KR20160110048A - Oxazolidone ring-containing epoxy resin, method for producing the thereof, epoxy resin composition and cured product - Google Patents

Abstract

Provided is an epoxy resin having excellent heat-resistance, dielectric properties, and adhesive properties, etc. The epoxy resin is an oxazolidone ring-containing epoxy resin which has an equivalent epoxy weight of 200-550 g/eq., obtainable from: (a) an epoxy resin containing 50 mass% or more of an epoxy resin (a1) represented by chemical formula (1); and (b) an isocyanate compound. In the chemical formula 1, X represents a cycloalkylidene group which has 5-8 ring atoms and at least one substituent group selected among an alkyl group having 1-4 carbon atoms, an aryl group having 6-10 carbon atoms, and an aralkyl group having 6-10 carbons; each R independently represents a hydrogen atom, an alkyl group having 1-8 carbon atoms, a cycloalkylidene group having 5-8 carbon atoms, an aryl group having 6-10 carbon atoms, or an aralkyl group having 6-10 carbon atoms; G represents a glycidyl group; and m indicates the number of repetitions and has an average value of 0-5.

Description

TECHNICAL FIELD [0001] The present invention relates to an epoxy resin containing an oxazolidone ring, a process for producing the epoxy resin, an epoxy resin composition, and a cured product of the epoxy resin composition,

The present invention relates to an epoxy resin containing an oxazolidone ring which gives a cured product excellent in low dielectric properties, high heat resistance and high adhesiveness, a process for producing the epoxy resin, an epoxy resin composition comprising the epoxy resin as an essential component, An epoxy resin cured product obtained from the epoxy resin composition, a prepreg, and an epoxy resin laminate.

Epoxy resins are used in various fields such as paints, civil engineering adhesives, molds, electric / electronic materials, and film materials because of their excellent adhesiveness, flexibility, heat resistance, chemical resistance, insulation and curing reactivity. Particularly, in the use of printed wiring boards which are one of electric and electronic materials, they are widely used by imparting flame retardancy to epoxy resins.

BACKGROUND ART [0002] In recent years, there has been always a demand for an infrastructure device such as a portable device, which is one of uses of a printed wiring board, and a base station connecting thereto, along with an increase in the amount of remarkable information. In portable devices, a multi-layered or micro-wiring has been progressed for the purpose of miniaturization, a material having a lower dielectric constant is required in order to thin a substrate, and a bonding material is reduced by fine wiring, Is required. In order to suppress the attenuation of the signal due to the high frequency in the substrate for the base station, a material with lower dielectric loss tangent is required.

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

Regarding the lowering of the dielectric constant of the epoxy resin, Patent Document 1 discloses a method for producing a low dielectric constant epoxy resin which comprises reacting diglycidyl of 4,4 '- [1,3-phenylene bis (1-methylethylidene)] bis [2,6- Ethers are disclosed. In Patent Document 2, the alcoholic hydroxyl equivalent is 1000 g / eq. (1.0 meq / g or less) and 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 constant And the glass transition temperature is also high.

Patent Document 3 discloses an epoxy resin containing an oxazolidone ring by reaction between an epoxy resin and an isocyanate. As a raw epoxy resin, a compound obtained by glycidylating a divalent phenol such as bisphenol A, a tris (glycidyloxy Phenyl) alkanols, aminophenols, and the like, and compounds obtained by glycidylating novolacs such as phenol novolak. However, the epoxy resin disclosed in any of the literatures does not sufficiently satisfy the requirements of dielectric properties based on recent high-performance, and the adhesiveness is also insufficient.

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

Therefore, an object to be solved by the present invention is to provide an epoxy resin which is excellent in properties of low dielectric constant, high heat resistance and high adhesiveness, and which is useful for applications such as lamination, molding, molding and bonding, an epoxy resin containing the epoxy resin as an essential component A resin composition and a cured product thereof.

In order to solve the above problems, the inventors of the present invention have made extensive studies on a low dielectric constant and low dielectric loss tangent material. As a result, the present inventors have found that an epoxy resin containing an oxazolidin ring, which is obtained by reacting an epoxy resin of the following formula (1) with an isocyanate compound Low dielectric constant tangent and high glass transition temperature which are not available in the prior art, and that the adhesive force is also good, thereby completing the present invention.

That is, the present invention relates to a resin composition comprising an epoxy resin (a) having an epoxy equivalent of 200 to 550 g / eq. Obtained from an epoxy resin (a) containing 50% by mass or more of an epoxy resin (a1) represented by the following formula (1) and an isocyanate compound Is an epoxy resin containing an oxazolidone ring.

[Chemical Formula 1]

(Wherein X represents a cycloalkylidene group having 5 to 8 ring atoms and having at least one substituent selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 6 to 10 carbon atoms. R represents independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms, and G denotes a glycidyl group. Represents the repetition, and the average value is 0 to 5.)

The alcoholic hydroxyl equivalent of the epoxy resin (a1) is 3000 g / eq. Or more.

The epoxy resin (a) is an epoxy resin other than the epoxy resin (a1) and has an alcoholic hydroxyl equivalent of 1000 g / eq. By mass or more of the epoxy resin (a2) in an amount of 50% by mass or less. The epoxy equivalent of the epoxy resin (a) is preferably 100 to 500 g / eq. .

The isocyanate compound (b) preferably has an average of at least 1.8 isocyanate groups in the molecule, and is preferably selected from tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, Trimethyl hexamethylene diisocyanate, isophorone diisocyanate, and the like.

In the epoxy resin containing an oxazolidone ring, the maximum value of the peak included in 1745 to 1760 cm ^-1 derived from the stretching vibration of the carbonyl group of the oxazolidone ring in the analysis by the infrared absorption spectrum is represented by the absorbance Ox, the urethane bonding structure The absorbance ratio Ox / Ur is preferably 1.35 or more when the maximum value of the peak at 1730 to 1740 cm ^-1 derived from the stretching vibration peak of the carbonyl group of the carbonyl group is taken as the absorbance Ur.

The softening point of the oxazolidone ring-containing epoxy resin is preferably 50 to 150 ° C.

The present invention also provides an epoxy resin composition comprising an epoxy resin (a) containing 50 mass% or more of the epoxy resin (a1) represented by the above formula (1) and an isocyanate compound (b) By weight, based on the weight of the oxazolidone ring-containing epoxy resin.

The isocyanate compound (b) preferably has an average of at least 1.8 isocyanate groups in the molecule, and is preferably selected from tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, Trimethyl hexamethylene diisocyanate, isophorone diisocyanate, and the like. The catalyst is preferably a basic catalyst.

The isocyanate group of the isocyanate compound (b) is preferably in the range of 0.02 to 0.5 mole, more preferably in the range of 0.05 to 0.48 mole per mole of the epoxy group of the epoxy resin (a), more preferably in the range of 0.1 Mol or more and 0.45 mol or less.

Further, the present invention is an epoxy resin composition characterized by comprising the above-mentioned oxazolidone ring-containing epoxy resin and a curing agent.

The active hydrogen group of the curing agent is preferably 0.2 to 1.5 moles relative to 1 mole of the epoxy group of the whole epoxy resin containing the oxazolidone ring-containing epoxy resin in the epoxy resin composition.

Further, the present invention is an epoxy resin cured product obtained by curing the above epoxy resin composition. Further, the present invention is a prepreg and an epoxy resin laminated board characterized by using the above epoxy resin composition.

The epoxy resin, the resin composition containing the same, and the cured product of the present invention exhibit a cured product having a high glass transition temperature while maintaining the adhesive strength. The epoxy resin cured product exhibits excellent characteristics in an epoxy resin laminated board which is excellent in dielectric properties and requires low dielectric constant and low dielectric loss tangent.

1 is a GPC chart of Resin 1 obtained in Example 1. Fig.
Fig. 2 is an IR chart of Resin 1 obtained in Example 1. Fig.
3 is a ¹³ C-NMR spectrum of Resin 1 obtained in Example 1. Fig.
4 is an absorbance spectrum of Resin 1 obtained in Example 1. Fig.
5 is an absorbance spectrum of Comparative Resin 2 obtained in Comparative Example 2. Fig.

Hereinafter, embodiments of the present invention will be described in detail.

The epoxy resin (a) used to obtain the oxazolidone ring-containing epoxy resin of the present invention contains the epoxy resin (a1) represented by the formula (1), and preferably contains 50 mass% or more.

The epoxy resin (a) may contain less than 50% by mass of an epoxy resin (a2) other than the epoxy resin (a1). The epoxy resin (a2) has an alcoholic hydroxyl equivalent of 1000 g / eq. Or more, and the epoxy equivalent of the epoxy resin (a2) is preferably 100 to 500 g / eq. .

In the formula (1), each R independently represents a hydrogen atom, a hydrocarbon group of 1 to 8 carbon atoms, a cycloalkyl group of 5 to 8 carbon atoms, an aryl group of 6 to 10 carbon atoms, or an aralkyl group of 6 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group and a hexyl group. Examples of the hydrocarbon group include a cycloalkyl group having 5 to 8 carbon atoms Include a cyclohexyl group and the like. Examples of the aryl group or the aralkyl group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a phenethyl group, a 1-phenylethyl group, a naphthyl group and the like. , They may be the same or different. Preferable R is a hydrogen atom, a 1-phenylethyl group or a methyl group from the viewpoints of ease of acquisition and physical properties such as heat resistance in the case of a cured product.

In the formula (1), the substitution position of R may be an ortho or meta position with respect to the carbon atom bonded to X, but an ortho position is preferable.

In the formula (1), X represents a cycloalkylidene group having 5 to 8 ring atoms and having at least one alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms as a substituent. The cycloalkane ring constituting the cycloalkylidene group is preferably a cyclopentane ring, a cyclohexane ring, a cycloheptane ring or a cyclooctane ring, and a cyclopentane ring or a cyclohexane ring is preferable.

The substituent bonded to the cycloalkane ring is preferably an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms, and at least one substituent is required to be substituted. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert- Examples of the aryl group or aralkyl group of 1 to 10 include a phenyl group, a benzyl group, a tolyl group, an o-xylyl group, and the like, but the present invention is not limited thereto. A preferable substituent is a methyl group or a phenyl group from the viewpoints of ease of obtaining and physical properties such as adhesiveness in laminate.

Further, the cycloalkylidene group is a 1,1-cycloalkylidene group, and the substituent is preferably a group having a cyclic alkylene ring moiety such as a benzene ring bonded to the carbon at the 1-position of the cycloalkylidene group, So as to improve the dielectric properties and improve the heat resistance. This substitution position may be bonded at any position as far as it can restrict motility, but it is preferable that the substitution position is bonded to a carbon atom close to the 1-position of the cycloalkylidene group. The position of a preferable substituent is a carbon atom at the 2-position or 5-position in the cyclopentane ring. Position, 3-position, 5-position or 6-position carbon atom in the cyclohexane ring, and more preferably 2-position or 6-position carbon atom in the cyclohexane ring. In the cycloheptane ring, the carbon atom at the 2-position, the 3-position, the 6-position, or the 7-position is more preferable the carbon atom at the 2- or 7-position. In the cyclooctane ring, the carbon atom at the 2-position, the 3-position, the 4-position, the 6-position, the 7-position or the 8-position is more preferable the carbon atom at the 2-, 3-, Is a carbon atom at the 2-position or the 8-position. However, depending on the influence of the steric hindrance with the adjacent benzene ring, it may be difficult to substitute with the carbon atom closest to the 1-position. In this case, it is preferable that the substituent is bonded to the carbon atom next to the substituent. For example, in the cyclohexane ring, the carbon atom at the 2-position or 6-position is closest to the 1-position, but when the substitution is difficult due to the steric hindrance, substituents may be bonded at the 3-position or 5-position next to the cyclo-hexane ring.

The number of substituents is required to be at least 1 for the above-described reasons, but is preferably 3 or more, and more preferably 3 from the viewpoint of heat resistance when formed into a cured product.

In the formula (1), m is a repetition number, and the average value (number average) is 0 to 5, preferably 0 to 3, more preferably 0 to 1, and still more preferably 0 to 0.5. It is preferable that the number of repetitions (integer) is usually in the range of 0 to 5. A single compound in which the number of repeats is any one of 0 to 5, or a mixture in which m is a multiple of 0 to 5 may be used. In the epoxidation of an ordinary polyhydric hydroxy resin with epichlorohydrin or the like, it is obtained as a mixture, so that it is advantageous that the mixture can be used as it is.

The alcoholic hydroxyl equivalent of the epoxy resin (a1) is 3000 g / eq. Or more. Therefore, the number of repeats (integer) is preferably 0 to 3, more preferably 0 to 2, still more preferably 0 to 1. 6 or more, the number of alcoholic hydroxyl groups in the epoxy resin (a1) is increased, and urethane bonds are formed by the reaction with the isocyanate, which is undesirable in that the glass transition point of the cured product is lowered. In addition, since the concentration of hydroxyl groups in the cured product increases, it is not preferable in terms of increasing the dielectric constant of the cured product. The larger the alcoholic hydroxyl group equivalent, the smaller the alcoholic hydroxyl group. When m is 0, the alcoholic hydroxyl group is lost and the alcoholic hydroxyl group equivalent is theoretically infinite, so that there is no need to set the upper limit value.

The epoxy resin (a1) can be obtained by a method in which a phenol compound represented by the following formula (2) and epihalohydrin are reacted in the presence of an alkali such as sodium hydroxide or a method in which a phenol compound represented by the formula (2) Followed by etherification, followed by epoxidation by oxidizing the allyl group with an oxidizing agent such as peroxide.

(2)

(Wherein R and X have the same meanings as R and X in the formula (1), respectively)

The epoxy equivalent of the epoxy resin (a1) is 100 g / eq. ~ 500 g / eq. And more preferably 150 g / eq. ~ 300 g / eq. Is more preferable. The alcoholic hydroxyl group equivalent was also 3000 g / eq. Or more, more preferably 4000 g / eq. Or more, more preferably 5000 g / eq. Or more.

The phenol compounds represented by the formula (2) are obtained by reacting corresponding cyclic aliphatic ketones and phenols with the methods disclosed in JP-A-4-282334 and JP-A-2015-51935. Examples of specific phenol compounds include phenolic compounds as shown below, but the present invention is not limited thereto.

(3)

These exemplified phenolic compounds are also available as commercial products and include, for example, BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, BisOCP- -nBZ, and BisOEP-2HBP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.).

Examples of the epoxy resin (a1) represented by the formula (1) include an epoxy resin obtained from the phenol compounds represented by the formula (2) and epihalohydrin. For example, 4,4 '- (2-methylcyclohexylidene) diphenol glycidyl ether, 4,4' - (3-methylcyclohexylidene) diphenol glycidyl ether, 4,4 ' - (4-methylcyclohexylidene) diphenol glycidyl ether, 4,4 '- (3,3,5-trimethylcyclohexylidene) diphenol glycidyl ether, Trimethylcyclohexylidene) -bis-phenylphenol glycidyl ether, 4,4 '- (3,3,5-trimethylcyclohexylidene) -bis-phenylphenol glycidyl ether, 4, 4'- (3,3,5-trimethylcyclohexylidene) -bis-dimethylphenol glycidyl ether, 4,4 '- (3,3,5-trimethylcyclohexylidene) -bis-tert- butyl Phenol glycidyl ether, and the like, but not limited thereto, and they may be used alone or in combination of two or more.

As the epoxy resin (a1), 4,4 '- (3,3,5-trimethylcyclohexylidene) diphenol, which is a phenol compound represented by the following formula (3), and epi An epoxy resin represented by the following formula (4) obtained from halohydrin is preferable.

[Chemical Formula 4]

[Chemical Formula 5]

(Wherein m has the same meaning as m in formula (1)),

As the epoxy resin (a) to be used in the present invention, an epoxy resin (a2) other than the epoxy resin (a1) may be used in an amount of 50 mass% or less insofar as the effect of the present invention is not impaired. It is understood that the epoxy resin (a2) does not have the structure represented by the formula (1). The combination in which the effect of the present invention is most expressed is the use (100% by mass) of the epoxy resin (a1) alone. If the amount of the epoxy resin (a1) is less than 50 mass%, the effect of the present invention may not be exhibited. The purpose of using the co-usable epoxy resin (a2) is for the purpose of imparting other properties such as, for example, further improvement in solvent solubility. Therefore, the use amount of the epoxy resin (a2) is preferably as small as possible.

The alcoholic hydroxyl group contained in the epoxy resin (a2) reacts with the isocyanate to form a urethane bond, which may lower the heat resistance of the cured product. Therefore, the alcoholic hydroxyl equivalent is 1000 g / eq. Or more, more preferably 3000 g / eq. Or more, more preferably 5000 g / eq. Or more.

The epoxy equivalent of the epoxy resin (a2) is not particularly limited, but is preferably 100 g / eq. ~ 300 g / eq. And more preferably 170 g / eq. ~ 300 g / eq. Is more preferable.

Examples of usable epoxy resin (a2) include epoxy resins such as bisphenol A type epoxy resins such as EOTOTT 速 YD-127, EOTOTT YD-128, EOTOTT YD-8125, EOTOT YD-825GS (Manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), Bisphenol F type epoxy resin such as Eptot YDF-170, Eptot YDF-1500, Eptot YDF-8170, Eptot YDF-870GS (Trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), tetramethyl bisphenol F type epoxy resin such as YSLV-80XY and YSLV-70XY A resin such as YX-4000 (trade name, manufactured by Mitsubishi Chemical Corporation), ZX-1251 (trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), hydroquinone type epoxy resin such as EOTOTT YDC- 1027 (trade name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), bisphenol- For example, ZX-1355 (trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), bisphenol S type epoxy resin (for example, ZX- Epoxy resin, for example, TX-0710 (trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), Epichron (registered trademark) EXA-1515 (trade name, manufactured by Dainippon Chemical Industry Co., Ltd.) For example, Epotho ZX-1684 (trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), phenol novolak type epoxy resin, (Trade name, manufactured by Mitsubishi Chemical Corporation), Epikote (registered trademark) 152, Epikote 154 (trade name, manufactured by Mitsubishi Chemical Corporation), Epikote (registered trademark) (Trade name, manufactured by DIC Corporation), cresol novolak type epoxy resin such as Ephotron YDCN-700 series (trade name, available from Shin-Tetsu Sumikin Chemical Co., Ltd.) Epiclon N-670, Epiclon N-670, Epiclon N-670, Epiclon N-673 and Epiclon N-695 (all trade names, manufactured by DIC Corporation), EOCN-1020 and EOCN-102S , EOCN-104S (trade name, manufactured by Nippon Yakusho Co., Ltd.), alkyl novolak type epoxy resin such as Epitot ZX-1071T, ZX-1270 and ZX-1342 (trade name, available from Shinnitetsu Sumikin Chemical Co., (Trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), naphthol novolak type epoxy resin, Nippon Pneumatic Mfg. Co., Ltd.), styrenated phenol novolak type epoxy resin such as Ecotot ZX-1247, GK- For example, Epotot ZX-1142L (trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), β-naphthol aralkyl type epoxy resin (For example, ESN-155, ESN-185V, ESN-175 (trade names, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), dinaphthol aralkyl type epoxy resins such as ESN- ESN-475V, ESN-485 (trade name, available from Shinnets Tetsu Sumikin Chemical Co., Ltd.) (trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.) Polyglycidyl ether compounds such as biphenylaralkylphenol type epoxy resins such as NC-3000 and NC-3000H (trade names, manufactured by Nippon Yakusho Co., Ltd.), diaminodiphenylmethane tetraglycidyl N, N ', N'-tetraglycidyl-1,3 (trifluoromethyl) benzoic acid, such as EOTOTO YH-434, EOTOTO YH-434GS (trade name, manufactured by Shinnitetsu Sumikin Chemical Co., -Benzene di (methane amine), such as TETRAD-X (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) Polyglycidyl ester compounds such as dimer acid type epoxy resins such as YD-171 (trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), aliphatic cyclic epoxy resins such as Celloxide (registered trademark) 2021 (Trade name, manufactured by Daicel Chemical Industries, Ltd.), and the like. However, the epoxy resin is not limited to these, and these epoxy resins may be used alone or in combination of two or more.

Of the epoxy resin (a2) that can be used in combination, an epoxy resin containing an aliphatic substituent is preferable for the purpose of lowering the dielectric constant. For the purpose of further improving the heat resistance, a polyfunctional phenol novolak type epoxy resin and a cresol novolak type epoxy resin Epoxy resins are preferable, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferable for the purpose of lowering the viscosity, but the present invention is not limited thereto.

The epoxy equivalent of the epoxy resin (a) used in the present invention is preferably 100 g / eq. ~ 500 g / eq. And more preferably 150 g / eq. ~ 300 g / eq. Is more preferable. When a plurality of epoxy resins are used in combination, measurement is carried out after mixing. When the respective epoxy equivalents are already known, they may be obtained by calculation.

The alcoholic hydroxyl group contained in the epoxy resin (a) reacts with the isocyanate to form a urethane bond, so that the heat resistance of the epoxy resin cured product obtained by curing the epoxy resin composition is lowered. Therefore, the alcoholic hydroxyl group equivalent in the epoxy resin (a) is 1000 g / eq. Or more, more preferably 3000 g / eq. Or more, more preferably 5000 g / eq. Or more. When a plurality of epoxy resins are used in combination, measurement is carried out after mixing. When the respective alcoholic hydroxyl group equivalents are already known, they may be obtained by calculation.

The alcoholic hydroxyl group of the epoxy resin (a) is an alcoholic hydroxyl group generated by the reaction of a phenolic compound and epihalohydrin. When the epihalohydrin is epichlorohydrin, the alcoholic hydroxyl group is an alcoholic hydroxyl group derived from a 2-chloro-3-hydroxypropyl group (a group derived from the addition of a phenol compound to the alpha position of epichlorohydrin ), An alcoholic hydroxyl group (?) Derived from a 1-chloromethyl-2-hydroxyethyl group resulting from the addition of a phenol compound to the? -Position of epichlorohydrin, a secondary alcoholic hydroxyl group (?), and? -glycol (?) generated by hydrolysis of an epoxy group of an epoxy resin. Since the alcoholic hydroxyl group in the present invention refers to both of (?), (?), (?) And (?), The alcoholic hydroxyl group equivalent is such that all of?,?,? It is an object of measurement.

To prepare the epoxy resin containing an oxazolidin ring of the present invention, an isocyanate compound (b) is used together with the epoxy resin (a). By the reaction of the epoxy resin (a) and the isocyanate compound (b), a desired oxazolidone ring-containing epoxy resin can be obtained. The isocyanate compound (b) may be any isocyanate compound having an average of not less than 1.8 isocyanate groups (-N = C = O) in the molecule, and may be an isocyanate compound for known purpose. Specific examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane isocyanate, xylylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, Diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, p-phenylenediisocyanate, transcyclohexane 1,4-diisocyanate, 4 , 4-dicyclohexylmethane diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, lysine ester triisocyanate, undecane triisocyanate, 1,8-diisocyanate -4-isocyanatomethyloctane, 1,3,6-hexamethylene Diisocyanate, butane-1,2-diisocyanate, trans-vinylene diisocyanate, propane-1,3-diisocyanate, propane-1,1-diisocyanate, Butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane- 1,5-diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, Ω'-1,3-dimethylbenzene diisocyanate, ω, ω'-1,4-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, Dimethylbenzene diisocyanate,?,? '- 1,3-dimethylcyclohexane diisocyanate,?,?' - 1,4- Dimethylcyclohexane diisocyanate,?,? '- 1,4-dimethylnaphthalene diisocyanate,?,?' - 1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane- Diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 1-methylbenzene-2,4-diisocyanate, 2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate, diphenylether-4,4'-diisocyanate, diphenylether- 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- Diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfate-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, etc. And a polyfunctional isocyanate compound such as polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate thiophosphate) -3,3 ', 4,4'-diphenylmethane tetraisocyanate, Or a block such as a polymer such as a dimer or a trimer of the isocyanate compound or a blocking agent such as an alcohol or a phenol, or a bis urethane compound, but the present invention is not limited thereto. These isocyanate compounds may be used alone or in combination of two or more.

Of these isocyanate compounds, bifunctional isocyanate compounds or trifunctional isocyanate compounds are preferable, and bifunctional isocyanate compounds are more preferable. If the number of functional groups of the isocyanate compound is large, there is a fear that the storage stability is lowered, and if it is small, heat resistance and dielectric properties may not be improved. Examples of the bifunctional isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, 1,3-bis (isocyanato Methyl) cyclohexane, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethyl xylylene diisocyanate, 1,5-naphthalene diisocyanate, tolylidine diisocyanate, isophorone diisocyanate, p-phenylenediisocyanate, transcyclohexane- 1,4-diisocyanate, 4,4-dicyclohexylmethane diisocyanate, lysine diisocyanate and tetramethyl xylene diisocyanate, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4-diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, Trimethylhexamethylene diisocyanate, and isophorone diisocyanate are preferable.

The reaction of the epoxy resin (a) and the isocyanate compound (b) can be carried out by a known method. Specific reaction methods include: (1) removing the moisture in the epoxy resin by melting the epoxy resin (a), purging with a dry gas or reducing the pressure in the system; adding an isocyanate compound (b) and a catalyst Or (2) after the epoxy resin (a) and the catalyst are mixed in advance and the moisture in the epoxy resin is removed by a method such as dry gas purge or depressurization in the system, the isocyanate compound (b) And then the reaction is carried out. In either method ^{, a} non-reactive solvent may be used if necessary, for example ^, when the resin viscosity is high and stirring is difficult.

The reaction mechanism for forming the oxazolidone ring is represented by the following reaction formula (5). The epoxy group of the epoxy resin (a) and the isocyanate group of the isocyanate compound (b) react with each other to form an oxazolidone ring by adding a catalyst to the epoxy resin (a) and the isocyanate compound (b).

[Chemical Formula 6]

When the epoxy resin (a) contains an alcoholic hydroxyl group, the isocyanate group of the isocyanate compound (b) undergoes an addition reaction with an alcoholic hydroxyl group to form a urethane bond, as shown in the following reaction formula (6).

(7)

The epoxy equivalence of the oxazolidone ring-containing epoxy resin can be estimated from the injection amount of the starting material according to the following formula (7). The epoxy equivalent weight of the oxazolidin ring-containing epoxy resin of the present invention is preferably 200 to 600 g / eq. to be. The content of the oxazolidone ring in the resin within the range can be adjusted by adjusting the NCO concentration of the isocyanate compound (b) to be used.

No: epoxy equivalent of epoxy resin containing oxazolidone ring (g / eq.)

Ne: Epoxy equivalent (g / eq.) Of epoxy resin (a)

Ni: equivalent of isocyanate group of isocyanate compound (b) (g / eq.)

Me: injection amount (g) of epoxy resin (a)

Mi: injection amount (g) of isocyanate compound (b)

For example, the epoxy equivalent of the epoxy resin (a) is 218 g / eq., The equivalent of the isocyanate group of the isocyanate compound (b) is 125 g / eq. , The epoxy equivalent of the oxazolidone ring-containing epoxy resin is 200 to 600 g / eq. The injection ratio Me / Mi in the mass portion of the epoxy resin (a) and the isocyanate compound (b) is 3.3 or more from the calculation formula (7).

The reaction between the epoxy resin (a) and the isocyanate compound (b) is preferably carried out by adding a catalyst. The addition temperature of the catalyst is preferably in the range of room temperature to 150 ° C, more preferably in the range of room temperature to 100 ° C.

The reaction temperature is preferably in the range of 100 占 폚 to 250 占 폚, more preferably in the range of 100 占 폚 to 200 占 폚, and still more preferably in the range of 120 占 폚 to 160 占 폚. When the reaction temperature is low, oxazolidone ring formation is not sufficiently carried out, and isocyanurate ring due to trimerization reaction of isocyanate group may be formed. In addition, if the reaction temperature is high, localized high molecular weight may occur and generation of an insoluble gel component may increase. Therefore, it is necessary to adjust the addition rate of the isocyanate compound (b). If the addition rate of the isocyanate compound (b) is high, the cooling may be delayed with respect to heat generation, and the desired reaction temperature may not be maintained. In addition, if the addition rate is low, the productivity may be remarkably lowered.

The reaction time is preferably from 15 minutes to 10 hours, more preferably from 30 minutes to 8 hours, even more preferably from 1 hour to 5 hours from the completion of addition of the isocyanate compound (b). This is because if the reaction time is short, there is a possibility that a large amount of an isocyanate group remains in the product. In addition, if the reaction time is long, there is a possibility that productivity is significantly lowered.

Specific examples of usable catalysts include lithium compounds such as lithium chloride and butoxy lithium, complex salts of boron trifluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide , Quaternary ammonium salts such as tetraethylammonium iodide, tertiary amines such as dimethylaminoethane, triethylamine, tributylamine, benzyldimethylamine and N-methylmorpholine, triphenylphosphine, tris (2, 6-dimethoxyphenyl) phosphine; amines such as amyltriphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, Tetrabutylphosphonium acetate-acetic acid complex, tetrabutylphosphonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphorus Phosphonium salts such as sodium bromide and tetrabutyl iodide, a combination of triphenylantimony and iodine, imidazoles such as 2-phenylimidazole, 2-methylimidazole and 2-ethyl-4-methylimidazole And alkali metal oxide such as sodium hydroxide. However, the present invention is not limited thereto. These catalysts may be used alone or in combination of two or more. Alternatively, it may be divided and used several times.

The kind of the catalyst is not particularly limited, but a preferred base catalyst in the catalyst is tetramethylammonium iodide in the reaction activity and the selectivity of the reaction. In the case of a catalyst having a low reaction activity, the reaction time may be prolonged and the productivity may be lowered. On the other hand, in the catalyst having low selectivity for the reaction, the polymerization reaction between the epoxy groups proceeds and the intended properties may not be obtained.

The amount of the catalyst is not particularly limited, but is preferably 0.001 mass% or more and 5 mass% or less based on the total mass of the epoxy resin (a) and the isocyanate compound (b), more preferably 0.005 mass% or more and 1 mass% More preferably not less than 0.5% by mass, and still more preferably not less than 0.001% by mass and not more than 0.2% by mass. If the amount of the catalyst is large, the autocopolymerization reaction of the epoxy group proceeds in some cases, which may increase the resin viscosity. Further, the self-polymerization reaction of the isocyanate is promoted, which may inhibit the formation of the oxazolidone ring. In addition, when used as a material for various applications, particularly as a laminate or a sealing material, the resulting resin remains as an impurity, which may result in deterioration of insulating properties and deterioration of moisture resistance. If the amount of the catalyst is small, there is a fear that the efficiency for obtaining an oxazolidone ring-containing epoxy resin is lowered.

When the reaction between the epoxy resin (a) and the isocyanate compound (b) is carried out, the molecular weight (epoxy equivalence) and the like can be adjusted by using various epoxy resin modifiers in addition to the effect of the present invention have. The amount that can be used is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less, based on 100 parts by mass of the epoxy resin (a).

Specific examples of epoxy resin modifiers that can be used include bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol A, tetrabutyl bisphenol A, bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol F, bisphenol S, dimethyl bisphenol S, tetra Bisphenol C, bisphenol E, bisphenol P, bisphenol AF, bisphenol AP, bisphenol fluorene, biscresol fluorene, bisphenol Z, tetramethyl bisphenol Z, bisphenol TMC, hydroquinone, methyl hydroquinone, dimethyl There may be mentioned hydroquinone, dibutyl hydroquinone, resorcin, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, dihydroxybenzophenone, dihydroxydiphenyl sulfide, di Phenol novolac resins, cresol novolak resins, bisphenol A novolak resins, dicyclopentadiene resins, Various phenols such as phenol resin, phenol aralkyl resin, naphthol novolak resin, styrenated phenol novolac resin, terpene phenol resin, and heavy oil-modified phenol resin, and various phenols and various phenols such as hydroxybenzaldehyde, crotonaldehyde, glyoxal The polyhydric phenol resin obtained by the condensation reaction of various aldehydes of the aldehyde group or the aldehyde group obtained by condensation reaction of various aldehydes of the aldehyde group such as aniline, phenylenediamine, toluidine, xylidine, diethyltoluenediamine, diaminodiphenylmethane, diaminodiphenylpropane, (Aminophenyl) fluorene, diaminodiethyldimethyldiphenylmethane, diaminodiphenyl ether, diaminobenzanilide, diaminobiphenyl, diaminodiphenylsulfone, diaminodiphenylsulfone, diaminodiphenylsulfone, diaminodiphenylsulfone, , Dimethyldiaminobiphenyl, biphenyltetramine, bisaminophenyl anthracene, bisaminophenoxybenzene, bisaminophenoxyphenyl ether , Bisaminophenoxybiphenyl, bisaminophenoxyphenylsulfone, bisaminophenoxyphenylpropane, diaminonaphthalene, and the like, but not limited thereto, and these epoxy resin modifiers may be used alone , Or two or more types may be used in combination.

If necessary, a non-reactive solvent may be used. Specific examples thereof include various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene and ethylbenzene, ethylether, isopropylether, But are not limited to, ethers such as methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, amyl ether, methylphenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methylfuran and tetrahydrofuran, methyl cellosolve, But are not limited to, acetone, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethyl formamide, and dimethyl sulfoxide. They may be used alone or in combination of two or more.

4 (Example 1) and Fig. 5 (Comparative Example 2) show the absorbance spectrum in the range of 1650 to 1800 cm < ^-1 > when the epoxy resin containing an oxazolidone ring was analyzed by the total reflection measurement method (ATR method) of an infrared spectrophotometer. Respectively.

In the absorbance spectrum of FIG. 4, a peak A originating from the stretching vibration of the carbonyl group of the oxazolidone ring appears at 1745 to 1760 cm ^-1 . The peak B derived from the stretching vibration of the carbonyl group of the urethane bond appears at 1730 to 1740 cm ^-1 .

In the absorbance spectrum of FIG. 5, a peak A originating from the stretching vibration of the carbonyl group of the oxazolidone ring appears at 1745 to 1760 cm ^-1 . Peak B derived from the stretching vibration of the carbonyl group of the urethane bond overlaps with the peak of the oxazolidone ring and does not show a definite peak top so that the maximum value of the absorbance within the range of 1730 to 1740 cm ^-1 is absorbed by the urethane bond do.

The maximum value of the peak included at 1745 to 1760 cm ^-1 derived from the stretching vibration of the carbonyl group of the oxazolidone ring is represented by the absorbance Ox. The maximum value of the peak included at 1730 to 1740 cm ^-1 derived from the stretching vibration of the carbonyl group of the urethane bond is taken as the absorbance Ur. At this time, the ratio of the oxazolidone ring to the urethane bond was expressed by the absorbance ratio Ox / Ur.

When an epoxy resin containing an oxazolidone ring is produced by the reaction of the epoxy resin (a) and the isocyanate compound (b), when the alcoholic hydroxyl group contained in the epoxy resin (a) reacts with the isocyanate group of the isocyanate compound (b) The reaction to form a urethane bond by the reaction formula (6) occurs instead of the reaction to form the oxazolidone ring of the compound (5). When the concentration of the urethane bond contained in the epoxy resin containing an oxazolidone ring is increased, there is a fear that the heat resistance of the epoxy resin cured product obtained by curing the epoxy resin composition is lowered. Therefore, the ratio of the oxazolidone ring contained in the oxazolidone ring-containing epoxy resin to the urethane bond is defined as the absorbance ratio Ox / Ur. The absorbance ratio Ox / Ur is preferably 1.35 or more, more preferably 2.0 or more. If the absorbance ratio Ox / Ur is less than 1.35, the heat resistance of the cured epoxy resin containing oxazolidone ring may be lowered.

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, more preferably 70 ° C to 110 ° C, More preferable. When the softening point is low, since the resin varnish is impregnated with glass cloth and then heated and dried in an oven, the viscosity is low, so that the adhesion amount of the resin may be reduced. When the softening point is high, the resin viscosity is increased, voids are generated when the laminated plate is produced from the point that the impregnation property to the prepreg deteriorates, the solvent solubility deteriorates, the diluting solvent remains in the resin when heated and dried, There is a fear that it becomes a big problem in use.

The epoxy equivalent of the oxazolidin ring-containing epoxy resin of the present invention is 200 g / eq. More than 550 g / eq. Or less, and 215 g / eq. More than 500 g / eq. Is preferably in the range of 230 g / eq. More than 450 g / eq. More preferably less than 250 g / eq. More than 350 g / eq. And the following range is more preferable. When the epoxy equivalent is low, the content of the oxazolidone ring is reduced and the hydroxyl group concentration in the cured product becomes high, which may increase the dielectric constant. On the other hand, if the epoxy equivalent is high, the content of the oxazolidone ring is increased more than necessary, and there is a possibility that adverse effects such as deterioration of solvent solubility and increase of resin viscosity are more likely than improvement of dielectric property. Further, since the cross-linking density of the cured product is lowered, the elastic modulus at the solder reflow temperature is lowered, which may cause a problem in use.

The oxazolidone ring-containing epoxy resin of the present invention can be made into a curable epoxy resin composition by blending a curing agent. As the curing agent, conventionally used epoxy resin curing agents such as various phenol resins, acid anhydrides, amines, hydrazides, acidic polyesters and the like can be used. These curing agents may be used alone or in combination of two or more. Among them, dicyandiamide or a phenolic curing agent is particularly preferable.

In the epoxy resin composition, the amount of the curing agent to be used is in the range of 0.2 to 1.5 moles of the active hydrogen group of the curing agent relative to 1 mole of the epoxy group of the whole epoxy resin containing the oxazolidone ring-containing epoxy resin. When the active hydrogen group is less than 0.2 mol or more than 1.5 mol per 1 mol of the epoxy group, the curing is incomplete and there is a possibility that good curing properties are not obtained. The preferable range is 0.3 mol or more and 1.5 mol or less, more preferably 0.5 mol or more and 1.5 mol or less, and still more preferably 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, the active hydrogen group is almost equimolarly added to the epoxy group, and when an acid anhydride-based curing agent is used, the acid anhydride group is used in an amount of 0.5 to 1.2 moles, 0.6 to 1.0 moles.

The active hydrogen group in the present invention is a functional group having an active hydrogen reactive with an epoxy group (including a functional group having a latent active hydrogen which generates active hydrogen by hydrolysis or the like, or a functional group exhibiting an equivalent curing action) Include an acid anhydride group, a carboxyl group, an amino group, and a phenolic hydroxyl group. With respect to the active hydrogen group, 1 mole of the carboxyl group (-COOH) and the phenolic hydroxyl group (-OH) and 2 moles of the amino group (-NH ₂ ) are calculated. When the active hydrogen group is not clear, the active hydrogen equivalent can be obtained by measurement. For example, by reacting a monoepoxy resin, such as phenyl glycidyl ether, whose epoxy equivalent is already known, with a curing agent whose active hydrogen equivalent is not yet known, and measuring the amount of monoepoxy resin consumed, the active hydrogen equivalent of the curing agent Can be obtained.

Specific examples of the phenol resin-based curing agent include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, tetramethyl bisphenol Z, Bisphenols such as 4,4'-thiobis (3-methyl-6-tert-butylphenol), and also bisphenols such as catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, Dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, dihydroxynaphthalene, dihydroxybenzene, dihydroxybenzene, dihydroxybenzene, (Trade name) manufactured by Nippon Kayaku Kogyo Kogyo Co., Ltd.) such as phenol novolak resin, cresol novolak resin, and Regist (registered trademark) TPM-100 Condensates of naphthols and aldehydes, condensation products of phenols and / or naphthols and xylylene glycol, such as SN-160, SN (methylenebisphenol), naphthol -395, SN-485 (product name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), condensates of phenols and / or naphthols with isopropenyl acetophenone, reaction products of phenols and / or naphthols with dicyclopentadiene, Phenol compounds such as condensates of phenols and / or naphthols with biphenyl condensation agents, and the like.

Examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol and phenylphenol. Naphthols include 1-naphthol, 2- Naphthol, and the like. Examples of the aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, Aldehyde, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like. Examples of the biphenyl-based condensing agent include bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl and bis (chloromethyl) biphenyl.

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

Specific examples of the amine-based curing agent include diethylenetriamine, triethylenetetramine, meta-xylylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, benzyldimethylamine , 2,4,6-tris (dimethylaminomethyl) phenol, dicyandiamide, dimer acid and the like, and amine compounds such as polyamide amine which is a condensate of polyamines.

Specific examples of other curing agents include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl- Imidazoles such as imidazoles, imidazole salts such as trimellitic acid, isocyanuric acid, boron and the like, imidazoles such as imidazole, Diazabicyclo compounds and salts such as phenols and phenol novolak resins, complexes such as boron trifluoride and amines and ether compounds, aromatic phosphonium salts, or iodonium salts such as iodonium salts And the like.

If necessary, an epoxy resin other than the oxazolidone ring-containing epoxy resin of the present invention may be used within a range that does not impair the physical properties of the epoxy resin composition. Specific examples of epoxy resins that can be used include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, bisphenol fluorene type epoxy resin, A phenol novolak type epoxy resin, a styrenated phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a cresol novolak type epoxy resin, a cresol novolak type epoxy resin, a cresol novolak type epoxy resin, Novolak type epoxy resins, novolak type epoxy resins, alkyl novolak type epoxy resins, bisphenol novolak type epoxy resins, naphthol novolak type epoxy resins,? -Naphthol aralkyl type epoxy resins, dinaphthol aralkyl type epoxy resins, Epoxy resin, trisphenylmethane type epoxy resin, trisphenylmethane type epoxy resin, An epoxy group-containing epoxy resin, an epoxy group-containing epoxy resin, a pentadiene type epoxy resin, an alkylene glycol type epoxy resin, an alicyclic epoxy resin, diaminodiphenylmethane tetraglycidylamine, Containing epoxy resin, but are not limited thereto. These epoxy resins may be used alone or in combination of two or more.

If necessary, a curing accelerator may be used in the epoxy resin composition. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) Tertiary amines such as 8-diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine and triphenylphosphine triphenylborane, Tin and the like. The curing accelerator is used in an amount of 0.02 parts by mass to 5 parts by mass based on 100 parts by mass of the epoxy resin component in the epoxy resin composition of the present invention. By using the curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

Organic solvents may also be used in the epoxy resin composition for viscosity adjustment. Examples of the organic solvent that can be used include amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol And aromatic hydrocarbons such as alcohols, benzene and toluene. These solvents may be used alone or in combination of two or more thereof in an amount of 20% by mass to 90% by mass as an epoxy resin concentration.

If necessary, a diluent may be used within a range that does not impair the physical properties of the epoxy resin composition. The diluent is preferably a reactive diluent, but may be a non-reactive diluent. Examples of the reactive diluent include monofunctional, resorcinol glycidyl ether such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether and phenyl glycidyl ether, neopentyl glycol glycidyl ether, 1,6- And hexanediol diglycidyl ether; and polyfunctional glycidyl ethers such as glycerol polyglycidyl ether, trimethylol propane polyglycidyl ether, and pentaerythritol polyglycidyl ether. Examples of the non-reactive diluent include benzyl alcohol, butyl diglycol, and pine oil.

The epoxy resin composition may be blended with other thermosetting resin or thermoplastic resin to the extent that the properties are not impaired. Examples of the resin include phenol resin, acrylic resin, petroleum resin, indene resin, coumarone resin, phenoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, polyetherimide resin , A polyphenylene ether resin, a modified polyphenylene ether resin, a polyether sulfone resin, a polysulfone resin, a polyether ether ketone resin, a polyphenylene sulfide resin, a polyvinyl formal resin and the like. It is not.

For the purpose of improving the flame retardancy of the resulting cured product, various publicly known flame retardants may be used in the epoxy resin composition. Examples of the flame retardant that can be used include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organometallic salt-based flame retardants. From the viewpoint of the environment, a halogen-free flame retardant is preferable, and a phosphorus flame retardant is particularly preferable. These flame retardants may be used alone or in combination of two or more.

As the phosphorus flame retardant, both an inorganic phosphorus compound and an organic phosphorus compound can be used. Examples of the inorganic phosphorus compound include inorganic phosphorus compounds such as ammonium phosphate, ammonium phosphate, ammonium phosphate, ammonium phosphate, ammonium triphosphate and ammonium polyphosphate, and inorganic nitrogenous compounds such as phosphoric acid amide. Examples of the organic phosphorus compound include organic phosphorus compounds such as aliphatic phosphate esters, phosphoric acid ester compounds, condensed phosphoric acid esters, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) Cyclic organophosphorus compounds such as 10-phosphaphenanthrene-10-oxide and 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene- Phosphorus-containing epoxy resins and phosphorus-containing curing agents, which are derivatives obtained by reacting them with a compound such as an epoxy resin or a phenol resin.

The blending amount of the flame retardant is appropriately selected according to the kind of the phosphorus-based flame retardant, the component of the epoxy resin composition, and the degree of desired flame retardancy. For example, the content of phosphorus 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 preferably not less than 0.6 mass% and not more than 3 mass%. When the phosphorus content is low, there is a fear that the flame retardancy can not be ensured, and if it is too much, the heat resistance may be adversely affected. When a phosphorus flame retardant is used, a flame retardant auxiliary such as magnesium hydroxide may be used in combination.

A filler may be optionally added to the epoxy resin composition. Specific examples of the filler include 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, A fiber, a glass fiber, an alumina fiber, a silica alumina fiber, a silicon carbide fiber, a polyester fiber, a cellulose fiber, an aramid fiber, a ceramic fiber, a particulate rubber, a thermoplastic elastomer and a pigment. Generally, the reason for using the filler is to improve the impact resistance. In addition, when a metal hydroxide such as aluminum hydroxide, boehmite, or magnesium hydroxide is used, it acts as a flame retardant adjuvant and has an effect of improving the flame retardancy. The blending amount of these fillers is preferably 1% by mass to 150% by mass, and more preferably 10% by mass to 70% by mass, based on the whole epoxy resin composition. If the blending amount is large, there is a fear that the adhesiveness required for laminated board applications is lowered, and further, the cured product is discarded and sufficient mechanical properties may not be obtained. If the compounding amount is too small, there is a possibility that the effect of compounding the filler may not be exhibited, such as the improvement of the impact resistance of the cured product.

When the epoxy resin composition is a plate-like substrate or the like, fibrous fillers can be mentioned as the filler in terms of dimensional stability and bending strength. More preferably, a glass fiber substrate in which glass fibers are woven in the form of a mesh is exemplified.

The epoxy resin composition may further contain a nuclide additive such as a silane coupling agent, an antioxidant, a releasing agent, a defoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant, and a pigment. These additives are preferably in the range of 0.01% by mass to 20% by mass with respect to the epoxy resin composition.

The epoxy resin composition can impregnate the fibrous substrate to produce a prepreg for use in a printed wiring board or the like. As the fibrous substrate, inorganic fibers such as glass, woven or nonwoven fabric of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, and aromatic polyamide resin can be used, but the present invention is not limited thereto . The method for preparing the prepreg from the epoxy resin composition is not particularly limited and includes, for example, impregnating and impregnating a resin varnish prepared by adjusting the viscosity of an epoxy resin composition with a solvent, (B stage), and can be heated and dried, for example, at 100 ° C to 200 ° C for 1 minute to 40 minutes. Here, the resin amount in the prepreg is preferably 30% by mass to 80% by mass of the resin component.

In order to harden the prepreg, a curing method of a laminated board generally used for producing a printed wiring board can be used, but the present invention is not limited thereto. For example, when a laminate is formed using a prepreg, a laminate is formed by laminating one prepreg or a plurality of prepregs and arranging a metal foil on one side or both sides of the prepreg, and heating and pressing the laminate to form a laminate do. As the metal foil, copper, aluminum, brass, nickel, etc. alone, an alloy, and a composite metal foil can be used. Then, the produced laminate is heated under pressure to cure the prepreg to obtain a laminate. At this time, it is preferable to set the heating temperature at 160 ° C to 220 ° C, the pressing pressure at 50 N / cm 2 to 500 N / cm 2, and the heating and pressurizing time at 40 minutes to 240 minutes to obtain the objective cured product. If the heating temperature is low, the curing reaction does not sufficiently proceed, and if the heating temperature is too high, decomposition of the epoxy resin composition may start. If the pressing pressure is low, bubbles may remain in the laminate to be obtained and electrical properties may be deteriorated. If the pressing pressure is high, the resin may flow before being cured, and a cured product having a desired thickness may not be obtained. If the heating and pressurizing time is short, there is a fear that the curing reaction will not proceed sufficiently, and if it is long, thermal decomposition of the epoxy resin composition in the prepreg may occur, which is not preferable.

An epoxy resin cured product can be obtained by curing the epoxy resin composition. As a method for obtaining the cured product, the same method as the known epoxy resin composition can be adopted. The method unique to the epoxy resin composition of the present invention is not required, and a mold, injection, potting, dipping, drip coating, Compression molding, etc., a resin sheet, a resin-coated copper foil, a prepreg, or the like, and heating and curing the mixture to form a laminated board. The curing temperature at that time is usually in the range of 100 占 폚 to 300 占 폚, and the curing time is usually about 1 hour to 5 hours.

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

Epoxy resin composition was prepared and the epoxy resin cured product of the laminate was evaluated by heat curing. As a result, it was found that the oxazolidone ring-containing epoxy resin of the present invention had a low dielectric property and a low viscosity And not only the workability was good but also the high heat resistance and the high adhesion were able to be obtained and the solvent solubility was also improved.

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 stated, " part " represents the mass part, and "% " The measurement methods were respectively measured by the following methods.

Epoxy equivalent: It is in conformity with JIS K7236 standard.

· Viscosity: It was conformed to JIS K7233 standard, single cylinder rotational viscometer method.

Softening point: Measured according to JIS K7234 standard, ring method (ring system). Specifically, an automatic softening point device (ASP-MG4, manufactured by Meitec Co., Ltd.) was used.

Solvent Solubility: The state when diluted with methyl ethyl ketone to a non-volatile content of 50% was visually determined. The completely dissolved and transparent ones were marked with o, the whitened or separated ones were marked with x, and the lightly browned was marked with △.

Absorbance ratio Ox / Ur: The absorbance at 1650 to 1800 cm ^-1 was measured by a total internal reflection measurement method (ATR method) of a Fourier transform infrared spectrophotometer (Spectrum One FT-IR Spectrometer 1760X manufactured by PerkinEler Precisely) Cm < ^-1 > and the maximum value of the absorbance in the range of 1730 to 1740 cm < ^-1 >

Copper Peel Strength and Interlaminar Adhesion: Measured according to JIS C6481, and the interlaminar adhesive strength was measured by peeling between the 7th layer and the 8th layer.

Glass transition temperature (DSC method): When measurement was carried out at 20 ° C / min temperature elevation with a differential scanning calorimeter (EXSTAR 6000 DSC6200, manufactured by Hitachi High-Tech Science Co., Ltd.) according to IPC-TM-650 2.4.25.c (The middle temperature of the transition curve with respect to the tangent line between the glassy state and the rubbery state).

Glass Transition Temperature (TMA Method): The glass transition temperature (TMA method) was measured using a thermomechanical analyzer (EXSTAR6000 TMA / SS120U, manufactured by Hitachi High-Tech Science Co., Ltd.) in accordance with IPC-TM-650 2.4.24.1 TMA extrapolated values.

Specific dielectric constant and dielectric loss tangent: The dielectric constant and dielectric loss tangent at a frequency of 1 GHz were evaluated by a capacitance method using a material analyzer (AGILENT Technologies) according to IPC-TM-650 2.5.5.9.

· Flammability: According to UL 94 (Safety Certification Standard of Underwriters Laboratories Inc.), it was evaluated by the vertical method.

GPC: Columns (TSKgel (registered trademark) G4000HXL, TSKgelG3000HXL, TSKgelG2000HXL, manufactured by Toso Co., Ltd.) in series were used in the main body (HLC-8220GPC manufactured by Tosoh Corporation) and the column temperature was 40 占 폚. Further, tetrahydrofuran was used as the eluent, the flow rate was 1 ml / min, and the detector was an RI (differential refractometer) detector. From the calibration curve obtained from standard monodisperse polystyrene.

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

NMR: A liquid measurement of ¹³ C was carried out using CDCL ₃ as a solvent by a Fourier transform nuclear magnetic resonance apparatus (manufactured by JEOL, JNM-ECA400).

Synthesis Example 1

100 parts of 4,4 '- (3,3,5-trimethylcyclohexylidene) diphenol (Bisp-TMC, manufactured by Honshu Chemical Industry Co., Ltd.), 358 parts of epichlorohydrin, Four parts of exchanged water were injected, and the temperature was raised to 50 캜 with stirring. After uniformly dissolving, 5.3 parts of a 49% sodium hydroxide aqueous solution was injected and the reaction was carried out for 3 hours. Next, the temperature was raised to 64 DEG C, the pressure was reduced to such an extent that reflux of water occurred, and 48 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours. Then, water and epichlorohydrin, Separately, epichlorohydrin was returned to the reaction vessel, and water was removed out of the system and reacted. After completion of the reaction, the temperature was raised to 70 캜 and dehydration was carried out, and the temperature was raised to 135 캜 to recover the remaining epichlorohydrin. The pressure was returned to normal pressure, and 204 parts of methyl isobutyl ketone (MIBK) was added and dissolved. 127 parts of ion-exchanged water was added, and the mixture was allowed to stand to dissolve the by-produced salt in water. Next, 2.9 parts of a 49% sodium hydroxide aqueous solution was injected, and the mixture was reacted at 80 DEG C for 90 minutes with stirring to carry out a purification reaction. MIBK was added and washed several times to remove ionic impurities. The solvent was recovered to obtain an epoxy resin (epoxy resin A) represented by the above formula (4). The resulting epoxy resin A had an epoxy equivalent of 219 g / eq., An alcoholic hydroxyl equivalent of 5510 g / eq. , And m (mean value) is 0.04.

Synthesis Example 2

282 parts of phenol and 14.8 parts of 98% sulfuric acid were charged into the same apparatus as in Synthesis Example 1, and the temperature was raised to 80 占 폚. After stirring at the same temperature for 1 hour, 33.6 parts of 4-methylcyclohexanone and 6 parts of n-dodecylmercaptan were added at 60 DEG C, and water was removed at 65 DEG C and 1.3 DEG C to remove remaining 4-methylcyclohexanone The reaction was allowed to be 50% of the input. After pressurizing to normal pressure with nitrogen gas, the mixture was cooled to room temperature and allowed to stand for 3 days. Thereafter, toluene and ion-exchanged water were added to the solidified reaction product to dissolve it, neutralized with sodium hydroxide, and washed with ion-exchanged water. The obtained organic layer was cooled as it was, and the precipitated crystals were separated by filtration and dried. The obtained crystals were recrystallized from methanol water, separated by filtration and dried. This operation was repeated twice to obtain 4,4 '- (4-methylcyclohexylidene) diphenol.

Subsequently, the same operation as in Synthesis Example 1 was carried out except that 100 parts of BisP-TMC was changed to 91 parts of 4,4 '- (4-methylcyclohexylidene) diphenol thus obtained, (Epoxy resin B) was obtained. The obtained epoxy resin B had an epoxy equivalent of 206 g / eq., An alcoholic hydroxyl equivalent of 5480 g / eq. And m is 0.05.

[Chemical Formula 8]

Synthesis Example 3

The same operation as in Synthesis Example 1 was carried out except that 100 parts of BisP-TMC was changed to 86.5 parts of 4,4'-cyclohexylidenebisphenol (Bis-Z, manufactured by Honshu Chemical Industry Co., Ltd.) 9) (epoxy resin F). The obtained epoxy resin F had an epoxy equivalent of 200 g / eq., An alcoholic hydroxyl equivalent of 5500 g / eq. And m is 0.06.

[Chemical Formula 9]

The abbreviations used in Examples and Comparative Examples are as follows.

(Epoxy resin)

Epoxy resin A: The epoxy resin obtained in Synthesis Example 1

Epoxy resin B: Epoxy resin obtained in Synthesis Example 2

Epoxy resin C: bisphenol A type liquid epoxy resin (Epotot YD-128, epoxy equivalent 186 g / eq., Alcoholic hydroxyl equivalent 2,000 g / eq., Manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)

Epoxy Resin D: dicyclopentadiene type epoxy resin (KDCP-130, epoxy equivalent 254 g / eq., Alcoholic hydroxyl equivalent 2500 g / eq. Manufactured by Gokuto Chemical Co., Ltd.)

Epoxy resin E: styrenated phenol novolac epoxy resin (TX-1210, epoxy equivalent 257 g / eq., Alcoholic hydroxyl equivalent 2800 g / eq., Manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)

Epoxy resin F: Epoxy resin obtained in Synthesis Example 3

(Isocyanate)

Isocyanate A: diphenylmethane diisocyanate (Kosonate (registered trademark) PH, NCO concentration 34%, manufactured by Mitsui Chemicals, Inc.)

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

Isocyanate C: Cyclohexane-1,3-diylbis methylene diisocyanate (Takenate (registered trademark) 600, manufactured by Mitsui Chemicals, Inc., NCO concentration: 43%

(catalyst)

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

Catalyst B: n-Butyltriphenylphosphonium bromide (HISCOLIN (registered trademark) BTPPBr manufactured by Nippon Chemical Industrial Co., Ltd.)

Catalyst C: Tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

Catalyst D: tetrabutylammonium iodide (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

Catalyst E: tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

Catalyst F: tetraethylammonium iodide (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

Catalyst G: Triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

Catalyst H: Tris (2,6-dimethoxyphenyl) phosphine (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

Catalyst I: N, N'-dimethylpiperazine (manufactured by Tokyo Chemical Industry Co., Ltd., reagent)

(Hardener)

PN: Phenol novolac resin (Shonol (registered trademark) BRG-557, manufactured by Showa Denko K.K., softening point 80 ° C)

DICY: Dicyandiamide (manufactured by Nippon Carbide Co., Ltd.)

(Hardening accelerator)

2E4MZ: 2-ethyl-4-methylimidazole (Curezol (registered trademark) 2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.)

(Flame retardant)

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

Example 1

100 parts of the epoxy resin A as the epoxy resin (a) and 0.11 part of the catalyst A as a catalyst were injected into the same apparatus as in Synthesis Example 1, and the temperature was raised while nitrogen gas was supplied. The temperature was maintained at 120 캜 for 30 minutes, The moisture was removed. Next, 11.5 parts of isocyanate A as the isocyanate compound (b) (the molar ratio of the isocyanate group of the isocyanate compound (b) to the 1 mole of the epoxy group of the epoxy resin (a) b) / (a)] = 0.20) as a 50% toluene solution over 3 hours. After completion of the dropwise addition, stirring was further continued for 60 minutes while maintaining the same temperature. After completion of the reaction, the solvent was removed under the conditions of recovery at 150 DEG C, 1.33 DEG C, and 30 minutes to obtain an oxazolidone ring-containing epoxy resin (Resin 1). The epoxy equivalent, the softening point, the solvent solubility, and the absorbance ratio of the obtained oxazolidone ring-containing epoxy resin were measured. The measurement results are shown in Table 1. Fig. 1 shows a GPC chart. (The elution time (min) is indicated on the abscissa and the signal intensity (㎷) is shown on the left ordinate), and the number average molecular weight M is represented by a logarithm (log) The measured value of the average molecular weight was plotted as a white circle to be a calibration curve.) An IR chart is shown in Fig. (In the figure, the abscissa shows the number of waves (cm ^-1 ) and the ordinate shows the transmittance (% T).) FIG. 3 shows a ¹³ C-NMR spectrum NMR chart. 4 shows the absorbance spectrum in the range of 1650 to 1800 cm ^-1 when analyzed by the total reflection measurement method (ATR method) of an infrared spectrophotometer.

Examples 2 to 18

An epoxy resin containing an oxazolidone ring was synthesized by the same operation using the same apparatus as in Example 1, in accordance with the injection amount (parts) of each raw material shown in Table 1 or Table 2. The reaction temperature was maintained at the reaction temperature of ± 5 ° C. shown in Table 1 or Table 2, and the dropping time shown in Table 1 or Table 2 of the isocyanate compound was carried out. The epoxy equivalent, softening point, solvent solubility, and absorbance ratio of the resulting epoxy resin containing oxazolidone ring were measured in the same manner as in Example 1, and the measurement results are shown in Table 1 or Table 2.

Comparative Examples 1 to 5

An epoxy resin containing an oxazolidone ring was synthesized by the same operation using the same apparatus as in Example 1, in accordance with the injection amount (parts) of each raw material shown in Table 3. The reaction temperature was maintained at the temperature range of the reaction temperature ± 5 ° C. shown in Table 3, and the dropping time shown in Table 3 was applied to the isocyanate compound. The epoxy equivalent, softening point, solvent solubility and absorbance ratio of the obtained epoxy resin containing an oxazolidone ring were measured in the same manner as in Example 1, and the measurement results are shown in Table 3. 5 shows the absorbance spectrum in the range of 1650 to 1800 cm ^-1 when analyzed by the total reflection measurement method (ATR method) of an infrared spectrophotometer with respect to the epoxy resin containing an oxazolidone ring obtained in Comparative Example 2. FIG.

The oxazolidone ring-containing epoxy resin obtained in Example 1 was used as Resin 1, and Resins 2 to 18 were used in the same manner as Resin 1. The oxazolidone ring-containing epoxy resin obtained in Comparative Example 1 was used as comparative resin 1, and comparative resins 2 to 5 were used as follows.

Example 19

100 parts of the resin 1 of Example 1 as an epoxy resin, 35.6 parts of PN as a curing agent, and 0.01 parts of 2E4MZ as a curing accelerator were mixed and mixed with a mixed solvent prepared by 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 (WEA 116E106S136, thickness: 0.1 mm, manufactured by Nitto Denki Co., Ltd.). The impregnated glass cloth was dried in a hot air circulating oven at 150 캜 for 11 minutes to obtain a prepreg. 8 prepregs and a copper foil (3EC-III, thickness: 35 탆, manufactured by Mitsui Mining & Metals Mfg. Co., Ltd.) were laminated on the upper and lower sides and subjected to a vacuum press at 2 MPa at a temperature condition of 130 캜 x 15 minutes + 190 캜 x 80 minutes To obtain a laminate having a thickness of 1 mm. The results of the copper foil peel strength, interlaminar adhesive strength, glass transition temperature (DSC method) (Tg · DSC) and glass transition temperature (TMA) (Tg · TMA) of the laminated board are shown in Table 4.

The obtained prepreg was loosened and sieved to prepare a 100-mesh-pass powdery prepreg powder. The obtained prepreg powder was placed in a mold made of a fluororesin and subjected to a vacuum press at 2 MPa at a temperature condition of 130 DEG C x 15 minutes + 190 DEG C x 80 minutes to prepare a test piece having a size of 50 mm x 2 mm ≪ / RTI > Table 4 shows the results of the relative dielectric constant and dielectric tangent of the test pieces.

Examples 20 to 36

The resin 2 to resin 18, PN, and 2E4MZ of Examples 2 to 18 were compounded in the amounts shown in Table 4 or 5 (parts), and the same operation as in Example 19 was carried out, And a test piece. The same test as in Example 19 was carried out, and the results are shown in Table 4 or Table 5. In the table, " - " indicates that it is not used.

Comparative Examples 6 to 13

The comparative resin 1 to comparative resin 5, epoxy resin A, epoxy resin D, epoxy resin E, PN, and 2E4MZ of Comparative Examples 1 to 5 were compounded in the compounding amounts (parts) shown in Table 6, The same operation was carried out to obtain a laminate and a test piece. The same test as in Example 19 was conducted, and the results are shown in Table 6. In the table, " - " indicates that it is not used.

Examples 37 to 41 and Comparative Examples 14 to 16

Resin 1, Resin 5, Resin 6, Resin 17, Resin 18, Resin 1, Resin 2, Resin 4, DICY and 2E4MZ were compounded in the formulations (parts) shown in Table 7, Using the apparatus, a laminate and a test piece were obtained by the same operation. The same test as in Example 19 was conducted, and the results are shown in Table 7. [ In the table, " - " indicates that it is not used.

Examples 42 to 44 and Comparative Examples 17 to 19

Resin 5, Resin 6, Resin 17, Comparative Resin 1, Comparative Resin 2, Comparative Resin 4, PN, 2E4MZ and PX-200 were compounded in the compounding amount (parts) of the prescription in Table 8, Using the same procedure, the same test as in Example 19 in which a laminated plate and a test piece were obtained was carried out. The test piece for flame retardancy measurement was obtained by etching both surfaces of the laminate. In the table, " - " indicates that it is not used.

INDUSTRIAL APPLICABILITY The present invention can be used as an epoxy resin for an electronic circuit board which is excellent in heat resistance, adhesiveness and dielectric properties, as an oxazolidone ring-containing epoxy resin obtained by reacting an epoxy resin (a) and an isocyanate compound (b) .

Claims (18)

An epoxy equivalent of 200 to 550 g / eq. Obtained from an epoxy resin (a) containing 50 mass% or more of an epoxy resin (a1) represented by the following formula (1) and an isocyanate compound (b) An epoxy resin containing an oxazolidone ring.
[Chemical Formula 1]

(Wherein X represents a cycloalkylidene group having 5 to 8 ring atoms and having at least one substituent selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 6 to 10 carbon atoms. R represents independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms, and G denotes a glycidyl group. Represents the repetition, and the average value is 0 to 5.) The method according to claim 1,
The alcoholic hydroxyl equivalent of the epoxy resin (a1) is 3000 g / eq. Or more epoxy resin containing an oxazolidone ring. 3. The method according to claim 1 or 2,
When the epoxy resin (a1) has an alcoholic hydroxyl equivalent of 1000 g / eq. Of an epoxy resin (a2) in an amount of 50 to 0 mass% in the epoxy resin (a). 4. The method according to any one of claims 1 to 3,
The epoxy equivalent of the epoxy resin (a) is 100 to 500 g / eq. An epoxy resin containing an oxazolidone ring. 5. The method according to any one of claims 1 to 4,
Wherein the isocyanate compound (b) has an average number of isocyanate groups of 1.8 or more in the molecule. 6. The method according to any one of claims 1 to 5,
Wherein the isocyanate compound (b) is at least one selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and isophorone diisocyanate. An epoxy resin containing an oxazolidone ring having a molecular weight greater than or equal to 100,000. 7. The method according to any one of claims 1 to 6,
In the analysis by the infrared absorption spectrum, the maximum value of the peak included in 1745 to 1760 cm ^-1 derived from the stretching vibration of the carbonyl group of the oxazolidone ring is represented by the absorbance Ox, 1730 derived from the stretching vibration peak of the carbonyl group of the urethane bonding structure To 1740 cm ^-1 as the maximum absorbance Ur and the absorbance ratio Ox / Ur is 1.35 or more. 8. The method according to any one of claims 1 to 7,
And an epoxy resin having an oxazolidone ring having a softening point of 50 to 150 ° C. (A) containing 50% by mass or more of an epoxy resin (a1) represented by the following formula (1) and an isocyanate compound (b) in the presence of a catalyst at a reaction temperature of 100 ° C or more and 250 ° C or less ≪ / RTI > wherein the epoxy resin comprises an oxazoline ring.
(2)

(Wherein X represents a cycloalkylidene group having 5 to 8 ring atoms and having at least one substituent selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 6 to 10 carbon atoms. R represents independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms, and G denotes a glycidyl group. Represents the repetition, and the average value is 0 to 5.) 10. The method of claim 9,
Wherein an isocyanate group of the isocyanate compound (b) is in a range of 0.02 mol or more and less than 0.5 mol based on 1 mol of the epoxy group of the epoxy resin (a). 11. The method according to claim 9 or 10,
Wherein the isocyanate compound (b) has an average number of isocyanate groups of 1.8 or more in the molecule. 12. The method according to any one of claims 9 to 11,
Wherein the isocyanate compound (b) is at least one selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and isophorone diisocyanate. Method for preparing epoxy resin containing oxazolidone ring having a number of species or more. 13. The method according to any one of claims 9 to 12,
A process for producing an epoxy resin containing an oxazolidone ring, wherein the catalyst is a basic catalyst. An epoxy resin composition characterized by containing an oxazolidone ring-containing epoxy resin according to any one of claims 1 to 8 and a curing agent. 15. The method of claim 14,
Wherein the active hydrogen group of the curing agent is 0.2 to 1.5 moles per mole of the epoxy group of the whole epoxy resin in the epoxy resin composition. An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 14 or 15. A prepreg characterized by using the epoxy resin composition according to claim 14 or 15. An epoxy resin laminate characterized by using the epoxy resin composition according to claim 14 or 15.

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