounds, etc. can be mentioned, but is not limited thereto. You may use these isocyanate compounds 1 type or in combination of 2 or more types.

Among these isocyanate compounds, Preferably it is a bifunctional isocyanate compound or a trifunctional isocyanate compound, More preferably, it is a bifunctional isocyanate compound. When there are many functional groups of an isocyanate compound, there exists a possibility that storage stability may fall, and when there are few, there exists a possibility that heat resistance or dielectric property may not improve. Examples of the bifunctional isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and 1,3-bis(isocyanato). Methyl) cyclohexane, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, transcyclohexane- 1,4-diisocyanate, 4,4-dicyclohexylmethane diisocyanate, lysine diisocyanate and tetramethylxylene diisocyanate are preferable.

Reaction of an epoxy resin (a) and an isocyanate compound (b) can be performed by a well-known method. As a specific reaction method, (1) melt the epoxy resin (a), remove moisture in the epoxy resin by a method such as dry gas purge or reduce the pressure in the system, and then add the isocyanate compound (b) and a catalyst After the water in the epoxy resin is removed by a method for performing the reaction, (2) mixing the epoxy resin (a) and the catalyst in advance, purging a dry gas or reducing the pressure in the system, the isocyanate compound (b) ) to carry out the reaction by adding . In either method, if necessary, such as when the resin viscosity is high and stirring is difficult ^, a non-reactive solvent can also be used.

The reaction mechanism for forming the oxazolidone ring is represented by the following reaction formula (7). The epoxy resin (a) and the isocyanate compound (b) react with the epoxy group of the epoxy resin (a) and the isocyanate group of the isocyanate compound (b) by adding a catalyst to form an oxazolidone ring.

[Formula 5]

It is preferable to make the isocyanate group of an isocyanate compound (b) react in 0.02 equivalent or more and 0.6 equivalent or less with respect to 1 equivalent of the epoxy group of an epoxy resin (a). When the ratio of isocyanate groups is low, there exists a possibility that the improvement effect of a dielectric characteristic or heat resistance may not be acquired. Moreover, when there are many ratios of an isocyanate group, there exists a possibility that a desired oxazolidone ring containing epoxy resin may not be obtained because thickening is intense at the time of reaction. Moreover, there exists a possibility that solvent solubility may deteriorate and it may become impossible to use for a laminated board use. The range of 0.1 equivalent or more and 0.5 equivalent or less is more preferable, and the range of 0.2 equivalent or more and 0.4 equivalent or less is still more preferable. Here, 1 equivalent of an epoxy group and 1 equivalent of an isocyanate group are the same as 1 mole of an epoxy group and 1 mole of an isocyanate group.

It is preferable to add a catalyst and to perform reaction of an epoxy resin (a) and an isocyanate compound (b). It is preferable to implement in the range of room temperature - 150 degreeC, and, as for the addition temperature of a catalyst, the range of room temperature - 100 degreeC is more preferable.

The reaction temperature is preferably in the range of 100°C or more and 250°C or less, more preferably in the range of 100°C or more and 200°C or less, and still more preferably in the range of 120°C or more and 160°C or less. When the reaction temperature is low, the oxazolidone ring is not sufficiently formed, and there is a risk of forming an isocyanurate ring by the trimerization of the isocyanate group. In addition, when the reaction temperature is high, local high molecular weight occurs and there is a fear that the production of insoluble gel components increases. Therefore, it is necessary to adjust the addition rate of the isocyanate compound (b). When the addition rate of the isocyanate compound (b) is high, cooling may be delayed due to heat generation, and there is a fear that the desired reaction temperature cannot be maintained. Moreover, when an addition rate is slow, there exists a possibility that productivity may fall.

The reaction time is preferably in the range of 15 minutes to 10 hours from completion of the addition of the isocyanate compound (b), more preferably 30 minutes to 8 hours, and still more preferably 1 hour to 5 hours. As for this, when reaction time is short, there exists a possibility that many isocyanate groups may remain in a product. Moreover, when reaction time is long, there exists a possibility that productivity may fall.

Specific examples of the catalyst that can be used include lithium compounds such as lithium chloride and lithium butoxy, complex salts of boron trifluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, Quaternary ammonium salts such as tetraethylammonium iodide, tertiary amines such as dimethylaminoethal, triethylamine, tributylamine, benzyldimethylamine, and N-methylmorpholine; triphenylphosphine, tris(2,6) -Phosphines such as dimethoxyphenyl) phosphine, amyltriphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, tetra Phosphonium salts such as butylphosphonium acetate/acetic acid complex, tetrabutylphosphonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and tetrabutyliodide, a combination of triphenylantimony and iodine, 2-phenylimidazole , 2-methylimidazole and imidazoles such as 2-ethyl-4-methylimidazole, and alkali metal oxides such as sodium hydroxide. Or you may use together 2 or more types. Moreover, you may divide and divide and use it several times.

Although the amount of catalyst is not particularly limited, with respect to the total mass of the epoxy resin (a) and the isocyanate compound (b), 0.001 mass% or more and 5 mass% or less may be used, preferably 0.005 mass% or more and 1 mass% or less, 0.005 Mass % or more and 0.5 mass % or less are more preferable, and 0.001 mass % or more and 0.2 mass % or less are still more preferable. When there is much catalyst amount, since self-polymerization reaction of an epoxy group advances in some cases, there exists a possibility that resin viscosity may become high. Moreover, there exists a possibility that the self-polymerization reaction of an isocyanate may be accelerated|stimulated, and generation|occurrence|production of an oxazolidone ring may be suppressed. Moreover, it remains as an impurity in the produced resin, and when it uses as a material for various uses, especially a laminated board or a sealing material, there exists a possibility of causing the fall of insulation or moisture resistance. When there is little catalyst amount, there exists a possibility of causing the fall of the efficiency for obtaining an oxazolidone ring containing epoxy resin.

When performing reaction of an epoxy resin (a) and an isocyanate compound (b), you can also use together other various epoxy resins as needed in the range which does not affect the effect of this invention. As an epoxy resin which can be used together, a bisphenol A epoxy resin, for example, Epototte YD-127, Epototte YD-128, Epototte YD-8125, Epototte YD-825GS (Shin-Nitetsu Sumikin) Chemical Co., Ltd.), bisphenol F-type epoxy resin, for example, EPOTOT YDF-170, EPOTOT YDF-1500, EPOTOT YDF-8170, EPOTOT YDF-870GS (made by Nippon Tetsu Sumikin Chemical Co., Ltd.) , tetramethylbisphenol F-type epoxy resin, for example YSLV-80XY, YSLV-70XY (manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd.), biphenol-type epoxy resin such as YX-4000 (manufactured by Mitsubishi Chemical Corporation), ZX- 1251 (manufactured by Nittetsu Sumikin Chemical Co., Ltd.), a hydroquinone type epoxy resin, such as EPOTOT YDC-1312, ZX-1027 (manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd.), a bisphenol fluorene type epoxy resin, such as ZX-1201 (manufactured by Nippon Sumikin Chemical Co., Ltd.), naphthalenediol type epoxy resin such as ZX-1355 (manufactured by Nippon Sumikin Chemical Co., Ltd.), bisphenol S type epoxy resin such as TX-0710 (Shin-Nippon Chemical Co., Ltd.) Sumikin Chemical Co., Ltd.), Epicron EXA-1515 (Dainippon Chemical Industry Co., Ltd.), bisthioether type epoxy resin, such as YSLV-120TE (made by Shin-Nippon Chemical Co., Ltd.), resorcinol type epoxy resin, For example, polyglycidyl ether compounds, such as Epototh ZX-1684 (made by Shin-Nitetsu Sumikin Chemical Co., Ltd.), diamino diphenylmethane tetraglycidyl ether, For example, Epototte YH-434, Epoto YH-434GS (manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine), such as TETRAD-X (Mitsubishi Gas Chemicals) Polyglycidylamine compounds, such as a polyglycidylamine compound (manufactured by Co., Ltd.), dimer acid type epoxy resins, for example, polyglycidyl ester compounds such as YD-171 (manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd.); Aliphatic cyclic epoxy resins, for example, alicyclic epoxy compounds such as Celoxide (registered trademark) 2021 (manufactured by Daicel Chemical Industry Co., Ltd.), etc. are mentioned, but are not limited thereto, and these epoxy resins may be used alone may be used, and two or more types may be used in combination. Among the epoxy resins that can be used in combination, 2 such as a biphenol type epoxy resin, a hydroquinone type epoxy resin, a bisphenol fluorene type epoxy resin, a naphthalenediol type epoxy resin, a bisthioether type epoxy resin, and a resorcinol type epoxy resin A functional epoxy resin is preferred. By using together a small amount of a bifunctional epoxy resin, the increase in the usage-amount of an isocyanate compound (b) becomes possible without impairing the effect of this invention, and a dielectric characteristic can be improved more. 35 mass % or less is preferable and, as for the quantity which can be used, 20 mass % or less is more preferable.

In addition, when carrying out the reaction of the epoxy resin (a) and the isocyanate compound (b), the molecular weight (epoxy equivalent), etc. can be adjusted by further using various epoxy resin modifiers within a range that does not affect the effect of the present invention. there is. 30 mass parts or less are preferable with respect to 100 mass parts of epoxy resins (a), as for the quantity which can be used, 20 mass parts or less are more preferable, and its 10 mass parts or less are still more preferable.

Specific examples of the epoxy resin modifier that can be used include bisphenol A, bisphenol F, bisphenol AD, tetrabutylbisphenol A, bisphenol Z, bisphenol TMC, hydroquinone, methylhydroquinone, dimethylhydroquinone, dibutylhydroquinone, resorcin , methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, dihydroxystilbenes, phenol novolac resin, cresol novolak resin, bisphenol A novolak resin, dicyclopenta Various phenols such as diene phenol resin, phenol aralkyl resin, naphthol novolak resin, styrenated phenol novolak resin, terpene phenol resin, heavy oil modified phenol resin, various phenols, hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc. Polyhydric phenol resins obtained by condensation reaction of various aldehydes, aniline, phenylenediamine, toluidine, xylidine, diethyltoluenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodi Phenyl ketone, diaminodiphenyl sulfide, diaminodiphenyl sulfone, bis(aminophenyl)fluorene, diaminodiethyldimethyldiphenylmethane, diaminodiphenyl ether, diaminobenzanilide, diaminobiphenyl, dimethyl Diaminobiphenyl, biphenyltetraamine, bisaminophenylanthracene, bisaminophenoxybenzene, bisaminophenoxyphenyl ether, bisaminophenoxybiphenyl, bisaminophenoxyphenylsulfone, bisaminophenoxyphenylpropane, diamino Although amine compounds, such as naphthalene, are mentioned, It is not limited to these, These epoxy resin modifiers may be used independently and may use 2 or more types together.

Moreover, you may use a non-reactive solvent as needed. Specifically, various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethyl ether, isopropyl ether, butyl ether, diisoamyl Ethers such as ether, methylphenyl ether, ethylphenyl ether, amylphenyl ether, ethylbenzyl ether, dioxane, methylfuran, tetrahydrofuran, methylcellosolve, methylcellosolve acetate, ethylcellosolve, cellosolve acetate , ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, dimethyl sulfoxide, etc., but are not limited thereto, and these non-reactive solvents can be used alone You may use it, and you may use it in mixture of 2 or more types.

The oxazolidone ring-containing epoxy resin of the present invention contains an oxazolidone ring in the structure of the epoxy resin. The presence of the oxazolidone ring can be confirmed by IR measurement. When analyzed by the total reflection measurement method (ATR method), a peak derived from stretching vibration of the carbonyl group of the oxazolidone ring appears at 1745 to 1760 cm ^-1 .

The epoxy equivalent of the oxazolidone ring-containing epoxy resin of the present invention is 200 g/eq. more than 500 g/eq. The following ranges are preferred, 250 g/eq. more than 400 g/eq. The following ranges are more preferable, 250 g/eq. more than 350 g/eq. The following ranges are more preferable. When the epoxy equivalent is low, the content of the oxazolidone ring decreases and the concentration of hydroxyl groups in the cured product increases, so that there is a fear that the dielectric constant becomes high. Moreover, when an epoxy equivalent is high, content of an oxazolidone ring increases more than necessary, and there exists a possibility that adverse effects, such as deterioration of solvent solubility and increase of resin viscosity, may increase rather than the improvement effect of a dielectric property. Moreover, since the crosslinking density of a hardened|cured material becomes low, there exists a possibility that it may become a problem in use, such as an elasticity modulus falling at the temperature of solder reflow.

Further, the softening point of the oxazolidone ring-containing epoxy resin of the present invention is preferably 50°C to 150°C, more preferably 65°C to 135°C, and more preferably 70°C to 110°C when used for a prepreg or film material. more preferably. When the softening point is low, the resin varnish is impregnated with glass cloth and then dried by heating in an oven, since the viscosity is low, there is a fear that the adhesion amount of the resin decreases. In addition, when the softening point is high, the resin viscosity increases, and the impregnation property to the prepreg deteriorates, the solvent solubility deteriorates, and the dilution solvent does not volatilize when heated and dried and remains in the resin. There is a possibility that it may cause problems in use.

The oxazolidone ring containing epoxy resin of this invention can be set as a curable epoxy resin composition by mix|blending a hardening|curing agent. As the curing agent, commonly used curing agents for epoxy resins such as various phenol resins, acid anhydrides, amines, hydrazides, and acidic polyesters can be used. You may use more than one. Of these, dicyandiamide or a phenol-based curing agent is particularly preferable.

The amount of the curing agent used in the epoxy resin composition is in the range of 0.2 mol or more and 1.5 mol or less of the active hydrogen groups of the curing agent with respect to 1 mol of the epoxy groups of all epoxy resins containing the oxazolidone ring-containing epoxy resin. When the active hydrogen groups are less than 0.2 mol or more than 1.5 mol with respect to 1 mol of the epoxy group, curing may be incomplete and good cured physical properties may not be obtained. A preferable range is 0.3 mol or more and 1.5 mol or less, A more preferable range is 0.5 mol or more and 1.5 mol or less, A more preferable range is 0.8 mol or more and 1.2 mol or less. For example, when a phenol-based curing agent or an amine-based curing agent is used, an active hydrogen group is blended in substantially equimolar amounts with respect to the epoxy group, and when an acid anhydride-based curing agent is used, 0.5 to 1.2 moles of an acid anhydride group with respect to 1 mole of the epoxy group, preferably 0.6-1.0 mol is mix|blended.

The active hydrogen group as used in the present invention is a functional group having active hydrogen reactive with an epoxy group (including a functional group having a latent active hydrogen generating active hydrogen by hydrolysis, etc., and a functional group exhibiting an equivalent curing action), specifically is an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group, or the like. In addition, regarding an active hydrogen group, 1 mol of a carboxyl group or phenolic hydroxyl group is calculated by 1 mol, and an amino group (NH2) is calculated by ₂ mol. Moreover, when an active hydrogen group is not clear, an active hydrogen equivalent can be calculated|required by measurement. For example, by reacting a monoepoxy resin such as phenyl glycidyl ether with a known epoxy equivalent and a curing agent with an unknown active hydrogen equivalent, and measuring the amount of monoepoxy resin consumed, the active hydrogen equivalent of the used curing agent is determined can be saved

Specific examples of the phenol resin curing agent include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydride Bisphenols such as hydroxydiphenyl sulfide and 4,4'-thiobis(3-methyl-6-tert-butylphenol), catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethyl Dihydroxybenzenes such as hydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, trihydroxynaphthalene Hydroxynaphthalenes such as hydroxynaphthalene, Shounol (registered trademark), phenol novolac resin such as BRG-555 (manufactured by Showa Denko Co., Ltd.), cresol novolak resin such as DC-5 (manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.), resin Trishydroxyphenylmethane type novolac resin such as TOP (registered trademark) TPM-100 (manufactured by Gunei Chemical Industry Co., Ltd.), phenols such as naphthol novolak resin and/or condensate of naphthols and aldehydes, SN-160 , SN-395, SN-485 (manufactured by New Nittetsu Sumikin Chemical Co., Ltd.) and/or condensates of naphthols and xylene glycol, condensates of phenols and/or naphthols and isopropenylacetophenone, phenols and/or phenol compounds such as a reaction product of naphthols and dicyclopentadiene, and a condensate of phenols and/or naphthols and a biphenyl-based crosslinking agent.

In this case, as phenols, phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, etc. are mentioned, As naphthols, 1-naphthol, 2- Naphthol etc. are mentioned. Aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde, pimel. Aldehydes, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like are exemplified. Examples of the biphenyl-based crosslinking agent include bis(methylol)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, and bis(chloromethyl)biphenyl.

Specific examples of the acid anhydride curing agent include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, and methylnadic acid.

Specific examples of the amine curing agent include diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, benzyldimethylamine, and amine compounds such as polyamideamine which is a condensate of polyamines with acids such as 2,4,6-tris(dimethylaminomethyl)phenol, dicyandiamide and dimer acid.

Specific examples of the other curing agent include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methyl imidazoles such as imidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole; imidazole salts which are salts of imidazole and trimellitic acid, isocyanuric acid, boron, etc. , quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds, diazabicyclo compounds and salts such as phenols and phenol novolac resins, complex compounds such as boron trifluoride and amines and ether compounds, aromatic phosphonium, or iodine nium salt etc. are mentioned.

Moreover, as needed, epoxy resins other than the oxazolidone ring containing epoxy resin of this invention can be used in the range which does not impair the physical property of an epoxy resin composition. Specific examples of the epoxy resin that can be used include the above-mentioned bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, bisphenol fluorene type epoxy resin Resin, bisphenol S type epoxy resin, bisthioether type epoxy resin, resorcinol type epoxy resin, biphenyl aralkylphenol type epoxy resin, naphthalenediol type epoxy resin, phenol novolak type epoxy resin, styrenated phenol novolak type epoxy resin Resin, cresol novolak type epoxy resin, alkyl novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, β-naphthol aralkyl type epoxy resin, dinaphthol aralkyl type epoxy resin, α-naphthol Aralkyl type epoxy resin, trisphenylmethane type epoxy resin, trisphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, aliphatic cyclic type epoxy resin, diaminodiphenylmethanetetraglycidyl Although an amine, an aminophenol type epoxy resin, phosphorus containing epoxy resin, a urethane-modified epoxy resin, and an oxazolidone ring containing epoxy resin are mentioned, it is not limited to these. Moreover, these epoxy resins may be used independently and may use 2 or more types together.

A hardening accelerator can be used for an epoxy resin composition as needed. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol, 1, Tertiary amines such as 8-diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, and triphenylphosphine triphenylborane, octylic acid and metal compounds such as tin. 0.02 mass part - 5 mass parts of hardening accelerators are used as needed with respect to 100 mass parts of epoxy resin components in the epoxy resin composition of this invention. By using a curing accelerator, the curing temperature can be lowered or the curing time can be shortened.

An organic solvent can also be used for the epoxy resin composition for viscosity adjustment. The organic solvent that can be used is not particularly limited, but amides such as N,N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, methanol, ethanol, etc. Aromatic hydrocarbons, such as alcohol, benzene, and toluene, etc. are mentioned, Among these solvents, single or a mixture of several types can be mix|blended in the range of 20 mass % - 90 mass % as an epoxy resin density|concentration.

Moreover, as needed, a diluent can be used in the range which does not impair the physical property of an epoxy resin composition. The diluent is preferably a reactive diluent, but may be a non-reactive diluent. Examples of the reactive diluent include monofunctional such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, resorcinol glycidyl ether, neopentyl glycol glycidyl ether, 1,6- Bifunctional, such as hexanediol diglycidyl ether, polyfunctional glycidyl ethers, such as glycerol polyglycidyl ether, trimethylol propane polyglycidyl ether, and pentaerythritol polyglycidyl ether, are mentioned. Examples of the non-reactive diluent include benzyl alcohol, butyldiglycol, and pine oil.

The epoxy resin composition may mix|blend another thermosetting resin and a thermoplastic resin in the range which does not impair a characteristic. For example, phenol resin, acrylic resin, petroleum resin, indene resin, coumarone indene resin, phenoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, polyetherimide resin , polyphenylene ether resin, modified polyphenylene ether resin, polyether sulfone resin, polysulfone resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formal resin, etc., but are limited to these not.

Various well-known flame retardants can be used for the purpose of the flame retardance improvement of the hardened|cured material obtained for an epoxy resin composition. Examples of the usable flame retardant include a halogen-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, a silicone-based flame retardant, an inorganic flame retardant, and an organometallic salt-based flame retardant. From the viewpoint of the environment, a halogen-free flame retardant is preferable, and a phosphorus-based flame retardant is particularly preferable. These flame retardants may be used independently and may use 2 or more types together.

As the phosphorus-based flame retardant, both inorganic phosphorus-based compounds and organic phosphorus-based compounds may be used. Examples of the inorganic phosphorus compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as amide phosphate. Examples of the organophosphorus compound include general purpose organophosphorus compounds such as aliphatic phosphate esters, phosphate ester compounds, condensed phosphate esters, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds. In addition to metal salts of phosphinic acid, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10 - cyclic organophosphorus compounds such as phosphaphenanthrene-10-oxide and 10-(2,7-dihydrooxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and phosphorus-containing epoxy resins, phosphorus-containing curing agents, and the like, which are derivatives obtained by reacting with a compound such as an epoxy resin or a phenol resin.

The compounding amount of the flame retardant is appropriately selected according to the type of the phosphorus-based flame retardant, the component of the epoxy resin composition, and the desired degree of flame retardancy. For example, the phosphorus content in the organic component (excluding the organic solvent) in the epoxy resin composition is preferably 0.2 mass% or more and 4 mass% or less, more preferably 0.4 mass% or more and 3.5 mass% or less, and further Preferably they are 0.6 mass % or more and 3 mass % or less. When there is little phosphorus content, there exists a possibility that ensuring a flame retardance may become difficult, and when too large, there exists a possibility of exerting a bad influence on heat resistance. Moreover, when using a phosphorus-type flame retardant, you may use together flame-retardant auxiliary agents, such as magnesium hydroxide.

A filler can be used for an epoxy resin composition as needed. Specifically, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber , glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, particulate rubber, thermoplastic elastomer, pigment, and the like. Generally, the reason for using a filler is the effect of improving impact resistance. In addition, when a metal hydroxide such as aluminum hydroxide, boehmite, or magnesium hydroxide is used, it acts as a flame retardant auxiliary agent to improve the flame retardancy. 1 mass % - 150 mass % are preferable with respect to the whole epoxy resin composition, and, as for the compounding quantity of these fillers, 10 mass % - 70 mass % are more preferable. When there is much compounding quantity, there exists a possibility that the adhesiveness required for a laminated board use may fall, and there exists a possibility that hardened|cured material may become brittle, and there exists a possibility that sufficient mechanical properties may not be acquired. Moreover, when there is little compounding quantity, there exists a possibility that the compounding effect of a filler, such as an improvement of the impact resistance of hardened|cured material, may not appear.

When making an epoxy resin composition into a plate-shaped board|substrate etc., a fibrous thing is mentioned as a preferable filler from points, such as the dimensional stability and bending strength. More preferably, the glass fiber board|substrate which woven glass fiber into the mesh form is mentioned.

The epoxy resin composition can further mix|blend nuclide additives, such as a silane coupling agent, antioxidant, a mold release agent, an antifoamer, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant, and a pigment. These additives have a preferable range of 0.01 mass % - 20 mass % with respect to an epoxy resin composition.

The epoxy resin composition can manufacture a prepreg used in a printed wiring board etc. by impregnating a fibrous base material. As the fibrous substrate, inorganic fibers such as glass, polyester resins, etc., polyamine resins, polyacrylic resins, polyimide resins, aromatic polyamide resins, woven or nonwoven fabrics of organic fibers can be used, but the present invention is not limited thereto. The method for producing a prepreg from the epoxy resin composition is not particularly limited, and for example, the epoxy resin composition is immersed in a resin varnish prepared by adjusting the viscosity with a solvent to be impregnated, and then heat-dried to semi-cur the resin component. It is obtained by carrying out (B-staging), for example, it can heat-dry at 100-200 degreeC for 1 to 40 minutes. Here, it is preferable to make the resin amount in a prepreg into 30-80 mass % of resin content.

Moreover, in order to harden a prepreg, although the hardening method of the laminated board generally used when manufacturing a printed wiring board can be used, it is not limited to this. For example, when a laminate is formed using a prepreg, one or a plurality of prepregs are laminated, a metal foil is arranged on one side or both sides to form a laminate, and the laminate is heated and pressurized to integrate the laminate. do. Here, as metal foil, single, alloy, composite metal foils, such as copper, aluminum, brass, and nickel, can be used. And the prepreg can be hardened by pressurizing and heating the manufactured laminated body, and a laminated board can be obtained. In that case, it is preferable to make heating temperature into 160-220 degreeC, pressurization pressure 50-500 N/cm<2>, and to make heat press time into 40 to 240 minutes, and the target hardened|cured material can be obtained. When the heating temperature is low, the curing reaction does not proceed sufficiently, and when the heating temperature is high, there is a fear that decomposition of the epoxy resin composition starts. Moreover, when the pressurization pressure is low, air bubbles remain inside the obtained laminated board, and electrical properties may fall, and when it is high, there exists a possibility that resin flows out before hardening and the hardened|cured material of a desired thickness may not be obtained. Moreover, when the heating and pressurization time is short, there is a fear that the curing reaction may not proceed sufficiently, and when the heating and pressurization time is long, there is a fear that thermal decomposition of the epoxy resin composition in the prepreg may occur, which is not preferable.

An epoxy resin composition can be obtained by hardening an epoxy resin composition by the method similar to a well-known epoxy resin composition. As a method for obtaining a cured product, the same method as that of a known epoxy resin composition can be taken, and casting, pouring, potting, dipping, drip coating, transfer molding, compression molding, etc., resin sheet, resin coated copper foil, prepreg, etc. A method such as laminating in the form of a laminated plate and curing by heating and pressurization to obtain a laminated plate is preferably used. The curing temperature in that case is normally in the range of 100 degreeC - 300 degreeC, and hardening time is about 1 hour - about 5 hours normally.

The cured epoxy resin product of the present invention may take the form of a laminate, a molded product, an adhesive, a coating film, a film, or the like.

As a result of preparing an epoxy resin composition and evaluating the cured epoxy resin product of the laminate by heat curing, the oxazolidone ring-containing epoxy resin in which the epoxy resin (a) and the isocyanate compound (b) were reacted is a conventionally known oxazolyl Compared with the don ring-containing epoxy resin, it is possible to have not only good workability with low viscosity, but also high heat resistance and high adhesiveness, and furthermore, it was possible to improve the low dielectric properties.

Example

The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "part" represents parts by mass, and "%" represents mass %. In addition, the measuring method was measured by the following methods, respectively.

Epoxy equivalent: according to JIS K7236 standard.

Viscosity: According to JIS K7233 standard, single cylinder rotational viscometer method.

Softening point: It was measured based on JISK7234 standard, the round-ball method. Specifically, an automatic softening point device (manufactured by Maytech Co., Ltd., ASP-MG4) was used.

Dinuclear content, trinuclear content, tetranuclear content, pentanuclear or more content, number average molecular weight (Mn), mass average molecular weight (Mw), and dispersion degree (Mw/Mn): Measure molecular weight distribution using GPC, Dinuclear content, trinuclear content, tetranuclear content, pentanuclear content content, number average molecular weight, weight average molecular weight, and dispersion degree are standard monodisperse polystyrene (Toso Corporation, A-500, A-1000 from the area % of the peak) , A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40, F-80, F-128) were converted into a calibration curve. Specifically, a main body (manufactured by Tosoh Corporation, HLC-8220GPC) equipped with a column (TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL, manufactured by Toso Corporation) in series was used, and the column temperature was set to 40°C. In addition, THF was used as an eluent, and it was set as the flow rate of 1 ml/min, and the RI (differential refractometer) detector was used as a detector. For data processing, GPC-8020 Model II version 4.10 manufactured by Tosoh Corporation was used. As the measurement sample, 100 µL of a sample obtained by dissolving 0.1 g of a sample in 10 ml of THF and filtering with a microfilter was used.

Copper foil peel strength and interlayer adhesive force: Measured according to JIS C6481, and interlayer adhesive force was measured by peeling between the 7th and 8th layers.

Glass transition temperature (DSC method): In accordance with IPC-TM-650 2.4.25.c, when the measurement was performed under a temperature increase condition of 20°C/min with a differential scanning calorimetry apparatus (Hitachi Hi-Tech Sciences, Ltd., EXSTAR6000 DSC6200) DSC·Tgm (the intermediate temperature of the transition curve with respect to the tangent between the glass state and the rubber state) was expressed as a temperature.

Glass transition temperature (TMA method): TMA when measured at a temperature increase condition of 10°C/min with a thermomechanical analyzer (manufactured by Hitachi HiTek Science, EXSTAR6000 TMA/SS120U) in accordance with IPC-TM-650 2.4.24.1 It is expressed as an extrapolated temperature.

Relative permittivity and dielectric loss tangent: In accordance with IPC-TM-650 2.5.5.9, using a material analyzer (manufactured by AGILENT Technologies), it was evaluated by determining the relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz by the capacitance method.

Flame retardancy: In accordance with UL94 (Safety certification standard of Underwriters Laboratories Inc.), the vertical method evaluated.

IR: The absorbance at a wave number of 650 to 4000 cm ^-1 was measured by a total reflection measurement method (ATR method) of a Fourier transform infrared spectrophotometer (manufactured by PerkinEler Precisely, Spectrum One FT-IR Spectrometer 1760X).

Synthesis Example 1 (Synthesis of phenol novolak resin)

To the glass separable flask, 2500 parts of phenol and 7.5 parts of oxalic acid dihydrate were injected|pouring, it stirred, injecting|pouring nitrogen gas, it heated and made it temperature up. Next, while stirring at 80 degreeC, 474.1 parts of 37.4% formalin were dripped over 30 minutes, and it was made to react. Furthermore, the reaction temperature was maintained at 92 degreeC, and reaction was performed for 3 hours. The temperature was raised and the temperature was raised to 110°C while removing the reaction product water out of the system. The residual phenol was recovered under reduced pressure at 160°C, and the temperature was further raised to 250°C to recover a part of the dinuclear to obtain a phenol novolak resin. The dinuclear content and the trinuclear content of the obtained phenol novolak resin were 10 area% and 38 area%, respectively, as measured by GPC.

Synthesis Example 2 (Synthesis of phenol novolak type epoxy resin)

Into the same apparatus as in Synthesis Example 1, 666 parts of the phenol novolak resin obtained in Synthesis Example 1, 2110 parts of epichlorohydrin, and 17 parts of ion-exchanged water were injected, and the temperature was raised to 50°C while stirring. After uniformly dissolving, 14.2 parts of a 49% aqueous sodium hydroxide solution was injected, and reaction was performed for 3 hours. Next, after raising the temperature to 64°C, the pressure was reduced to such a degree that reflux of water occurred, 457.7 parts of 49% aqueous sodium hydroxide solution were added dropwise over 3 hours, and the water and epichlorohydrin which flowed out under reflux during this dropping were added dropwise. was separated from the separation tank, epichlorohydrin was returned to the reaction vessel, and water was removed out of the system to react. After completion of the reaction, the temperature was raised to 70°C to perform dehydration, and the temperature was adjusted to 135°C to recover the remaining epichlorohydrin. It returned to normal pressure, and 1232 parts of methyl isobutyl ketone (MIBK) were added and dissolved. 1200 parts of ion-exchanged water was added, and it was stirred and left still, and the salt produced by it was dissolved in water and removed. Next, 37.4 parts of 49% sodium hydroxide aqueous solution was injected, and it was made to react with stirring at 80 degreeC for 90 minutes, and purification reaction was performed. MIBK was added and washed several times to remove ionic impurities. The solvent was collect|recovered and the phenol novolak-type epoxy resin was obtained. The obtained phenol novolak-type epoxy resin had a dinuclear content of 10 area%, a trinuclear content of 35 area%, a total of trinuclear and tetranuclear content of 52 area%, a pentanuclear or more content of 38 area%, a number average molecular weight of 635, and a weight average. Molecular weight 884, dispersion 1.39, epoxy equivalent 174 g/eq. it was

A GPC measurement chart is shown in FIG. 1 . In the figure, the peak represented by A represents a dinuclear body, the peak represented by B represents a trinuclear body, and the peak group represented by C represents a pentanuclear body or more. The abscissa shows the elution time, the left ordinate shows the signal intensity, and the right ordinate shows the number average molecular weight M as a commercial log (log). The measured value of the number average molecular weight of the standard substance used was plotted by the black circle, and it was set as the calibration curve.

Synthesis Example 3 (Synthesis of mixed epoxy resin)

In the same apparatus as in Synthesis Example 1, 90 parts of the phenol novolac-type epoxy resin obtained in Synthesis Example 2 was added, and a bisphenol F-type liquid epoxy resin (manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., EPOTOT YDF-1500, epoxy equivalent 168 g/ eq., viscosity of 2500 mPa·s) was injected in 10 parts, the temperature was raised while stirring to 50°C, and the mixture was uniformly dissolved to obtain a mixed epoxy resin. As a result of measuring the molecular weight distribution of the obtained mixed-type epoxy resin, the total of the dinuclear content 18 area%, trinuclear content 32 area%, trinuclear and tetranuclear content 48 area%, pentanuclear or more content 34 area%, number average molecular weight 597, weight average molecular weight 824, dispersion degree 1.38, epoxy equivalent 173 g/eq. it was

The description of the symbol used in the Example and the comparative example is as follows.

(epoxy resin)

Epoxy resin A: phenol novolac type epoxy resin obtained in Synthesis Example 2

Epoxy resin B: Mixed epoxy resin obtained in Synthesis Example 3

Epoxy resin C: general-purpose type phenol novolac type epoxy resin (manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., Epototte YDPN-638, dunclear content of 22 area%, trinuclear content of 15 area%, trinuclear and tetranuclear content of 15 area%) is 25 area%, pentanuclear or more content 53 area%, number average molecular weight 528, weight average molecular weight 1127, dispersion degree 2.13, epoxy equivalent 176 g/eq. The GPC measurement chart is shown in Fig. 2. A, B and C are same as in 1)

Epoxy resin D: bisphenol A liquid epoxy resin (manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd., EPOTOT YD-8125, epoxy equivalent 174 g/eq., viscosity 4100 mPa·s)

Epoxy resin E: orthocresol novolak type epoxy resin (manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd., EPOTOT YDCN-703, epoxy equivalent 202 g/eq., softening point °C)

Epoxy resin F: phosphorus-containing epoxy resin (manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., EPOTOT TX-1320A, epoxy equivalent 763 g/eq., phosphorus content 5.0%)

(isocyanate)

Isocyanate A: diphenylmethane diisocyanate (manufactured by Mitsui Chemical Co., Ltd., Cosmonate PH, NCO concentration 34%)

Isocyanate B: Polymethylene polyphenyl polyisocyanate (manufactured by Mitsui Chemical Co., Ltd., Cosmonate M-50, NCO concentration 34%)

Isocyanate C: A mixture of 2,4-tolylene diisocyanate (80%) and 2,6-tolylene diisocyanate (20%) (manufactured by Mitsui Chemicals Co., Ltd., Cosmonate T-80, NO concentration 48%)

Isocyanate D: cyclohexane-1,3-diylbismethylene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd., Takenate 600, NCO concentration 43%)

(catalyst)

Catalyst A: tetramethylammonium iodide (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

Catalyst B: n-butyltriphenylphosphonium bromide (manufactured by Nippon Chemical Industries, Ltd., Hisikorin (registered trademark) BTPPBr)

(hardener)

PN: Phenol novolak resin (manufactured by Showa Denko Co., Ltd., Shounol BRG-557, softening point 80 ° C.)

DICY: dicyandiamide (manufactured by Nippon Carbite Co., Ltd.)

(curing accelerator)

2E4MZ: 2-ethyl-4-methylimidazole (Shikoku Chemical Industry Co., Ltd., Curesol 2E4MZ)

(flame retardant)

PX-200: Aromatic condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd., PX-200, phosphorus content 9.0%)

Example 1

In the same apparatus as in Synthesis Example 1, 100 parts of epoxy resin A and 0.17 parts of catalyst A as the epoxy resin (a) were injected, the temperature was raised while introducing nitrogen gas, and the temperature was maintained at 120 ° C. for 30 minutes to remove moisture in the system. removed. Next, while maintaining the temperature of 130°C to 140°C, 14.4 parts of isocyanate A (equivalent ratio of isocyanate group b/epoxy group a [(b)/(a)] = 0.20) as isocyanate compound (b) is added to 50% toluene solution , and was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for an additional 60 minutes while maintaining the same temperature. After completion of the reaction, the solvent was removed at 150°C, 1.33 kPa, and 30 minutes of recovery conditions to obtain an oxazolidone ring-containing epoxy resin (resin 1). Epoxy equivalent and softening point were measured with respect to the obtained resin 1. Table 1 shows the measurement results. Moreover, a GPC chart is shown in FIG. 3, and an IR chart is shown in FIG. 4, respectively.

Examples 2 to 7

According to the injection amount (part) of each raw material shown in Table 1, an oxazolidone ring-containing epoxy resin was synthesized in the same operation using the same apparatus as in Example 1. The epoxy equivalent and softening point of the resin obtained similarly to Example 1 were measured, and the measurement result is shown in Table 1. In addition, the dripping time of the isocyanate of Example 2, Example 4, Example 6, and Example 7 was changed from 3 hours to 6 hours in order to make the dripping rate substantially the same as Example 1. The oxazolidone ring containing epoxy resins obtained in these Examples 2-7 were used as Resins 2-7.

Comparative Example 1 to Comparative Example 7

According to the injection amounts (parts) of each raw material shown in Table 2, an oxazolidone ring-containing epoxy resin was synthesized in the same manner as in Example 1 using the same apparatus. The epoxy equivalent and softening point of the comparative resin obtained similarly to Example 1 were measured, and the measurement result is shown in Table 2. In addition, the dripping time of the isocyanate of Comparative Example 4 was changed from 3 hours to 6 hours in order to make the dripping rate substantially the same as that of Example 1. Moreover, in Comparative Example 1, Comparative Example 6, and Comparative Example 7, gelation occurred during the dropping time, and the reaction was stopped. The oxazolidone ring-containing epoxy resins obtained in these comparative examples were referred to as Comparative Resins 2 to 5.

"Equivalent ratio [(b)/(a)]" in Tables 1 and 2 means that the equivalent ratio of the isocyanate group of the isocyanate compound (b) to 1 equivalent of the epoxy group of the epoxy resin (a) is not used, and "-" is not used. , &quot;X&quot; indicates that measurement is impossible.

Example 8

100 parts of Resin 1 obtained in Example 1, 41.0 parts of PN as a curing agent, and 0.01 parts of 2E4MZ as a curing accelerator were blended, and dissolved in a mixed solvent prepared with MEK, propylene glycol monomethyl ether and N,N-dimethylformamide. to obtain an epoxy resin composition varnish.

The obtained epoxy resin composition varnish was impregnated with glass cloth (made by Nitto Spinning Co., Ltd., WEA 7628 XS13, thickness 0.18mm). The impregnated glass cloth was dried in a hot air circulation oven at 150°C for 11 minutes to obtain a prepreg. The obtained prepreg 8 sheets and copper foil (manufactured by Mitsui Metals Mining Co., Ltd., 3EC-III, thickness 35 µm) were superposed on top and bottom, and a vacuum press of 2 MPa was performed at a temperature of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes. It carried out and obtained the laminated board of thickness 1.6mm. Table 3 shows the results of the copper foil peel strength of the laminate, the interlayer adhesive force, the glass transition temperature DSC (Tg·DSC), and the glass transition temperature TMA (Tg·TMA).

Moreover, the obtained prepreg was unwound, and it was set as the powdery prepreg powder of 100 mesh pass through a sieve. The obtained prepreg powder was put in a mold made of a fluororesin, vacuum pressed at 2 MPa under the temperature conditions of 130° C. × 15 minutes + 190° C. × 80 minutes, and a test piece having a width of 50 mm and a thickness of 2 mm got Table 3 shows the results of the relative permittivity and dielectric loss tangent of the specimen.

Examples 9 to 17

Resins 1 to 7, PN, DICY, and 2E4MZ obtained in Examples 1 to 7 were blended in the amount (parts) shown in Table 3, and using the same apparatus as in Example 8, the same operation was carried out to obtain a laminate and A test piece was obtained. The test similar to Example 8 was implemented, and the result is shown in Table 3. In addition, "-" in a table|surface shows that it is not used.

Comparative Example 8 to Comparative Example 14

Comparative Resins 2 to 5, epoxy resins E, PN, DICY, and 2E4MZ obtained in Comparative Examples 2 to 5 were blended in the amount (parts) shown in Table 4, using the same apparatus as in Example 8, and the same operation was performed to obtain a laminate and a test piece. The test similar to Example 8 was implemented, and the result is shown in Table 4. In addition, "-" in a table|surface shows that it is not used.

Examples 18 to 20 and Comparative Examples 15 to 17

Resin 1, Resin 2, Comparative Resin 2, Comparative Resin 3, Epoxy Resin F, PN, 2E4MZ, and PX-200 were blended in the amount (parts) of the formulation shown in Table 5, using the same apparatus as in Example 8, A laminate and a test piece were obtained by the same operation. The test similar to Example 8 was implemented, and the result is shown in Table 5. Moreover, the test piece for flame retardance measurement was obtained by etching both surfaces of a laminated board. In addition, "-" in a table|surface shows what is not used.

As is clear from these results, the oxazolidone ring-containing epoxy resins and compositions thereof of Examples have low viscosity and good workability, and can have high heat resistance and high adhesion, and further improve dielectric properties. Could.

The oxazolidone ring-containing epoxy resin of the present invention, its composition and cured product are excellent in heat resistance, adhesiveness and dielectric properties, and can be used as an epoxy resin for various high-performance materials such as electronic circuit board materials in response to the current high-functionalization demand. there is.

Claims (14)

An oxazolidone ring-containing epoxy resin obtained from an epoxy resin (a) and an isocyanate compound (b), wherein the epoxy resin (a) has a dinuclear content of 20 area% or less as measured by gel permeation chromatography, 3 The nucleoid content is 15 area% or more and 60 area% or less, the sum of the trinuclear and tetranuclear content is 15 area% or more and 85 area% or less, the pentanuclear or more content is 45 area% or less, and the number average molecular weight is 350 or more. An oxazolidone ring-containing epoxy resin, characterized in that it is a novolak-type epoxy resin having a molecular weight distribution of 700 or less. The method of claim 1,
The oxazolidone ring containing epoxy resin whose novolak-type epoxy resin is an epoxy resin represented by following formula (1).
[Formula 1]

(Wherein, Ar is an aromatic group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic groups may have an alkyl group having 1 to 6 carbon atoms substituted with an aromatic ring. X is a divalent aliphatic hydrocarbon group or any of the crosslinking groups represented by the following formula (1a) or (1b), and G represents a glycidyl group. m represents 1 or 2, and n represents an integer of 0 or more as a repeating unit.)
[Formula 2]

(Wherein, R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and B is an aromatic group selected from a benzene ring, a biphenyl ring or a naphthalene ring, and these aromatic groups You may have a C1-C6 alkyl group substituted with an aromatic ring) The method of claim 1,
An oxazolidone ring-containing epoxy resin in which the isocyanate compound (b) has an average of 1.8 or more isocyanate groups in the molecule. The method of claim 1,
The oxazolidone ring containing epoxy resin obtained by making the isocyanate group of an isocyanate compound (b) react in 0.02 mol or more and 0.6 mol or less with respect to 1 mol of the epoxy groups of an epoxy resin (a). The method of claim 1,
Epoxy equivalent of 200 to 500 g/eq. Epoxy resin containing phosphorus oxazolidone ring. The method of claim 1,
An oxazolidone ring-containing epoxy resin having a softening point of 50 to 150°C. In the method for producing an oxazolidone ring-containing epoxy resin according to claim 1, in which an epoxy resin (a) and an isocyanate compound (b) are reacted, the epoxy resin (a) is measured by gel permeation chromatography The dinuclear content is 20 area% or less, the trinuclear content is 15 area% or more and 60 area% or less, the sum of the trinuclear and tetranuclear content is 15 area% or more and 85 area% or less, and the pentanuclear or more content is 45 It is an area % or less, and a number average molecular weight is a novolak-type epoxy resin which has a molecular weight distribution of 350 or more and 700 or less, It is 0.02 mol or more and 0.6 mol or less of the isocyanate group of an isocyanate compound (b) with respect to 1 mol of epoxy groups of an epoxy resin (a). A method for producing an oxazolidone ring-containing epoxy resin, characterized in that it is used in the range of. 8. The method of claim 7,
The manufacturing method of the oxazolidone ring containing epoxy resin whose novolak-type epoxy resin is an epoxy resin represented by following formula (1).
[Formula 3]

(Wherein, Ar is an aromatic group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic groups may have an alkyl group having 1 to 6 carbon atoms substituted with an aromatic ring. X is a divalent aliphatic hydrocarbon group or any of the crosslinking groups represented by the following formula (1a) or (1b), and G represents a glycidyl group. m represents 1 or 2, and n represents an integer of 0 or more as a repeating unit.)
[Formula 4]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and B represents any of an aromatic group consisting of a benzene ring, a biphenyl ring or a naphthalene ring, and these The aromatic group may have an alkyl group having 1 to 6 carbon atoms substituted with an aromatic ring) 9. The method according to claim 7 or 8,
A method for producing an oxazolidone ring-containing epoxy resin in which the isocyanate compound (b) has an average of 1.8 or more isocyanate groups in the molecule. An oxazolidone ring-containing epoxy resin according to any one of claims 1 to 6 and a curing agent as essential components, and the amount of active hydrogen groups in the curing agent is 0.2 mol or more and 1.5 mol or less with respect to 1 mol of the epoxy groups of all epoxy resins. Epoxy resin composition characterized in that it is blended in the range. An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 10. The prepreg characterized by using the epoxy resin composition of Claim 10. The laminated board characterized by using the epoxy resin composition of Claim 10. It was obtained using the epoxy resin composition of Claim 10, The printed wiring board characterized by the above-mentioned.

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