TWI675047B - Oxazolidone ring-containing epoxy resin, method for producing the same, epoxy resin composition and usage thereof and epoxy resin cured product - Google Patents

Abstract

The present invention provides an epoxy resin having the characteristics of maintaining a conventional adhesive force and further improving heat resistance. An oxazolidone ring-containing epoxy resin is an oxazolidone ring-containing epoxy resin obtained from an epoxy resin (a) and an isocyanate compound (b), and the epoxy resin (a ) Is measured by gel permeation chromatography, with a dinuclear content rate of 20 area% or less, a trinuclear content rate of 15 area% or more and 60 area% or less, and a pentanuclear body content rate of 45 or more Novolac-type epoxy resin having an area% or less and a molecular weight distribution of a number average molecular weight of 350 to 700.

Description

An oxazolidone ring-containing epoxy resin, a method for producing the same, an epoxy resin composition and use thereof, and an epoxy resin hardened product

The present invention relates to an oxazolidone ring-containing epoxy resin that provides a hardened material having excellent dielectric properties, high heat resistance, low hygroscopicity, and high adhesion. The epoxy resin containing the resin as an essential component Resin composition, and hardened epoxy resin, prepreg, laminate, and printed circuit board obtained from the composition.

Epoxy resins are excellent in adhesion, flexibility, heat resistance, chemical resistance, insulation, and hardening reactivity, so they are used in many areas such as coatings, civil bonding, casting, electrical and electronic materials, and film materials. In particular, in printed circuit board applications, which are one of electrical and electronic materials, they are widely used by imparting flame retardancy to epoxy resins.

Infrastructure devices such as portable devices and base stations that maintain the use of printed circuit boards as one of the uses of the printed circuit boards have been required to be highly functional with the rapid increase in the amount of information in recent years. In portable devices, high-level multilayers or fine lines are used for the purpose of miniaturization. Materials with a lower dielectric constant are required to make the substrate thinner. The number of bonding surfaces is reduced due to fine lines. Highly adhesive material. In the substrate facing the base station, in order to suppress the attenuation of high-frequency signals, a material with a lower dielectric loss tangent is required.

Although the characteristics such as low dielectric constant, low dielectric loss tangent, and high adhesive force are derived from the structure of an epoxy resin as a base resin of a printed circuit board, a new epoxy resin or a modification technology thereof is required to a large extent.

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

The oxazolidone ring-containing epoxy resin obtained by the reaction between an epoxy resin and an isocyanate is also disclosed in Patent Document 3. As a raw material epoxy resin, a glycidyl group of a dihydric phenol such as bisphenol A is exemplified. Compounds obtained by chemical conversion, tris (glycidyloxyphenyl) alkanes, compounds obtained by glycidizing amine phenol and the like, and compounds obtained by glycidizing novolacs such as phenol novolak.

However, the epoxy resins disclosed in any of the literatures have not sufficiently satisfied the requirements for dielectric properties based on high functionality in recent years, and the adhesiveness has also been insufficient. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 5-293929 [Patent Literature 2] Japanese Patent Laid-Open No. 9-278867 [Patent Literature 3] Japanese Patent Laid-Open No. 5-43655

[Problems to be Solved by the Invention]

Therefore, the problem to be solved by the present invention is to provide an epoxy resin having properties such as low dielectric properties, high heat resistance, and high adhesiveness, which are useful in applications such as lamination, molding, casting, and bonding. Oxygen resin is an epoxy resin composition having an essential component and a cured product thereof.

[Technical means to solve the problem]

In order to solve the problem, the present inventors conducted active research on a material having a low dielectric constant and a low dielectric loss tangent. As a result, it was found that the content of an epoxy resin and an isocyanate compound having a specific molecular weight distribution in the epoxy resin was used. The oxazolidone ring epoxy resin can simultaneously achieve low dielectric constant, low dielectric loss tangent, and high glass transition temperature, which are not available at present, and further has good adhesion, thereby completing the present invention.

That is, the present invention is an oxazolidone ring-containing epoxy resin, which is an oxazolidone ring-containing epoxy resin obtained from an epoxy resin (a) and an isocyanate compound (b). The epoxy resin (a) is measured by Gel Permeation Chromatography (GPC), and has a dinuclear content rate of 20 area% or less, a trinuclear content rate of 15 area% or more and 60 area % Or less, novolac-type epoxy resin having a content ratio of pentahedron or more of 45 area% or less, and a molecular weight distribution of a number average molecular weight of 350 or more and 700 or less. The GPC measurement conditions are as follows.

A GPC measuring device HLC-8220GPC manufactured by Tosoh Corporation was used. A string including TSKgelG4000HXL, TSKgelG3000HXL, and TSKgelG2000HXL manufactured by Tosoh Corporation was used, and the column temperature was set to 40 ° C. Tetrahydrofuran (THF) was used as the eluent, and the flow rate was set to 1 mL / min. The detector was an RI (differential refractometer) detector. The data was processed using GPC-8020 Model II version 4.10 manufactured by Tosoh Corporation. A 100 μL sample was used as a measurement sample, and the sample was a sample obtained by dissolving a 0.1 g sample in 10 mL of THF and filtering the sample with a microfilter. From the obtained chromatogram, calculate the dinuclear content rate and trinuclear content rate. According to the standard monodisperse polystyrene (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), and the number average molecular weight was measured.

The novolak-type epoxy resin is preferably an epoxy resin represented by the following formula (1). [Chemical 1] (In the formula, Ar is an aromatic group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic groups may further have an alkyl group having 1 to 6 carbon atoms substituted for the aromatic ring. X represents a divalent Aliphatic cyclic hydrocarbon group or a cross-linking group represented by the following formula (1a) or the following formula (1b), G represents a glycidyl group, m represents 1 or 2, and n represents a repeating unit and an integer of 0 or more)

(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 represents an aromatic group including a benzene ring, a biphenyl ring, or a naphthalene ring, and these aromatic groups (It may have an alkyl group having 1 to 6 carbon atoms which substitutes an aromatic ring.)

The isocyanate compound (b) preferably has an average of 1.8 or more isocyanate groups in the molecule.

The isocyanate group of the isocyanate compound (b) is preferably reacted with respect to 1 mol earring oxy group of the epoxy resin (a) within a range of 0.02 mol to 0.6 mol.

The epoxy equivalent of the oxazolidone ring-containing epoxy resin is preferably 200 g / eq. To 500 g / eq., And the softening point is preferably 50 ° C to 150 ° C.

In addition, the present invention is an epoxy resin composition characterized in that the oxazolidone ring-containing epoxy resin and the hardener are essential components, and the oxazolidone ring-containing epoxy resin is used as an essential component. The active hydrogen group of the hardener is blended in the range of 0.2 mol to 1.5 mol of all the epoxy resins in the range of 0.2 mol to 1.5 mol. The present invention is an epoxy resin cured product obtained by curing the epoxy resin composition. Moreover, the present invention is a prepreg, a laminate, and an electronic circuit substrate, which is characterized by using the epoxy resin composition.

The present invention is a method for producing an oxazolidone ring-containing epoxy resin, which is a method for producing an oxazolidone ring-containing epoxy resin obtained from an epoxy resin (a) and an isocyanate compound (b). , Characterized in that the epoxy resin (a) is a GPC measurement having the GPC measurement conditions, the dinuclear content rate is 20 area% or less, the trinuclear content rate is 15 area% or more and 60 area% In the following, novolac-type epoxy resins having a content ratio of pentads or more of 45% by area or less and a molecular weight distribution of a number-average molecular weight of 350 or more and 700 or less; The isocyanate group of the isocyanate compound (b) is set to a range of 0.02 mol or more and 0.6 mol or less.

The novolak epoxy resin is preferably an epoxy resin represented by the formula (1), and the isocyanate compound (b) preferably has an average of 1.8 or more isocyanate groups in the molecule.

[Effect of the invention]

The oxazolidone ring-containing epoxy resin of the present invention exhibits a hardened physical property that maintains adhesion and has a high glass transition temperature. In addition, the epoxy resin hardened product has excellent dielectric characteristics, and exhibits good characteristics in a laminate and an electronic circuit board that require a low dielectric constant and a low dielectric loss tangent.

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

The epoxy resin (a) used in the oxazolidone ring-containing epoxy resin of the present invention is preferably a polyfunctional novolak resin represented by the following formula (2), and a formula obtained by reacting with an epihalohydrin ( 1) A polyfunctional novolak-type epoxy resin having a specific molecular weight distribution represented by the following formula (2): The polyfunctional novolac resin represented by the following formula (2) crosslinks phenols and aldehydes in the presence of an acid catalyst Agent condensation. [Chemical 3]

(In the formula, Ar, X, m, and n are synonymous with Ar, X, m, and n in formula (1), respectively.)

In the formula (1) and the formula (2), Ar is an aromatic group selected from a group including a benzene ring, a naphthalene ring, or a biphenyl ring which may further have a substituent. When these aromatic groups have a substituent, examples thereof include alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl, The third butyl group, hexyl group, cyclohexyl group and the like are not limited to these groups, and when there are a plurality of groups, they may be the same or different. From the viewpoints of ease of availability and physical properties such as adhesiveness in a laminate, a preferred substituent is a methyl group.

X is a divalent aliphatic cyclic hydrocarbon group or a crosslinking group represented by formula (1a) or formula (1b). The carbon number of the divalent aliphatic cyclic hydrocarbon group is preferably 5 to 15, and more preferably 5 to 10. 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 including a benzene ring, a biphenyl ring, or a naphthalene ring. 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 the raw material phenols. n is a repeating unit, and represents an integer of 0 or more. An average value of 0.5 to 4 is a preferred range, 1 to 3.5 is a more preferred range, and 1.5 to 3 is a more preferred range.

Examples of the phenols used to obtain the novolak resin represented by formula (2) include phenol, cresol, ethylphenol, butylphenol, styrenated phenol, cumylphenol, naphthol, catechol, m-phenol Hydroquinone, naphthalene, and the like are not limited to these compounds, and these phenols may be used alone or in combination of two or more. Among these phenols, monophenols such as phenol and alkylphenol are preferred. The alkyl group in the case of an alkylphenol is preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the cross-linking agent used to obtain the novolac resin include formaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and benzaldehyde, or the following formula (4) Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, or p-xylylene glycol, p-xylylene glycol dimethyl ether, and p-dichlorobenzyl represented by the following formula (5) (P-xylylene dichloride), 4,4'-dimethoxymethylbiphenyl, 4,4'-dichloromethylbiphenyl, dimethoxymethylnaphthalenes, dichloromethylnaphthalenes, etc. Crosslinking agents, or crosslinkers such as divinylbenzenes, divinylbiphenyls, and divinylnaphthalenes represented by the following formula (6), or cycloalkanes such as cyclopentadiene or dicyclopentadiene Although these are not limited to these compounds, these crosslinking agents may be used alone or in combination of two or more. X of Formula (1) and Formula (2) becomes a bivalent aliphatic cyclic hydrocarbon group when a cycloalkyl diene is used, and when using a crosslinking agent of Formula (3) or Formula (4) It becomes a crosslinking group represented by Formula (1a), and when using a crosslinking agent of Formula (5) or Formula (6), it becomes a crosslinking group represented by Formula (1b). Among these crosslinking agents, formaldehyde, acetaldehyde, benzaldehyde, acetone, p-dichlorobenzyl, 4,4'-dichloromethylbiphenyl are preferred, and formaldehyde is particularly preferred. Preferable forms when formaldehyde is used in the reaction include formalin aqueous solution, paraformaldehyde, trioxane, and the like. [Chemical 4] (Wherein, R R ₁ and R ₂ in the formula (1a) is _1, and R ₂ is synonymous, R R _3, R _4, and B, respectively of formula (1a), _3, R ₄ and B are synonymous, Y independently represents Hydroxyl, alkoxy, or halogen atom)

Examples of acidic catalysts used to obtain novolac resins 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 ferric chloride. Acids, oxalic acid, monochloroacetic acid, and the like are not limited to these compounds, and these acidic catalysts may be used alone or in combination of two or more. Among these acidic catalysts, phosphoric acid, toluenesulfonic acid, and oxalic acid are preferred.

Examples of commonly used novolak-type epoxy resins include phenol novolak-type epoxy resins, such as Epotohto (registered trademark) YDPN-638 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and Epico (Epikote) (registered trademark) 152, Epikote (registered trademark) 154 (Mitsubishi Chemical Corporation), Epiclon (registered trademark) N-740, Epiclon (Epiclon) N-770 Epiclon N-775 (manufactured by Dickson Co., Ltd.); cresol novolac epoxy resin, such as Epotohto YDCN-700 series (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) , Epiclon N-660, Epiclon N-665, Epiclon N-670, Epiclon N-673, Epiclon N-695 (Manufactured by Di Edison Co., Ltd.), EOCN-1020, EOCN-102S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.); alkyl novolac epoxy resins such as Epotohto ZX-1071T, Epotohto ZX-127 0. Epotohto ZX-1342 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); styrenated phenol novolac epoxy resin, such as Epotohto ZX-1247, Epotohto ) GK-5855, Epotohto TX-1210 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); naphthol novolac epoxy resin, such as Epotohto ZX-1142L (Nippon Steel & Sumikin) Chemical Co., Ltd.); β-naphthol aralkyl type epoxy resins, such as ESN-155, ESN-185V, ESN-175 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); peronaphthol aralkyl type Epoxy resins, such as ESN-355 and ESN-375 of ESN-300 series (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); α-naphthol aralkyl type epoxy resins, such as ESN-475V of ESN-400 series , ESN-485 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); biphenylaralkyl phenol type epoxy resins, such as NC-3000, NC-3000H (manufactured by Nippon Kayaku Co., Ltd.), etc., these commonly used phenolic aldehydes Varnish-type epoxy resin may not have the same as used in the present invention Molecular Weight Distribution in Novolac Epoxy Resins.

The novolak-type epoxy resin used in the present invention is preferably a novolak resin using a compound having a specific molecular weight distribution as a raw material. Such a novolak resin can be adjusted with the molar ratio of phenols to aldehydes, and It is obtained by the method of removing a low molecular weight component from the obtained novolak resin. Moreover, such a novolak resin can also be obtained by a manufacturing method shown in Japanese Patent Laid-Open No. 2002-194041 or Japanese Patent Laid-Open No. 2007-126683. Here, the "specific molecular weight distribution" means that in the measurement of GPC, the dinuclear content rate is 20 area% or less, the trinuclear content rate is 15 area% or more and 60 area% or less, and the The content rate is 45% by area or less. The number average molecular weight is preferably 350 to 700.

The molar ratio of phenols and cross-linking agents is expressed by the molar ratio of phenols to 1 molar cross-linking agent (phenol / crosslinking agent), and is produced at a ratio of 1 or more of the molar ratio, but When the mole ratio is large, more dinuclear bodies and trinuclear bodies are generated. Conversely, when the mole ratio is small, more high-molecular weight bodies, dinuclear bodies, and trinuclear bodies are more frequently formed. Body becomes less. Here, in the novolak resin represented by the formula (2) or the novolak-type epoxy resin represented by the formula (1), a so-called "nucleus" such as a dinuclear body, a trinuclear body, and the like means that it is present in a molecule The number of Ar. That is, the "i-nuclear body" is a compound of the structural formula of n = i-2 in formula (1) and formula (2). In addition, the ratio of dinuclear and trinuclear bodies is also related to the ratio of novolac resins before epoxidation, but it varies depending on the conditions of epoxidation. Therefore, novolac epoxy resins are述 范围。 The range. Therefore, the molar ratio (phenol / crosslinking agent) of the phenols and the crosslinking agent is preferably 3 or more and 6 or less, and more preferably 4 or more and 5 or less.

Regarding the novolak resins obtained by adjusting the molar ratio of the phenols and the crosslinking agent as described above, a novolak resin having a specific molecular weight distribution can be obtained by reducing or removing low molecular weight components. In this case, as a method for reducing or removing low-molecular-weight components, particularly dinuclear bodies, a method using various solvents having poor solubility, a method of dissolving in an alkaline aqueous solution, other known separation methods, and the like can be mentioned.

A well-known epoxidation method is used for a novolak resin having a specific molecular weight distribution, and a novolak-type epoxy resin having a specific molecular weight distribution used in the present invention can be obtained. Alternatively, low-molecular-weight components, particularly dinuclear components, can be reduced or removed from commercially available novolac-type epoxy resins by various methods, whereby novolak-type epoxy resins having a specific molecular weight distribution can also be obtained.

The novolak-type epoxy resin used in the present invention has the following molecular weight distribution: in the GPC measurement, the dinuclear content rate is 20 area% or less, the trinuclear content rate is 15 area% or more and 60 area% or less, The content rate of pentanuclear bodies or more is 45% by area or less, and the number average molecular weight is 350 or more and 700 or less. Thus, a desired oxazolidone ring-containing epoxy resin having excellent dielectric properties, heat resistance, and adhesiveness can be obtained. In addition, the total area is the total of the areas of two or more core bodies.

The dinuclear content rate is 20 area% or less, preferably 15 area% or less, and more preferably 5 area% or more and 12 area% or less. When the content of the dinuclear body exceeds 20 area%, the heat resistance gradually decreases. When there are too few dinuclear bodies, there exists a possibility that resin viscosity as an oxazolidone ring containing epoxy resin may become high. The trinuclear content rate 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 content rate of the trinuclear body is less than 15 area%, there is a concern that the content of the oxazolidone ring cannot be increased and the heat resistance is poor. When the content rate of the trinuclear body exceeds 60 area%, there is a concern that the adhesion is poor. . The content rate of the pentanuclear body or more is 45 area% or less, more preferably 40 area% or less, and even more preferably 30 area% or less. When the content rate of the pentanuclear body or more is 45% by area or less, a cured product having higher heat resistance can be obtained without lowering the adhesiveness. If the content of the pentanuclear body is too high, there is a concern that the content of the oxazolidone ring cannot be increased, the effect of improving the dielectric properties cannot be exhibited, or gelation during manufacture cannot be achieved, and the target oxazolidine-containing content cannot be obtained. Ketone ring epoxy. In addition, the content rate of the tetranuclear body is not particularly limited, and the total content rate of the trinuclear body and the tetranuclear body is preferably 15 area% or more and 85 area% or less, and more preferably 30 area% or more and 70 area%. Hereinafter, it is more preferably 40 area% or more and 60 area% or less. By setting it as this range, since the molecular weight increase at the time of isocyanate modification can be suppressed, the ratio of the epoxy resin containing an oxazolidone ring can be raised. If the effects of the tri- and tetra-nuclear bodies are compared, the tri-nuclear body can further improve the adhesion, and the tetra-nuclear body can further improve the heat resistance. This can improve resin physical properties such as dielectric properties, heat resistance, and adhesiveness.

The number average molecular weight is 350 or more and 700 or less, and more preferably 380 or more and 600 or less. When the number average molecular weight exceeds 700, there is a concern that the viscosity of the obtained oxazolidone ring-containing epoxy resin becomes high, which adversely affects workability or impregnation of the substrate. On the other hand, if the number average molecular weight becomes less than 350, there is a concern that the heat resistance is significantly deteriorated.

When producing the oxazolidone ring-containing epoxy resin of the present invention, an isocyanate compound (b) is used together with the epoxy resin (a). The desired oxazolidone ring-containing epoxy resin can be obtained by the reaction between the epoxy resin (a) and the isocyanate compound (b). As long as this isocyanate compound (b) is an isocyanate compound which has a some isocyanate group (-N = C = O) in a molecule | numerator, a well-known and usual isocyanate compound can be used.

Specific examples include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4-diphenylmethane diisocyanate, xylene diisocyanate, 1,3-bis (isocyanatomethyl) ) Cyclohexane, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, benzylamine diisocyanate, isophorone diisocyanate , P-phenylene diisocyanate, trans cyclohexane-1,4-diisocyanate, 4,4-dicyclohexylmethane diisocyanate, lysine diisocyanate, tris (isocyanatephenyl) thiophosphate, lysine Ester triisocyanate, undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, methane diisocyanate Isocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, butane-1,2-diisocyanate, trans ethylene diisocyanate, propane-1,3-diisocyanate, butane- 1,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methyl Alkane-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-dimethylbenzene diisocyanate, ω, ω'-1,3-dimethylcyclohexane diisocyanate, ω, ω'-1,4-dimethylcyclohexane diisocyanate, ω, ω'-1,4-dimethylnaphthalene diisocyanate, ω, ω'-1,5-dimethylnaphthalene diisocyanate, Cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-benzenediisocyanate, 1,4-benzenediisocyanate , 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 Acid ester, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4 '-Diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, di Bifunctional isocyanate compounds such as phenylsulfite-4,4'-diisocyanate, diphenylfluorene-4,4'-diisocyanate, or polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, tri ( 4-phenyl isocyanate thiophosphate) polyfunctional isocyanate compounds such as 3,3 ', 4,4'-diphenylmethane tetraisocyanate, or polymers such as dimers or trimers of the isocyanate compound Or block isocyanate or biscarbamate compound or the like blocked with a blocking agent such as alcohol or phenol, but it is not limited to these compounds. These isocyanate compounds may be used singly or in combination of two or more kinds.

Among these isocyanate compounds, a bifunctional isocyanate compound or a trifunctional isocyanate compound is preferable, and a bifunctional isocyanate compound is more preferable. When the number of functional groups of the isocyanate compound is large, there is a concern that the storage stability will decrease, and when the number of functional groups of the isocyanate compound is small, there is a concern that heat resistance or dielectric properties will not be improved. The bifunctional isocyanate compound is preferably 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4-diphenylmethane diisocyanate, xylene diisocyanate, 1,3-bis (isocyanatomethyl) Group) cyclohexane, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, benzylamine diisocyanate, isophorone di Isocyanates, terephthalic diisocyanates, transcyclohexane-1,4-diisocyanates, 4,4-dicyclohexylmethane diisocyanates, lysine diisocyanates, tetramethylxylene diisocyanates.

The reaction between the epoxy resin (a) and the isocyanate compound (b) can be performed by a known method. The specific reaction methods are: (1) melting the epoxy resin (a), removing the moisture in the epoxy resin by using dry gas flushing or reducing the pressure in the system, and then adding the isocyanate compound (b) and A method for reacting with a catalyst; and (2) pre-mixing the epoxy resin (a) with the catalyst, removing the moisture in the epoxy resin by a method such as flushing with dry gas or reducing the pressure in the system, and then adding the Method of reacting isocyanate compound (b) and the like. In any method, if the resin has high viscosity and it is difficult to stir, etc., a non-reactive solvent may be used if necessary.

The reason why the oxazolidone ring is formed is represented by the following reaction formula (7). The epoxy resin (a) and the isocyanate compound (b) react with an epoxy group of the epoxy resin (a) and an isocyanate group of the isocyanate compound (b) by adding a catalyst to form an oxazolidone ring. [Chemical 5]

The isocyanate group of the isocyanate compound (b) is preferably reacted with respect to 1 equivalent of the epoxy group of the epoxy resin (a) within a range of 0.02 equivalent to 0.6 equivalent. If the ratio of isocyanate groups is low, there is a fear that the effect of improving the dielectric properties or heat resistance cannot be obtained. Moreover, when there are many ratios of isocyanate groups, there exists a possibility that the thickening at the time of reaction may become severe and a desired oxazolidone ring containing epoxy resin may not be obtained. In addition, there is a concern that the solubility of the solvent deteriorates and it cannot be used for laminate applications. The range is more preferably 0.1 equivalent to 0.5 equivalent, and still more preferably the range of 0.2 equivalent to 0.4 equivalent. Here, 1 equivalent of an epoxy group is the same as 1 equivalent of an isocyanate group, and 1 mol earring oxy group is the same as 1 mol isocyanate group.

It is preferable to add a catalyst to perform the reaction of the epoxy resin (a) and the isocyanate compound (b). The addition temperature of the catalyst is preferably in the range of room temperature to 150 ° C, and more preferably in the range of room temperature to 100 ° C.

The reaction temperature is preferably in the range of 100 ° C or higher and 250 ° C or lower, more preferably in the range of 100 ° C or higher and 200 ° C or lower, and even more preferably in the range of 120 ° C or higher and 160 ° C or lower. If the reaction temperature is low, there is a concern that the formation of the oxazolidone ring cannot proceed sufficiently, and an isotricyanate ring is formed due to the trimerization reaction of the isocyanate group. Further, if the reaction temperature is high, there is a concern that a local high molecular weight is generated, and an insoluble gel component is generated more. Therefore, it is necessary to adjust the addition speed of the isocyanate compound (b). If the addition rate of the isocyanate compound (b) is high, there is a concern that it is not possible to cool it with respect to heat generation, and it becomes impossible to maintain a preferable reaction temperature. In addition, if the addition speed is slow, there is a concern that productivity will decrease.

The reaction time is preferably in the range of 15 minutes to 10 hours after the addition of the isocyanate compound (b) is completed, more preferably 30 minutes to 8 hours, and still more preferably 1 hour to 5 hours. The reason is that if the reaction time is short, there is a concern that a large number of isocyanate groups remain in the product. In addition, if the reaction time is long, there is a concern that productivity will decrease.

Specific examples of usable catalysts include lithium compounds such as lithium chloride and lithium butoxylate, salts of boron trifluoride, tetramethylammonium chloride, tetramethylammonium bromide, and tetrabutyl bromide. Quaternary ammonium salts such as ammonium, tetramethylammonium iodide, tetraethylammonium iodide, dimethylaminoethanol, triethylamine, tributylamine, benzyldimethylamine, N-methylmorpholine, etc. Tertiary amines, phosphines such as triphenylphosphine, tri (2,6-dimethoxyphenyl) phosphine, pentyltriphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyl Triphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, tetrabutylphosphonium acetate · acetic acid complex, tetrabutylphosphonium acetate, tetrabutylphosphonium chloride, Samarium salts such as butylphosphonium bromide and tetrabutylphosphonium iodide, combinations of triphenylantimony and iodine, imidazoles such as 2-phenylimidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole And the like, alkali metal oxides such as sodium hydroxide, and the like, but are not limited to these catalysts, and these catalysts may be used singly or in combination of two or more. In addition, it can be divided and used several times.

The amount of catalyst is not particularly limited, and it may be used in an amount of 0.001% by mass or more and 5% by mass or less with respect to the total mass of the epoxy resin (a) and the isocyanate compound (b), preferably 0.005% by mass or more, 1 It is more preferably 0.005% by mass or more and 0.5% by mass or less, and still more preferably 0.001% by mass or more and 0.2% by mass or less. If the amount of the catalyst is large, there is a concern that the epoxy group undergoes a self-polymerization reaction depending on the situation, and thus the resin viscosity becomes high. In addition, there is a concern that the self-polymerization reaction of the isocyanate is promoted and the generation of the oxazolidone ring is suppressed. In addition, there is a concern that it may remain as an impurity in the generated resin, and when it is used as a material for a laminate or a sealing material in various applications, it may cause a decrease in insulation or moisture resistance. If the amount of the catalyst is small, there is a concern that the efficiency for obtaining an oxazolidone ring-containing epoxy resin decreases.

When carrying out the reaction of the epoxy resin (a) and the isocyanate compound (b), if necessary, various other epoxy resins may be used in a range that does not affect the effect of the present invention. Examples of epoxy resins that can be used in combination include bisphenol A epoxy resins, such as Epotohto YD-127, Epotohto YD-128, Epotohto YD-8125, and Epotohto (Epotohto) YD-825GS (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); bisphenol F-type epoxy resins, such as Epotohto YDF-170, Epotohto YDF-1500, Epotohto (Epotohto) YDF-8170, Epotohto YDF-870GS (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); tetramethyl bisphenol F-type epoxy resin, such as YSLV-80XY, YSLV-70XY (Sinichi (Made by Tetsusumi Chemical Co., Ltd.); biphenol type epoxy resins, such as YX-4000 (manufactured by Mitsubishi Chemical Co., Ltd.), ZX-1251 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); hydroquinone ring Oxygen resin, such as Epotohto YDC-1312, Epotohto ZX-1027 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); bisphenol fluorene type epoxy resin, such as ZX-1201 (Nippon (Made by Tetsusui Jin Chemical Co., Ltd.); naphthalene-type epoxy resin, For example, ZX-1355 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); bisphenol S type epoxy resin, such as TX-0710 (made by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epiclon EXA-1515 ( Dainippon Chemical Industry Co., Ltd.); Disulfide type epoxy resin, such as YSLV-120TE (Nippon Steel & Sumikin Chemical Co., Ltd.); Resorcinol type epoxy resin, such as Epotohto ZX-1684 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and other polyglycidyl ether compounds; diaminodiphenylmethane tetraglycidyl ether, such as Epotohto YH-434, Epotohto YH-434GS (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.); N, N, N ', N'-tetraglycidyl-1,3-benzenedi (methaneamine), such as TETRAD-X (Mitsubishi Gas Chemical Co., Ltd. Co., Ltd.) and other polyglycidylamine compounds; dimer acid epoxy resins, such as YD-171 (Nippon Steel & Sumikin Chemical Co., Ltd.) and other polyglycidyl ester compounds; aliphatic cyclic epoxy resins, such as Celloxid (Celloxide) ( Registered trademark) 2021 (manufactured by Daicel Chemical Industries, Ltd.) and the like alicyclic epoxy compounds, but are not limited to, those epoxy resins may be used alone, or two or more may be used. Among these epoxy resins that can be used in combination, biphenol-type epoxy resins, hydroquinone-type epoxy resins, bisphenol fluorene-type epoxy resins, naphthalene diphenol-type epoxy resins, disulfide-type epoxy resins, and epoxy resins are preferred. Bifunctional epoxy resins such as hydroquinone epoxy resin. By using a small amount of a bifunctional epoxy resin in combination, the amount of the isocyanate compound (b) can be increased without impeding the effect of the present invention, and the dielectric characteristics can be further improved. The usable amount is preferably 35% by mass or less, and more preferably 20% by mass or less.

When the reaction between the epoxy resin (a) and the isocyanate compound (b) is performed, the molecular weight can be adjusted by further using various epoxy resin modifiers within a range that does not affect the function and effect of the present invention. (Epoxy equivalent) and so on. The usable amount is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of the epoxy resin (a).

Specific usable epoxy resin modifiers include bisphenol A, bisphenol F, bisphenol AD, tetrabutyl bisphenol A, bisphenol Z, bisphenol TMC, hydroquinone, and methyl p-benzene Diphenol, dimethylhydroquinone, dibutylhydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, Dihydroxystilbene, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolac resin, styrenated phenol novolac resin , Terpene phenol resins, heavy oil modified phenol resins and other phenols, or polyphenol resins obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, or aniline, benzene Diamine, toluidine, xylylamine, diethyltoluenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenylketone, Diaminodiphenylsulfide, diaminodiphenylphosphonium, bis (aminophenyl) phosphonium, diaminodiethyldimethyldiphenylmethyl , Diamino diphenyl ether, diamino benzamidine aniline, diamino biphenyl, dimethyl diamino biphenyl, biphenyl tetramine, bisaminophenylanthracene, bisaminophenoxybenzene Amine compounds such as bisaminophenoxyphenyl ether, bisaminophenoxybiphenyl, bisaminophenoxyphenylfluorene, bisaminophenoxyphenylpropane, diaminonaphthalene, but not Limited to these compounds, these epoxy resin modifiers may be used alone or in combination of two or more.

Furthermore, a non-reactive solvent may be used as necessary. Specific examples include various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and ethylbenzene. Ethers such as diethyl ether, isopropyl ether, butyl ether, diisopentyl ether, methyl phenyl ether, ethyl phenyl ether, pentyl phenyl ether, ethyl benzyl ether, dioxane, methyl furan, tetrahydrofuran, etc. Base cellosolve, methyl cellosolve acetate, ethyl cellosolve, acetic cellosolve, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methyl ethyl carbitol, propylene glycol mono Methyl ether, dimethylformamide, dimethylmethane, and the like are not limited to these compounds, and these non-reactive solvents may be used alone or in combination of two or more.

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 oxazolidinone ring can be confirmed by IR measurement. When analyzed by total reflection measurement (ATR method), the peak of the stretching vibration of the carbonyl group derived from the oxazolidone ring appeared in 1745 cm ^-1 to 1760 cm ^-1 .

The epoxy equivalent of the oxazolidone ring-containing epoxy resin of the present invention is preferably in a range of 200 g / eq. Or more and 500 g / eq. Or less, and more preferably 250 g / eq. Or more and 400 g / eq. The following range is more preferably a range of 250 g / eq. Or more and 350 g / eq. Or less. If the epoxy equivalent is low, there is a concern that the content of the oxazolidone ring becomes small and the hydroxyl group concentration in the cured product becomes high, so that the dielectric constant becomes high. In addition, if the epoxy equivalent is high, there is a concern that the content of the oxazolidone ring becomes more than necessary, the solvent solubility is deteriorated due to the effect of improving the dielectric properties, or the resin viscosity is increased. Adverse effects increase. In addition, there is a concern that the crosslinked density of the hardened material becomes low, the elastic modulus decreases at the temperature of reflow soldering, and the like, which is a problem in use.

Moreover, when the oxazolidone ring-containing epoxy resin of the present invention is used in a prepreg or a film material, the softening point is preferably 50 ° C to 150 ° C, more preferably 65 ° C to 135 ° C, and even more preferably It is preferably 70 ° C to 110 ° C. If the softening point is low, there is a concern that after impregnating the resin varnish into the glass cloth, the viscosity is low when heating and drying in an oven, so that the amount of resin adhesion is reduced. In addition, if the softening point is high, there is a concern that the resin viscosity becomes high, impregnation in the prepreg deteriorates, solvent solubility deteriorates, and the dilution solvent does not volatilize and remains in the resin during heating and drying. When a laminate is formed, voids and the like are generated, which is 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 hardener. As the hardener, various phenol resins, acid anhydrides, amines, hydrazines, acid polyesters, and the like can be used as the hardener for the epoxy resin. These hardeners can be used alone or in combination of two or more. Among these hardeners, dicyandiamine or a phenol-based hardener is particularly preferred.

In the epoxy resin composition, the amount of the hardener used is 1 mole of the epoxy group of all epoxy resins including the epoxy resin containing an oxazolidone ring, and the active hydrogen group of the hardener is set to The range is from 0.2 mol to 1.5 mol. When the active hydrogen group is less than 0.2 mol or more than 1.5 mol with respect to 1 mol earring oxy group, there is a concern that hardening becomes incomplete and good hardened physical properties are not 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, and a further more preferable range is 0.8 mol or more and 1.2 mol or less. For example, when a phenol-based hardener or an amine-based hardener is used, a substantially equal mole of active hydrogen group is prepared for an epoxy group, and when an acid anhydride-based hardener is used, it is 1 mole of an earring oxy group. An acid anhydride group of 0.5 mol to 1.2 mol, preferably 0.6 mol to 1.0 mol is prepared.

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 potential active hydrogen that generates active hydrogen due to hydrolysis and the like, and a function exhibiting an equivalent hardening effect Group), specifically, an acid anhydride group, a carboxyl group, an amine group, or a phenolic hydroxyl group. Regarding the active hydrogen group, one mole of a carboxyl group or a phenolic hydroxyl group is calculated as one mole, and an amine group (NH ₂ ) is calculated as two moles. If the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, the activity of the hardener used can be determined by reacting a single epoxy resin such as phenyl glycidyl ether with a known epoxy equivalent with a hardener whose active hydrogen equivalent is unknown, and measuring the amount of the single epoxy resin consumed. Hydrogen equivalent.

Specific examples of the phenol resin-based hardener include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, and tetramethyl Bisphenols such as bisphenol S, tetramethyl bisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis (3-methyl-6-third butyl phenol), and the like Catechol, resorcinol, methyl resorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, and monobutadiene Dihydroxybenzenes such as hydroquinone and di-tert-butylhydroquinone; hydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, and trihydroxynaphthalene; Shonol (registered trademark) BRG- 555 (manufactured by Showa Denko Corporation) and other phenol novolac resins, DC-5 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and other cresol novolac resins, Resitop (registered trademark) TPM-100 (Manufactured by Qun Rong Chemical Industry Co., Ltd.), such as trihydroxyphenylmethane novolac resin, naphthol novolac resin and other phenols and / or naphthols and aldehyde condensation products, SN-160, SN-395, S N-485 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and other condensates of phenols and / or naphthols with benzyl alcohol, and condensates of phenols and / or naphthols with isopropenylacetophenone, Reactants of phenols and / or naphthols with dicyclopentadiene, phenol compounds such as condensates of phenols and / or naphthols and biphenyl-based crosslinking agents, and the like.

In this case, phenols include phenol, cresol, xylenol, butylphenol, pentylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, etc., and naphthols include 1-naphthol, 2-naphthol and the like. Examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glutaraldehyde, hexanal, benzaldehyde, chloroaldehyde, bromaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, Pimelic aldehyde, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, o-phthalaldehyde, hydroxybenzaldehyde, etc. Examples of the biphenyl-based crosslinking agent include bis (hydroxymethyl) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, and bis (chloromethyl) biphenyl.

Specific examples of the acid anhydride-based hardener include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, phthalic anhydride, trimellitic anhydride, and methylnadic anhydride Wait.

Specific examples of the amine-based hardener include diethylenetriamine, triethylenetriamine, m-xylylenediamine, isophoronediamine, diaminodiphenylmethane, and diaminodiphenyl. Condensation of hydrazone, diaminodiphenyl ether, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, dicyandiamine, acids such as dimer acids, and polyamines Amine compounds such as polyamidoamine.

Specific examples of other curing agents include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2 -Undecyl imidazole, 1-cyanoethyl-2-methylimidazole and other imidazoles; imidazole salts as salts of imidazole and trimellitic acid, isotricyanic acid, boric acid, etc., trimethyl chloride Quaternary ammonium salts such as ammonium chloride, diazabicyclic compounds, salts of diazabicyclic compounds and phenols or phenol novolac resins, complex compounds of boron trifluoride and amines or ether compounds, Aromatic sulfonium, or iodonium salts.

In addition, 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, if necessary. Specific examples of usable epoxy resins include the bisphenol A epoxy resin, bisphenol F epoxy resin, tetramethylbisphenol F epoxy resin, and hydroquinone epoxy resin. , Biphenyl epoxy resin, Bisphenol fluorene epoxy resin, Bisphenol S epoxy resin, Disulfide epoxy resin, Resorcinol epoxy resin, Biphenylaralkylphenol epoxy Resin, naphthalene-type epoxy resin, phenol novolac-type epoxy resin, styrenated phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, alkyl novolac-type epoxy resin, bisphenol novolac Varnish type epoxy resin, naphthol novolac type epoxy resin, β-naphthol aralkyl type epoxy resin, perinaphthol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, Triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, alkanediol type epoxy resin, aliphatic cyclic epoxy resin, diaminodiphenylmethane tetraglycidylamine, aminophenol Type epoxy resin, phosphorus-containing epoxy resin, urethane modified epoxy resin, epoxy resin containing oxazolidone ring , But not limited to these epoxy resins. These epoxy resins may be used alone or in combination of two or more.

If necessary, a hardening accelerator may be used in the epoxy resin composition. Examples of usable hardening accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1 Tertiary amines such as 8-diaza-bicyclo [5.4.0] undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphine and triphenylborane, tin octoate, etc. Metal compounds. A hardening accelerator may be used in an amount of 0.02 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 as needed. By using a hardening accelerator, the hardening temperature can be reduced or the hardening time can be shortened.

An organic solvent for viscosity adjustment may also be used in the epoxy resin composition. The organic solvent that can be used is not particularly limited, and examples thereof include ammoniums such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, methanol, Alcohols such as ethanol, and aromatic hydrocarbons such as benzene and toluene can be prepared by mixing one or more of these solvents in an epoxy resin concentration range of 20% to 90% by mass.

If necessary, a diluent is 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 glycidyl ethers such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether, resorcinol glycidyl ether, and neopentyl glycol glycidyl ether. Polyfunctional glycidyl ethers such as 1,6-hexanediol diglycidyl ether, polyfunctional glycidyl ethers such as glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether . Examples of the non-reactive diluent include benzyl alcohol, butyl diglycol, and pine oil.

The epoxy resin composition can be blended with other thermosetting resins and thermoplastic resins within a range that does not impair the characteristics. Examples include phenol resin, acrylic resin, petroleum resin, indene resin, benzofuran-indene resin, phenoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, and polyimide resin. Fluorene amine imine resin, polyether amine imine resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether fluorene resin, polyfluorene resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formaldehyde Resins and the like are not limited to these resins.

In the epoxy resin composition, in order to improve the flame retardancy of the obtained cured product, various known flame retardants can be used. Examples of usable flame retardants include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. From the viewpoint of environment, a halogen-free flame retardant is preferred, and a phosphorus-based flame retardant is particularly preferred. These flame retardants may be used alone or in combination of two or more.

As the phosphorus-based flame retardant, any of an inorganic phosphorus-based compound and an organic phosphorus-based compound can be used. Examples of the inorganic phosphorus-based 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 phosphatidamine. Examples of the organic phosphorus-based compound include general-purpose organic phosphorus-based compounds such as aliphatic phosphates, phosphate compounds, condensed phosphates, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, orthophosphine compounds, and organic nitrogen-containing phosphorus compounds. Or metal salts of phosphinic acid, other than 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -10H Cyclic organic phosphorus such as -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide A compound, or a phosphorus-containing epoxy resin or a phosphorus-containing hardener, which is a derivative obtained by reacting these compounds with a compound such as an epoxy resin or a phenol resin.

The blending amount of the flame retardant can be appropriately selected depending on the type of the phosphorus-based flame retardant, the components of the epoxy resin composition, and the degree of desired flame retardancy. For example, the phosphorus content in organic components (excluding organic solvents) in the epoxy resin composition is preferably 0.2% by mass or more and 4% by mass or less, more preferably 0.4% by mass or more and 3.5% by mass or less, and still more preferably 0.6. Above mass% and below 3 mass%. If the phosphorus content is small, there is a concern that it becomes difficult to ensure flame retardancy; if the phosphorus content is too large, there is a concern that heat resistance may be adversely affected. When a phosphorus-based flame retardant is used, a flame retardant auxiliary such as magnesium hydroxide may be used in combination.

A filler may be used in the epoxy resin composition as necessary. 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, aluminosilicate fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aromatic polyamide fiber, ceramic Fiber, micro rubber, thermoplastic elastomer, pigment, etc. The reason for generally using a filler includes the effect of improving impact resistance. Moreover, when metal hydroxides, such as aluminum hydroxide, boehmite, and magnesium hydroxide, are used, it has the effect which functions as a flame retardant adjuvant, and improves flame retardance. 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 entire epoxy resin composition. When there are many formulation amounts, there exists a possibility that the adhesiveness required for the use of a laminated board may fall, and there exists a possibility that a hardened | cured material may become brittle and sufficient mechanical physical property may not be obtained. In addition, if the blending amount is small, there is a concern that the impact resistance of the cured product is improved, etc., and this is not the blending effect of the filler.

When the epoxy resin composition is made into a plate-like substrate or the like, fibrous fillers can be cited as preferable fillers in terms of dimensional stability, bending strength, and the like. More preferably, a glass fiber substrate obtained by knitting glass fibers into a mesh shape is used.

The epoxy resin composition may further be formulated with various additives such as a silane coupling agent, an antioxidant, a mold release agent, a defoaming agent, an emulsifier, a thixotropy imparting agent, a lubricant, a flame retardant, and a pigment. These additives are preferably in a range of 0.01 to 20% by mass based on the epoxy resin composition.

A prepreg used in a printed wiring board or the like can be prepared by impregnating an epoxy resin composition with a fibrous substrate. As the fibrous substrate, woven or non-woven fabrics of inorganic fibers such as glass, or polyester resins, polyamine resins, polyacrylic resins, polyimide resins, and aromatic polyimide resins can be used. Limited to this. The method for producing a prepreg from an epoxy resin composition is not particularly limited. For example, the resin is impregnated with a resin varnish prepared by adjusting the viscosity of the epoxy resin composition with a solvent, and is then dried by heating to dry the resin. The prepreg obtained by semi-hardening the components (B-staged) can be heated and dried at, for example, 100 ° C to 200 ° C for 1 minute to 40 minutes. Here, the amount of the resin in the prepreg is preferably set to a resin content of 30% to 80% by mass.

Moreover, when hardening a prepreg, the hardening method of the laminated board generally used at the time of manufacture of a printed wiring board can be used, It is not limited to this. For example, when a prepreg is used to form a laminate, one or more prepregs are laminated, metal foils are arranged on one or both sides to form a laminate, and the laminate is heated and heated. Laminate and integrate. Here, as the metal foil, a single, alloy, or composite metal foil such as copper, aluminum, brass, or nickel can be used. Second, the prepreg can be hardened by applying pressure and heating to the produced laminate to obtain a laminate. In this case, it is preferable to obtain a target by setting the heating temperature to 160 ° C to 220 ° C, the pressing pressure to 50 N / cm ² to 500 N / cm ² , and the heating and pressing time to 40 minutes to 240 minutes. Hardened. If the heating temperature is low, there is a concern that the curing reaction does not proceed sufficiently; if the heating temperature is high, there is a concern that the epoxy resin composition starts to decompose. In addition, if the pressing pressure is low, bubbles may remain in the obtained laminate and the electrical characteristics may be reduced. If the pressing pressure is high, there is a concern that the resin flows before hardening and the desired thickness cannot be obtained. Hardened. In addition, if the heating and pressing time is short, there is a concern that the curing reaction cannot be sufficiently performed; if the heating and pressing time is long, there is a concern that the epoxy resin composition in the prepreg may be thermally decomposed, which is not preferable.

An epoxy resin hardened | cured material can be obtained by hardening an epoxy resin composition by the same method as a well-known epoxy resin composition. The method for obtaining a cured product can be the same as that of a known epoxy resin composition, and casting, injection, pouring, dipping, drip coating, transfer molding, compression molding, etc., or a resin sheet can be suitably used. Resin-coated copper foil, prepreg, and the like are laminated and heated and pressure-cured to form a laminate. The curing temperature at this time is usually in the range of 100 ° C to 300 ° C, and the curing time is usually about 1 hour to 5 hours.

The hardened epoxy resin of the present invention can be in the form of a laminate, a molded product, an adhesive, a coating film, or a film.

An epoxy resin composition was prepared, and the cured epoxy resin of the laminate was evaluated by heat curing. As a result, the epoxy resin (a) and the isocyanate compound (b) reacted and the oxazolidone ring-containing epoxy resin and Compared with the conventionally known oxazolidone ring-containing epoxy resins, not only has low viscosity and good workability, but also has high heat resistance and high adhesion, and also has improved low dielectric properties. [Example]

The present invention will be specifically described with examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means mass parts, and "%" means mass%. The measurement methods can be measured by the following methods, respectively. Epoxy equivalent: According to JISK7236. Viscosity: According to JISK7233 standard, single cylinder rotating viscometer method. Softening point: Measured in accordance with JISK7234 standard and ring and ball method. Specifically, an automatic softening point device (manufactured by Mintec Corporation, ASP-MG4) was used.

Binuclear content rate, trinuclear content rate, tetranuclear content rate, pentanuclear content rate, number average molecular weight (Mn), weight average molecular weight (Mw), and dispersion (Mw / Mn): GPC The molecular weight distribution is measured, and the dinucleotide content rate, trinuclear content rate, tetranuclear content rate, and pentanuclear content rate are determined based on the area percentage of the peak. The number-average molecular weight, weight-average molecular weight, and dispersion degree are based on utilization. Standard monodisperse polystyrene (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). Specifically, a device including a column (manufactured by Tosoh Corporation, TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL) in series in a body (manufactured by Tosoh Corporation, HLC-8220GPC) was used, and the column temperature was set to 40 ° C. In addition, THF was used as the eluent, and a flow rate of 1 mL / min was used, and an RI (differential refractometer) detector was used as the detector. The data was processed using GPC-8020 Model II version 4.10 manufactured by Tosoh Corporation. A 100 μL sample was used as a measurement sample, and the sample was a sample obtained by dissolving a 0.1 g sample in 10 mL of THF and filtering the sample with a microfilter.

Copper foil peeling strength and layer indirect force: It is measured in accordance with JISC6481, and the layer indirect force is measured by peeling between the seventh layer and the eighth layer.

Glass transition temperature (differential scanning calorimetry (DSC) method): In accordance with IPC-TM-6502.4.25.c, a differential scanning calorimeter (manufactured by Hitachi High-tech Co., Ltd., EXSTAR6000DSC6200) is used at 20 ° C. The temperature of DSC · Tgm (the middle temperature of the variation curve with respect to the tangent between the glass state and the rubber state) when measured under a temperature rising condition per minute.

Glass transition temperature (Thermomechanical analysis (TMA) method): According to IPC-TM-6502.4.24.1, use a thermomechanical analysis device (manufactured by Hitachi High-tech Co., Ltd., EXSTAR6000TMA / SS120U) at 10 ° C / min The temperature of the TMA extrapolated value when the measurement is performed under a temperature rising condition is shown.

Relative permittivity and tangent of dielectric loss: According to IPC-TM-6502.5.5.9, a material analyzer (manufactured by Agilent Technologies) was used to obtain the relative permittivity and permittivity at a frequency of 1 GHz using a capacitance method The loss tangent was evaluated from this.

Flame retardancy: According to UL94 (Underwriters Laboratories Inc. safety certification standard), the vertical method is used for evaluation.

IR: Total reflection measurement method (Attenuated Total Reflection (ATR) method) using a Fourier transform infrared spectrophotometer (PerkinElmer Precisely, Spectrum One FT-IR Spectrometer 1760X) ) And the absorbance at a wave number of 650 cm ^-1 to 4000 cm ^-1 was measured. Synthesis example 1 (synthesis of phenol novolac resin)

A separable flask made of glass was charged with 2500 parts of phenol and 7.5 parts of oxalic acid dihydrate, stirred while injecting nitrogen, and heated to raise the temperature. Next, while stirring at 80 ° C, 474.1 parts of 37.4% formalin was added dropwise over 30 minutes to cause a reaction. The reaction was further carried out for 3 hours while maintaining the reaction temperature at 92 ° C. The temperature was raised to 110 ° C while the water produced by the reaction was removed from the system. The remaining 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 body to obtain a phenol novolac resin. The content of dinuclear bodies and trinuclear bodies of the obtained phenol novolak resin were measured by GPC, and were 10 area% and 38 area%, respectively. Synthesis example 2 (synthesis of phenol novolac epoxy resin)

666 parts of the phenol novolak resin obtained in Synthesis Example 1, 2110 parts of epichlorohydrin, and 17 parts of ion-exchanged water were charged into the same device as Synthesis Example 1, and the temperature was raised to 50 ° C while stirring. After uniformly dissolving, 14.2 parts of a 49% aqueous sodium hydroxide solution was charged and reacted for 3 hours. Next, the temperature was raised to 64 ° C, and the pressure was reduced to the extent that water refluxed. 457.7 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours. During the dropwise addition, the distilled water and epichlorohydrin were separated by reflux in a separation tank. The epichlorohydrin was returned to the reaction vessel, and water was removed from the system to perform the reaction. After completion of the reaction, the temperature was raised to 70 ° C to perform dehydration, and the remaining epichlorohydrin was recovered by setting the temperature to 135 ° C. The pressure was returned to normal pressure, and 1232 parts of methyl isobutyl ketone (MIBK) was added to dissolve. 1200 parts of ion-exchanged water was added, and the mixture was allowed to stand still to dissolve by-product salt in water to remove it. Next, 37.4 parts of a 49% aqueous sodium hydroxide solution was charged, and the reaction was stirred at 80 ° C. for 90 minutes to perform a purification reaction. MIBK was added and washed several times to remove ionic impurities. The solvent was recovered to obtain a phenol novolac epoxy resin. The obtained phenol novolak-type epoxy resin had a content of 10 cores in a dinuclear body, a content of 3 cores in a hard core, and a total content of the cores in a tri- and tetra-core was 52 area%. The content rate above the core was 38 area%, the number average molecular weight was 635, the weight average molecular weight was 884, the degree of dispersion was 1.39, and the epoxy equivalent was 174 g / eq.

The GPC measurement chart is shown in FIG. 1. In the figure, the peak indicated by A indicates a dinuclear body, the peak indicated by B indicates a trinuclear body, and the peak group indicated by C indicates a pentanuclear body or more. The horizontal axis represents the dissolution time, the left vertical axis represents the signal intensity, and the right vertical axis represents the number-average molecular weight M by a common logarithm (log). The measurement value of the number average molecular weight of the standard substance used was plotted with a black dot as a calibration curve. Synthesis example 3 (synthesis of hybrid epoxy resin)

90 parts of the phenol novolac-type epoxy resin obtained in Synthesis Example 2 and 10 parts of the bisphenol F-type liquid epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Epotohto YDF-1500, epoxy equivalent is 168 g / eq., Viscosity is 2500 mPa · s), while stirring, the temperature is raised to 50 ° C, and it is uniformly dissolved to make a mixed epoxy resin. The molecular weight distribution of the obtained mixed-type epoxy resin was measured. As a result, the content of the dinuclear body was 18 area%, the content of the trinuclear body was 32 area%, and the total content of the trinuclear body and the tetranuclear body was total. It was 48 area%, the content rate of the pentanuclear body or more was 34 area%, the number average molecular weight was 597, the weight average molecular weight was 824, the dispersion degree was 1.38, and the epoxy equivalent was 173 g / eq. Explanations of abbreviations used in the examples and comparative examples are as follows. (Epoxy resin)

Epoxy resin A: phenol novolac epoxy resin obtained in Synthesis Example 2 epoxy resin B: mixed type epoxy resin epoxy resin obtained in Synthesis Example 3 C: general-purpose phenol novolac epoxy resin ( Manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Epotohto YDPN-638, the content rate of the dinuclear body is 22 area%, the content rate of the trinuclear body is 15 area%, The total content rate is 25 area%, the content rate of the pentanuclear body or more is 53 area%, the number average molecular weight is 528, the weight average molecular weight is 1127, the dispersion degree is 2.13, and the epoxy equivalent is 176 g / eq. The measurement chart is shown in Figure 2. A, B, and C are the same as those described in Figure 1.) Epoxy resin D: Bisphenol A liquid epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Epotohto ) YD-8125, epoxy equivalent is 174 g / eq., Viscosity is 4100 mPa · s) Epoxy resin E: o-cresol novolac epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Aibaotao (Epotohto) YDCN-703, epoxy equivalent is 202 g / eq.) Epoxy resin F: Phosphorous epoxy resin Grease (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Epotohto TX-1320A, epoxy equivalent 763 g / eq., Phosphorus content 5.0%) (isocyanate)

Isocyanate A: Diphenylmethane diisocyanate (manufactured by Mitsui Chemicals Co., Ltd., Cosmonate PH, NCO concentration: 34%) Isocyanate B: polymethylene polyphenyl polyisocyanate (Mitsui Chemical Co., Ltd. Manufacture, Cosmonate M-50, NCO concentration 34%) Isocyanate C: A mixture of 2,4-toluene diisocyanate (80%) and 2,6-toluene diisocyanate (20%) (Mitsui Manufactured by Chemical Co., Ltd., Cosmonate T-80, NCO concentration is 48%) Isocyanate D: Cyclohexane-1,3-diylbismethylene diisocyanate (Mitsui Chemical Co., Ltd. , Takenate 600, NCO concentration is 43%) (catalyst)

Catalyst A: Tetramethylammonium iodide (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) Catalyst B: n-butyltriphenylphosphonium bromide (manufactured by Japan Chemical Industry Co., Ltd., HISHICOLIN) (registered Trademark) BTPPBr) (hardener)

PN: phenol novolac resin (manufactured by Showa Denko Corporation, Shonol BRG-557, softening point: 80 ° C) DICY: dicyandiamine (manufactured by Japan's Denshi Corporation) (hardening accelerator)

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

PX-200: Aromatic Condensed Phosphate (manufactured by Daba Chemical Industry Co., Ltd., PX-200, phosphorus content is 9.0%) Example 1

In the same apparatus as in Synthesis Example 1, 100 parts of epoxy resin A as epoxy resin (a) and 0.17 parts of catalyst A were charged, and the temperature was raised while nitrogen was introduced, and the system was maintained at 120 ° C for 30 minutes to set the system. The moisture inside is removed. Next, while maintaining a temperature of 130 ° C to 140 ° C, 14.4 parts of isocyanate A as an isocyanate compound (b) (equivalent ratio of isocyanate group b / epoxy group [[b] / (a)] = 0.20) A 50% toluene solution was added, and the solution was added dropwise over 3 hours. After the dropwise addition was completed, stirring was continued for 60 minutes while maintaining the same temperature. After completion of the reaction, the solvent was removed under a recovery condition of 150 ° C., 1.33 kPa, and 30 minutes to obtain an oxazolidone ring-containing epoxy resin (resin 1). About the obtained resin 1, the epoxy equivalent and softening point were measured. The measurement results are shown in Table 1. A GPC chart is shown in FIG. 3, and an IR chart is shown in FIG. 4. Example 2 to Example 7

An epoxy resin containing an oxazolidone ring was synthesized by the same operation using the same device as in Example 1 in accordance with the amount (parts) of each raw material shown in Table 1. The epoxy equivalent and softening point of the resin obtained in the same manner as in Example 1 were measured, and the measurement results are shown in Table 1. In addition, as the dropping time of the isocyanate of Example 2, Example 4, Example 6, and Example 7, since the dropping acceleration was set to be substantially the same as that of Example 1, it was changed from 3 hours to 6 hours. The oxazolidone ring-containing epoxy resins obtained in Examples 2 to 7 were used as resins 2 to 7. Comparative Example 1 to Comparative Example 7

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 amount (parts) of each raw material shown in Table 2. The epoxy equivalent and softening point of the comparative resin obtained in the same manner as in Example 1 were measured, and the measurement results are shown in Table 2. In addition, as the dripping time of the isocyanate of Comparative Example 4, since the dripping acceleration was made substantially the same as that of Example 1, it changed from 3 hours to 6 hours. Further, 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 used as Comparative resin 2 to Comparative resin 5.

The "equivalent ratio [(b) / (a)]" in Tables 1 and 2 represents the equivalent ratio of the isocyanate group of the isocyanate compound (b) to the one equivalent epoxy group of the epoxy resin (a), and "-" Indicates that it is not used, and "×" indicates that it cannot be measured.

[Table 1]

[Table 2] Example 8

100 parts of the resin obtained in Example 1 and 41.0 parts of PN as a hardener and 0.01 part of 2E4MZ as a hardening accelerator were prepared and dissolved in MEK, propylene glycol monomethyl ether, N, N-dimethylformamidine An epoxy resin composition varnish was obtained in a mixed solvent prepared from an amine.

The obtained epoxy resin composition varnish was impregnated into glass cloth (manufactured by Nitto Textile Co., Ltd., WEA 7628 XS13, 0.18 mm thick). The impregnated glass cloth was dried in a hot air circulation oven at 150 ° C. for 11 minutes to obtain a prepreg. 8 pieces of the obtained prepreg were laminated on top and bottom of copper foil (manufactured by Mitsui Metals Mining Co., Ltd., 3EC-III, thickness: 35 μm), and the temperature was 130 ° C × 15 minutes + 190 ° C × 80 minutes for 2 Vacuum compression of MPa yields a 1.6 mm thick laminate. Table 3 shows the results of the copper foil peel strength of the laminate, the layer indirect stress, the glass transition temperature DSC (Tg · DSC), and the glass transition temperature TMA (Tg · TMA).

Then, the obtained prepreg was unraveled, and a sieve was passed through a 100-mesh powdery prepreg powder. The obtained prepreg powder was put into a fluororesin mold, and vacuum-pressed at 2 MPa under a temperature condition of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes to obtain a test piece of 50 mm square × 2 mm thickness . Table 3 shows the results of the relative dielectric constant and dielectric loss tangent of the test piece. Example 9 to Example 17

The resins 1 to 7, PN, DICY, and 2E4MZ obtained in Example 1 to Example 7 were prepared at the compounding amount (parts) in Table 3, and the same operation was performed using the same device as in Example 8 to obtain a laminate. And test strips. The same experiment as in Example 8 was performed, and the results are shown in Table 3. In addition, "-" in the table indicates not used. Comparative Example 8 to Comparative Example 14

The comparative resin 2 to comparative resin 5, epoxy resin E, PN, DICY, and 2E4MZ obtained in Comparative Example 2 to Comparative Example 5 were blended in the blending amount (parts) in Table 4 using the same device as in Example 8. In the same manner, a laminate and a test piece were obtained. The same experiment as in Example 8 was performed, and the results are shown in Table 4. In addition, "-" in the table indicates not used.

[table 3]

[Table 4] 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 prepared at the formulation amount (parts) of Table 5 using the same device as in Example 8, A laminate and a test piece were obtained in the same manner. The same experiment as in Example 8 was performed, and the results are shown in Table 5. The test piece for measuring the flame retardancy is obtained by etching both sides of the laminate. In addition, "-" in the table indicates not used.

[table 5]

From these results, it can be seen that the oxazolidone ring-containing epoxy resin and its composition of the examples not only have low viscosity and good workability, but also have high heat resistance and high adhesion, and also have dielectric properties. Improved. [Industrial availability]

The oxazolidone ring-containing epoxy resin of the present invention, its composition, and hardened material are excellent in heat resistance, adhesion, and dielectric properties, and can be used for various electronic circuit board materials, etc., which are compatible with current high-performance requirements. Epoxy resin for high-performance materials.

no

FIG. 1 shows a GPC chart of a phenol novolak epoxy resin of Synthesis Example 2. FIG. FIG. 2 shows a GPC chart of a general-purpose phenol novolak epoxy resin YDPN-638. 3 is a GPC chart of an oxazolidone ring-containing epoxy resin of Example 1. FIG. FIG. 4 shows an IR chart of an oxazolidone ring-containing epoxy resin of Example 1. FIG.

Claims (13)

An oxazolidone ring-containing epoxy resin is an oxazolidone ring-containing epoxy resin obtained from an epoxy resin (a) and an isocyanate compound (b), wherein the epoxy resin ( a) In the measurement of gel permeation chromatography, the content of dinuclear bodies is 20 area% or less, the content of trinuclear bodies is 15 area% or more and 60 area% or less. The total content ratio is 15 area% or more and 85 area% or less, the content ratio of pentanuclear body or more is 45 area% or less, and the number average molecular weight is 350 or more and novolac-type epoxy resin; The 1 mol earring oxy group of the oxyresin (a) uses an isocyanate group of the isocyanate compound (b) in a range of 0.02 mol to 0.6 mol. The oxazolidone ring-containing epoxy resin according to item 1 of the scope of the patent application, wherein the novolak epoxy resin is an epoxy resin represented by the following formula (1); In the formula (1), Ar is an aromatic group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic groups may further have an alkyl group having 1 to 6 carbon atoms substituted for the aromatic ring; X represents A divalent aliphatic cyclic hydrocarbon group or a cross-linking group represented by the following formula (1a) or the following formula (1b), G represents a glycidyl group; m represents 1 or 2, and n is a repeating unit and represents 0 or more Integer In formula (1a) and formula (1b), 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 selected from a benzene ring, a biphenyl ring, or a naphthalene ring. Aromatic groups, and these aromatic groups may further have an alkyl group having 1 to 6 carbon atoms in which an aromatic ring is substituted. The oxazolidone ring-containing epoxy resin according to item 1 or item 2 of the scope of patent application, wherein the isocyanate compound (b) has an average of 1.8 or more isocyanate groups in the molecule. The epoxy equivalent of the oxazolidone ring-containing epoxy resin according to item 1 or item 2 of the scope of the patent application has an epoxy equivalent of 200 g / eq. To 500 g / eq. The softening point of the epoxy resin containing an oxazolidone ring according to item 1 or item 2 of the scope of application for a patent is 50 ° C to 150 ° C. A method for manufacturing an oxazolidone ring-containing epoxy resin, which is the method for manufacturing an oxazolidone ring-containing epoxy resin as described in item 1 of the scope of patent application, characterized in that: a) Reaction with isocyanate compound (b); The epoxy resin (a) has a dinuclear content rate of 20 area% or less and a trinuclear content rate of 15 areas in a gel permeation chromatography measurement. % Or more and 60 area% or less, the total content of the tri- and tetra-nuclear bodies is 15 area% or more and 85 area% or less, and the content ratio of the penta-core body or more is 45 area% or less. The number average molecular weight Novolac-type epoxy resin having a molecular weight distribution of 350 or more and 700 or less; the above-mentioned epoxy resin (a) is used in a range of 0.02 mol or more and 0.6 mol or less relative to 1 mol earring oxy group of the epoxy resin (a). The isocyanate group of the isocyanate compound (b). The method for producing an oxazolidone ring-containing epoxy resin according to item 6 of the scope of application for a patent, wherein the novolak-type epoxy resin is an epoxy resin represented by the following formula (1); In the formula (1), Ar is an aromatic group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic groups may further have an alkyl group having 1 to 6 carbon atoms substituted for the aromatic ring; X represents A divalent aliphatic cyclic hydrocarbon group or a cross-linking group represented by the following formula (1a) or the following formula (1b), G represents a glycidyl group; m represents 1 or 2, and n is a repeating unit and represents 0 or more Integer In formula (1a) and formula (1b), 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 including a benzene ring, a biphenyl ring, or a naphthalene ring. These aromatic groups may further have an alkyl group having 1 to 6 carbon atoms in which an aromatic ring is substituted. Contains oxazolidinone as described in item 6 or 7 of the scope of patent application The method for producing a cyclic epoxy resin, wherein the isocyanate compound (b) has an average of 1.8 or more isocyanate groups in the molecule. An epoxy resin composition, characterized in that the oxazolidone ring-containing epoxy resin and the hardener as described in any one of claims 1 to 5 of the scope of patent application are essential components, and The active hydrogen group of the hardener is prepared in the range of 0.2 mol to 1.5 mol of 1 molar oxygen of the epoxy resin. A hardened epoxy resin is obtained by hardening the epoxy resin composition according to item 9 of the scope of patent application. A prepreg using an epoxy resin composition as described in item 9 of the patent application scope. A laminate using an epoxy resin composition as described in item 9 of the scope of patent application. A printed circuit board obtained by using the epoxy resin composition described in item 9 of the scope of patent application.