KR102375986B1 - Oxazolidone ring-containing epoxy resin, method for producing the thereof, epoxy resin composition and cured product - Google Patents

Abstract

(식 중, X 는 탄소수 1 ∼ 4 의 알킬기, 탄소수 6 ∼ 10 의 아릴기 및 탄소수 6 ∼ 10 의 아르알킬기에서 선택되는 치환기를 적어도 1 개 갖는 고리 원자수 5 ∼ 8 의 시클로알킬리덴기를 나타낸다. R 은 각각 독립적으로 수소 원자, 탄소수 1 ∼ 8 의 알킬기, 탄소수 5 ∼ 8 의 시클로알킬기, 탄소수 6 ∼ 10 의 아릴기 또는 탄소수 6 ∼ 10 의 아르알킬기를 나타내고, G 는 글리시딜기를 나타낸다. m 은 반복을 나타내고, 평균값은 0 ∼ 5 이다.)(Project) To provide an epoxy resin excellent in heat resistance, dielectric properties, adhesive properties, and the like.
(Solution) The epoxy equivalent obtained from the epoxy resin (a) and the isocyanate compound (b) containing 50 mass % or more of the epoxy resin (a1) represented by following formula (1) 200-550 g/eq. Epoxy resin containing phosphorus oxazolidone ring.

(Wherein, X represents a cycloalkylidene group having 5 to 8 ring atoms 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 each independently represents 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 is a glycidyl group. represents repetition, and the average value is 0 to 5.)

Description

Oxazolidone ring-containing epoxy resin, its manufacturing method, epoxy resin composition, and cured product TECHNICAL FIELD

The present invention provides an oxazolidone ring-containing epoxy resin that gives a cured product excellent in low dielectric properties, high heat resistance, high adhesion, etc., a method for producing the epoxy resin, an epoxy resin composition comprising the epoxy resin as an essential component, and It is related with the epoxy resin hardened|cured material obtained from this epoxy resin composition, a prepreg, and an epoxy resin laminated board.

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

BACKGROUND ART In the recent years, with the rapid increase in the amount of information, a high-functionalization request is always required for portable devices, which are one of the uses of printed wiring boards, and infrastructure devices such as base stations to connect them. In portable devices, high multilayering and fine wiring are progressing for the purpose of miniaturization. In order to make the substrate thinner, a material with a lower dielectric constant is required, and since the adhesive surface is reduced by fine wiring, a more highly adhesive material is is being demanded In base station substrates, in order to suppress attenuation of signals due to high frequency, a material with a lower dielectric loss tangent is required.

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

Regarding the low dielectric constant of the epoxy resin, Patent Document 1 discloses 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[2,6-dimethyl]phenol diglycidyl Etherides are disclosed. Moreover, in patent document 2, alcoholic hydroxyl group equivalent is 1000 g/eq. An epoxy resin obtained by reacting the above (1.0 meq/g or less) epoxy resin with an isocyanate compound having two or more isocyanate groups in the molecule is disclosed, and the epoxy resin polymerized by an oxazolidone ring has a low dielectric constant, low dielectric constant It is tangent, and it is disclosed that a glass transition temperature is also high.

Patent Document 3 also discloses an oxazolidone ring-containing epoxy resin by reaction of an epoxy resin and an isocyanate, and as a raw material epoxy resin, a compound obtained by glycidylating dihydric phenols such as bisphenol A, tris(glycidyloxy) Examples of compounds obtained by glycidylation of phenyl) alkanes, aminophenols, and the like, and compounds obtained by glycidylation of novolacs such as phenol novolac are exemplified. However, neither the epoxy resins disclosed in any of the literatures satisfactorily satisfies the requirements for dielectric properties based on recent high functionalization, and the adhesiveness was also insufficient.

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

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

In order to solve the above problems, the present inventors have intensively studied low-dielectric constant and low-dielectric dissipation tangent materials. Among epoxy resins, oxazolidone ring-containing epoxy resins obtained by reacting an epoxy resin of the following formula (1) with an isocyanate compound are The present invention was completed by discovering that a conventional low dielectric constant, a low dielectric loss tangent and a high glass transition temperature were compatible, and the adhesive force was also good.

That is, in this invention, the epoxy equivalent obtained from the epoxy resin (a) and the isocyanate compound (b) containing 50 mass % or more of the epoxy resin (a1) represented by following formula (1) 200-550 g/eq. It is an epoxy resin containing phosphorus oxazolidone ring.

[Formula 1]

(Wherein, X represents a cycloalkylidene group having 5 to 8 ring atoms 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 each independently represents 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 is a glycidyl group. represents repetition, and the average value is 0 to 5.)

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

The said epoxy resin (a) is an epoxy resin other than the said epoxy resin (a1), Comprising: An alcoholic hydroxyl group equivalent is 1000 g/eq. It is preferable to contain the above epoxy resin (a2) in 50 mass % or less. Moreover, the epoxy equivalent of an epoxy resin (a) is 100-500 g/eq. It is preferable to be

The isocyanate compound (b) preferably has an average of 1.8 or more isocyanate groups in the molecule, tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate, It is more preferable that it is 1 or more types chosen from trimethyl hexamethylene diisocyanate and isophorone diisocyanate.

The oxazolidone ring-containing epoxy resin has, in the analysis by infrared absorption spectrum, the maximum value of the peak contained in 1745 to 1760 cm ^-1 derived from stretching vibration of the carbonyl group of the oxazolidone ring absorbance Ox, urethane bond structure When the absorbance Ur is the maximum value of the peak included in 1730-1740 cm ^-1 derived from the stretching vibration peak of the carbonyl group, the absorbance ratio Ox/Ur is preferably 1.35 or more.

It is preferable that the softening point of the said oxazolidone ring containing epoxy resin is 50-150 degreeC.

Moreover, in this invention, the epoxy resin (a) containing 50 mass % or more of the epoxy resin (a1) represented by said Formula (1), and an isocyanate compound (b) in catalyst presence, reaction temperature 100 degreeC or more and 250 degrees C or less It is a method for producing an oxazolidone ring-containing epoxy resin, characterized in that it is reacted in the range of

The isocyanate compound (b) preferably has an average of 1.8 or more isocyanate groups in the molecule, tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate, It is more preferable that it is 1 or more types chosen from trimethyl hexamethylene diisocyanate and isophorone diisocyanate. Moreover, it is preferable that the said catalyst is a basic catalyst.

With respect to 1 mol of the epoxy group of the epoxy resin (a), the isocyanate group of the isocyanate compound (b) is preferably in the range of 0.02 mol or more and less than 0.5 mol, more preferably 0.05 mol or more and 0.48 mol or less, 0.1 It is more preferable that it is in the range of more than mol and not more than 0.45 mol.

Moreover, this invention is an epoxy resin composition containing the said oxazolidone ring containing epoxy resin and a hardening|curing agent as essential.

It is preferable that the active hydrogen group of the said hardening|curing agent is 0.2-1.5 mol with respect to 1 mol of the epoxy groups of all the epoxy resins containing the said oxazolidone ring containing epoxy resin in the said epoxy resin composition.

Moreover, this invention is the epoxy resin hardened|cured material formed by hardening|curing the said epoxy resin composition. Moreover, this invention uses the said epoxy resin composition, The prepreg and epoxy resin laminated board characterized by the above-mentioned.

The epoxy resin of the present invention, a resin composition containing the same, and a cured product thereof exhibit physical properties of a cured product having a high glass transition temperature while maintaining adhesive strength. In addition, this cured epoxy resin product is excellent in dielectric properties and exhibits favorable properties in epoxy resin laminates requiring low dielectric constant and low dielectric loss tangent.

1 is a GPC chart of Resin 1 obtained in Example 1. 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.

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

The epoxy resin (a) used in order to obtain the oxazolidone ring containing epoxy resin of this invention contains the epoxy resin (a1) represented by Formula (1), Preferably it contains 50 mass % or more.

The said epoxy resin (a) can contain less than 50 mass % of other epoxy resins (a2) other than an epoxy resin (a1). The epoxy resin (a2) has an alcoholic hydroxyl equivalent of 1000 g/eq. The above is preferable, and the epoxy equivalent of an epoxy resin (a2) is 100-500 g/eq. is preferable

In formula (1), R each independently represents a hydrogen atom, a C1-C8 hydrocarbon group, a C5-C8 cycloalkyl group, a C6-C10 aryl group, or a C6-C10 aralkyl group. For example, as a C1-C8 hydrocarbon group, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, tert-butyl group, hexyl group, etc. are mentioned, A C5-C8 cycloalkyl group is a cyclohexyl group, and the aryl group or aralkyl group having 6 to 10 carbon atoms includes, but is not limited to, a phenyl group, a benzyl group, a phenethyl group, a 1-phenylethyl group, and a naphthyl group. , may be the same as or different from each other. Preferred R is a hydrogen atom, a 1-phenylethyl group, or a methyl group from the viewpoint of physical properties such as ease of availability and heat resistance when a cured product is used.

In Formula (1), although any of an ortho position and a meta position may be sufficient as the substitution position of R with respect to the carbon atom couple|bonded with X, an ortho position is preferable.

In the formula (1), X represents a cycloalkylidene group having 5 to 8 ring atoms 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 these cycloalkylidene groups is any of a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or a cyclooctane ring, and a cyclopentane ring or a cyclohexane ring is preferable.

Moreover, the substituent couple|bonded with a cycloalkane ring is a C1-C4 alkyl group, a C6-C10 aryl group, or a C6-C10 aralkyl group, and it needs to be substituted by at least one. For example, as a C1-C4 alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, etc. are mentioned, C6 Although phenyl group, a benzyl group, a tolyl group, o-xylyl group etc. are mentioned as -10 aryl group or aralkyl group, It is not limited to these, When there exists a plurality, each may be same or different. Preferable substituents are a methyl group and a phenyl group from the viewpoints of physical properties such as ease of availability and adhesiveness in a laminate.

Further, the cycloalkylidene group is a 1,1-cycloalkylidene group, and the substituent is a benzene ring bonded to the 1-position carbon of the cycloalkylidene group or the cycloalkane ring mobility due to a steric repulsion action between the substituents. It aims to improve dielectric properties by limiting and to improve heat resistance at the same time. The substitution position may be bonded anywhere as long as it is a position capable of restricting mobility, but bonding to a carbon atom close to the 1-position of the cycloalkylidene group is preferable. A preferred position of the substituent is a carbon atom at the 2-position or 5-position in the cyclopentane ring. In a cyclohexane ring, it is a 2-position, 3-position, 5-position, or 6-position carbon atom, More preferably, it is a 2-position or 6-position carbon atom. In a cycloheptane ring, it is a 2-position, 3-position, 6-position, or 7-position carbon atom, More preferably, it is a 2-position or 7-position carbon atom. In the cyclooctane ring, it is a carbon atom at the 2nd, 3rd, 4th, 6th, 7th or 8th position, more preferably a carbon atom at the 2nd, 3rd, 7th or 8th position, still more preferably is a carbon atom in the 2-position or 8-position. However, there are cases in which it is difficult to substitute the carbon atom closest to the 1-position due to the influence of steric hindrance with the adjacent benzene ring, and in that case, it is suitable for the substituent to be bonded to the next closest carbon atom. For example, in the cyclohexane ring, the carbon atom at the 2-position or 6-position is closest to the 1-position, but when substitution is difficult due to steric hindrance, a substituent may be bonded to the next nearest 3-position or 5-position.

Moreover, although at least 1 is needed for the reason mentioned above, the number of substituents is preferable from a viewpoint of the heat resistance when it is set as hardened|cured material, 3 or more are more preferable.

In Formula (1), m is the number of repetitions, the average value (number average) is 0-5, 0-3 are a preferable range, 0-1 are more preferable ranges, and 0-0.5 are still more preferable ranges. And it is preferable that the repetition number (integer) exists in the range of the integer of normally 0-5. It may be a single compound whose repetition number is any integer of 0-5, or the mixture whose m is an integer of any one of 0-5 may be sufficient. In normal polyvalent hydroxy resin epoxidation with epichlorohydrin, etc., since it is obtained as a mixture, there exists an advantage that it can be used as it is if it is a mixture.

The alcoholic hydroxyl equivalent of the epoxy resin (a1) was 3000 g/eq. more preferably. Therefore, 0-3 are preferable, as for the number of repetitions (integer), 0-2 are more preferable, and 0-1 are still more preferable. Since the alcoholic hydroxyl group in an epoxy resin (a1) increases and a urethane bond arises when this and isocyanate react when 6 or more compound is contained, it is unpreferable from the point of reducing the glass transition point of hardened|cured material. Moreover, since the hydroxyl group density|concentration in hardened|cured material increases, it is also unpreferable from the point which raises the dielectric constant of hardened|cured material. Moreover, it shows that there are few alcoholic hydroxyl groups, so that alcoholic hydroxyl group equivalent is large. When m is 0, an alcoholic hydroxyl group disappears, and since the alcoholic hydroxyl group equivalent becomes infinite theoretically, it is not necessary to set an upper limit in particular.

The epoxy resin (a1) is 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 phenol compound represented by the formula (2) is allyl etherified with an allyl ether. It can be obtained by a known method such as epoxidation by oxidizing the allyl group with an oxidizing agent such as peroxide after etherification.

[Formula 2]

(wherein R and X have the same meaning as R and X in formula (1), respectively)

The epoxy equivalent of the epoxy resin (a1) is 100 g/eq. -500 g/eq. is preferred, 150 g/eq. -300 g/eq. is more preferable. Moreover, the alcoholic hydroxyl group equivalent is also 3000 g/eq. More preferably, 4000 g/eq. More preferably, 5000 g/eq. The above is more preferable.

The phenolic compound represented by Formula (2) is obtained by making corresponding cyclic aliphatic ketones and phenols react by the method etc. disclosed by Unexamined-Japanese-Patent No. 4-282334 and Unexamined-Japanese-Patent No. 2015-51935, respectively. Although a phenol compound etc. which are shown below are mentioned as a specific phenol compound example, It is not limited to these.

[Formula 3]

These exemplified phenolic compounds are commercially available as well, for example, BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, BisOCP-IPZ, BisP -nBZ, BisOEP-2HBP (above, a brand name, Honshu Chemical Industry make) etc. are mentioned.

As an epoxy resin (a1) represented by Formula (1), the epoxy resin obtained from the phenol compounds represented by the said Formula (2), and epihalohydrin is mentioned. 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, 4,4'-(3, 3,5-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 Although phenol glycidyl ether etc. are mentioned, It is not limited to these, It may be used independently and may use 2 or more types together.

As the epoxy resin (a1), 4,4'-(3,3,5-trimethylcyclohexylidene)diphenol and epi which are phenolic compounds represented by the following formula (3) from the viewpoint of ease of availability and good physical properties of the cured product. The epoxy resin represented by the following formula (4) obtained from halohydrin is preferable.

[Formula 4]

[Formula 5]

(wherein m has the same meaning as m in formula (1))

As an epoxy resin (a) used for this invention, unless the effect of this invention is impaired, you may use together epoxy resins (a2) other than an epoxy resin (a1) at 50 mass % or less. It is understood that the epoxy resin (a2) does not have a structure represented by Formula (1). The compounding in which the effect of this invention is expressed most is single use (100 mass %) of an epoxy resin (a1). Moreover, if the usage-amount of an epoxy resin (a1) is less than 50 mass %, there exists a possibility that the effect of this invention may not be expressed. The objective of using the epoxy resin (a2) which can be used together is for provision of other characteristics, such as the further improvement of solvent solubility, for example. Therefore, it is preferable that the usage-amount of an epoxy resin (a2) is as small as possible.

Since the alcoholic hydroxyl group contained in the epoxy resin (a2) reacts with isocyanate and forms a urethane bond, there exists a possibility of reducing the heat resistance of hardened|cured material. Therefore, the alcoholic hydroxyl equivalent is 1000 g/eq. More preferably, 3000 g/eq. More preferably, 5000 g/eq. The above is more preferable.

Moreover, although the epoxy equivalent of an epoxy resin (a2) is not specifically limited, 100 g/eq. -300 g/eq. is preferred, 170 g/eq. -300 g/eq. is more preferable.

As an epoxy resin (a2) which can be used, a bisphenol A epoxy resin, for example, Epototte (trademark) YD-127, Epototte YD-128, Epototte YD-8125, Epototte YD-825GS. (above, brand name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), bisphenol F-type epoxy resin, for example, EPOTOT YDF-170, EPOTOT YDF-1500, EPOTOT YDF-8170, EPOTOT YDF-870GS (above, a brand name, the Shin-Nitetsu Sumikin Chemical Co., Ltd. make), tetramethylbisphenol F-type epoxy resin, for example, YSLV-80XY, YSLV-70XY (above, a brand name, the Shin-Nitetsu Sumikin Chemical Co., Ltd. make), a biphenol-type epoxy Resins such as YX-4000 (trade name, manufactured by Mitsubishi Chemical Co., Ltd.), ZX-1251 (trade name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), hydroquinone-type epoxy resins such as EPOTOT YDC-1312, ZX- 1027 (above, trade name, manufactured by Nippon-Sumikin Chemical Co., Ltd.), bisphenol fluorene type epoxy resin such as ZX-1201 (trade name, manufactured by Nippon Sumikin Chemical Co., Ltd.), naphthalenediol type epoxy resin such as ZX -1355 (trade name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), bisphenol S-type epoxy resin such as TX-0710 (trade name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), Epicron (registered trademark) EXA-1515 (trade name, Dainippon Chemical Industry Co., Ltd. product), bisthioether type epoxy resin, for example, YSLV-120TE (trade name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), resorcinol type epoxy resin such as Epotot ZX-1684 (trade name) , Shin-Nitetsu Sumikin Chemical Co., Ltd.), phenol novolak-type epoxy resin, for example, EPOTOT YDPN-638 (above, trade name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), Epicoat (registered trademark) 152, Epicoat 154 (above, trade name, manufactured by Mitsubishi Chemical Co., Ltd.), Epicron N-740, Epicron N-770, Epicron N-775 (above, trade name, manufactured by DIC Corporation), cresol novolak type epoxy resin, for example, Epototte YDCN-700 series (trade name, manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.), EPICRON N-660, EPICRON N-665, Epicron N-670, Epicron N-673, Epicron N-695 (above, trade name, manufactured by DIC Corporation), EOCN-1020, EOCN-102S, EOCN-104S (above, trade name, Nippon Kayaku Co., Ltd.) manufacture), alkyl novolak-type epoxy resins, such as Epotot ZX-1071T, ZX-1270, ZX-1342 (above, trade names, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), styrenated phenol novolac-type epoxy resins; For example, EPOTOT ZX-1247, GK-5855, TX-1210 (above, trade name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), naphthol novolak type epoxy resin, such as EPOTOT ZX-1142L (trade name, Shin-Nippon Sumikin Chemical Co., Ltd.), β-naphthol aralkyl type epoxy resin, such as ESN-155, ESN-185V, ESN-175 (above, trade name, manufactured by Shin-Nippon Sumikin Chemical Co., Ltd.), dinaphthol aralkyl type Epoxy resins, for example ESN-355 of ESN-300 series, ESN-375 (above, trade name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), α naphthol aralkyl type epoxy resin, such as ESN-400 series of ESN- 475V, ESN-485 (above, trade name, manufactured by Nippon Chemicals Co., Ltd.), biphenyl aralkylphenol type epoxy resin, such as NC-3000, NC-3000H (above, trade name, manufactured by Nippon Kayaku Co., Ltd.) Polyglycidyl ether compound, diaminodiphenylmethane tetraglycidyl ether, for example, Epototh YH-434, Epototh YH-434GS (above, trade names, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), N; Polyglycidylamine compounds such as N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine), for example, TETRAD-X (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.); Immeric acid-type epoxy resins, for example, polyglycidyl ester compounds such as YD-171 (trade name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), aliphatic cyclic epoxy resins such as Celoxide (registered trademark) 2021 (trade name, Although alicyclic epoxy compounds, such as Daicel Chemical Industry Co., Ltd. make), are mentioned, It is not limited to these, These epoxy resins may be used independently and may use 2 or more types together.

Among the epoxy resins (a2) that can be used in combination, epoxy resins containing aliphatic substituents are preferable for the purpose of further lowering the dielectric constant, and polyfunctional phenol novolac-type epoxy resins and cresol novolac-type epoxy resins for the purpose of further improving heat resistance An epoxy resin is preferable, and although a bisphenol A epoxy resin and a bisphenol F epoxy resin are preferable for the objective of reducing a viscosity, respectively, it is not limited to these.

The epoxy equivalent of the epoxy resin (a) used for this invention is 100 g/eq. -500 g/eq. is preferred, 150 g/eq. -300 g/eq. is more preferable. When using a some epoxy resin together, it calculates|requires by measuring after mixing. Moreover, when each epoxy equivalent is already known, you may obtain|require by calculation.

Since the alcoholic hydroxyl group contained in the epoxy resin (a) reacts with isocyanate to form a urethane bond, the heat resistance of the epoxy resin hardened|cured material obtained by hardening an epoxy resin composition is reduced. Therefore, the alcoholic hydroxyl group equivalent in an epoxy resin (a) is 1000 g/eq. More preferably, 3000 g/eq. More preferably, 5000 g/eq. The above is more preferable. When using a some epoxy resin together, it calculates|requires by measuring after mixing. Moreover, when each alcoholic hydroxyl group equivalent is already known, you may calculate|require by calculation.

The alcoholic hydroxyl group of an epoxy resin (a) is an alcoholic hydroxyl group generated with reaction of a phenol compound and epihalohydrin. When the epihalohydrin is epichlorohydrin, these alcoholic hydroxyl groups are an alcoholic hydroxyl group derived from the 2-chloro-3-hydroxypropyl group (α ), an alcoholic hydroxyl group derived from 1-chloromethyl-2-hydroxyethyl group generated by the addition of a phenol compound to the beta position of epichlorohydrin (β), a secondary alcoholic hydroxyl group generated by adding a phenol compound to an epoxy resin (γ) and α glycol (δ) generated by hydrolysis of the epoxy group of the epoxy resin. Since the alcoholic hydroxyl group in the present invention refers to all of (α), (β), (γ) and (δ), the alcoholic hydroxyl group equivalent is (α), (β), (γ) and (δ) all object to be measured.

In order to manufacture the oxazolidone ring containing epoxy resin of this invention, an isocyanate compound (b) is used with an epoxy resin (a). A desired oxazolidone ring containing epoxy resin can be obtained by reaction of this epoxy resin (a) and an isocyanate compound (b). This isocyanate compound (b) should just be an isocyanate compound which has an average of 1.8 or more isocyanate groups (-N=C=O) in a molecule|numerator, and a well-known and usual isocyanate compound can be used. Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane isocyanate, xylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, hexamethylene Diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, 4 , 4-dicyclohexylmethane diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, lysine ester triisocyanate, undecane triisocyanate, 1,8-diisocyanate -4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, methane diisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, butane-1, 2-diisocyanate, transvinylene diisocyanate, propane-1,3-diisocyanate, butane-1,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate , 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7 -diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω,ω'-1,3 -dimethylbenzene diisocyanate, ω,ω'-1,4-dimethylbenzenediisocyanate, ω,ω'-1,3-dimethylcyclohexanediisocyanate, ω,ω'-1,4-dimethylcyclohexanediisocyanate, ω,ω'-1,4-dimethylnaphthalene diisocyanate, ω,ω'-1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, dicyclo Hexylmethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate Anate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate , diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-4,4' -diisocyanate, 3,3'-dimethylbisphenyl-4,4'-diisocyanate, 2,3'-dimethoxybisphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate , 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfite-4,4'-di Bifunctional isocyanate compounds such as isocyanate and diphenylsulfone-4,4'-diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, tris(4-phenylisocyanatethiophosphate)-3,3',4; Polyfunctional isocyanate compounds such as 4'-diphenylmethane tetraisocyanate, polymers such as dimers and trimers of the isocyanate compound, block-type isocyanates masked with a blocking agent such as alcohol or phenol, bisurethane compounds, etc. , but is not limited thereto. These isocyanate compounds may be used independently and may be used in combination of 2 or more type.

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

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

The reaction mechanism for forming the oxazolidone ring is represented by the following Reaction Formula (5). By adding a catalyst to the epoxy resin (a) and the isocyanate compound (b), the epoxy group of the epoxy resin (a) and the isocyanate group of the isocyanate compound (b) react to form an oxazolidone ring.

[Formula 6]

Moreover, when an epoxy resin (a) contains an alcoholic hydroxyl group, as shown by following reaction formula (6), the isocyanate group of an isocyanate compound (b) addition-reacts with an alcoholic hydroxyl group, and forms a urethane bond.

[Formula 7]

In addition, the epoxy equivalent of an oxazolidone ring containing epoxy resin can be estimated according to the following formula (7) from the injection amount of a raw material. The preferred epoxy equivalent of the oxazolidone ring-containing epoxy resin of the present invention is 200 to 600 g/eq. am. Adjusting the content of the oxazolidone ring in the resin within the range is possible by adjusting the NCO concentration of the isocyanate compound (b) to be used.

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

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

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

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

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

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

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

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

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

Specific examples of the catalyst that can be used include lithium compounds such as lithium chloride and butoxylithium, complex salts of boron trifluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, and tetramethylammonium iodide. , quaternary ammonium salts such as tetraethylammonium iodide, tertiary amines such as dimethylaminoether, triethylamine, tributylamine, benzyldimethylamine, N-methylmorpholine, triphenylphosphine, tris(2, phosphines such as 6-dimethoxyphenyl) phosphine, amyltriphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, Phosphonium salts such as tetrabutylphosphonium acetate/acetic acid complex, tetrabutylphosphonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide and tetrabutyliodide, a combination of triphenylantimony and iodine, 2-phenylimida Although imidazoles, such as sol, 2-methylimidazole, 2-ethyl-4-methylimidazole, etc., alkali metal oxides, such as sodium hydroxide, are mentioned, It is not limited to these, These catalysts are It may be used independently and may use 2 or more types together. Moreover, you may divide and divide and use it several times.

Although the kind of catalyst is not specifically limited, Among the catalysts, a preferable base catalyst is tetramethylammonium iodide in reaction activity and reaction selectivity. In a catalyst with low reaction activity, there is a fear that the reaction time is prolonged and a decrease in productivity is caused.

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

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

Specific examples of the epoxy resin modifier that can be used include bisphenol A, dimethylbisphenol A, tetramethylbisphenol A, tetrabutylbisphenol A, bisphenol F, dimethylbisphenol F, tetramethylbisphenol F, bisphenol S, dimethylbisphenol S, and tetramethylbisphenol A. Methylbisphenol S, bisphenol B, bisphenol C, bisphenol E, bisphenol P, bisphenol AF, bisphenol AP, bisphenolfluorene, biscresolfluorene, bisphenol Z, tetramethylbisphenol Z, bisphenol TMC, hydroquinone, methylhydroquinone, dimethyl Hydroquinone, dibutylhydroquinone, resorcinol, methylresorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, dihydroxybenzophenone, dihydroxydiphenylsulfide, dihydroxydiphenylsulfide Hydroxystilbenes, phenol novolac resin, cresol novolak resin, bisphenol A novolac resin, dicyclopentadienephenol resin, phenol aralkyl resin, naphthol novolac resin, styrenated phenol novolak resin, terpene phenol resin, heavy oil Various phenols such as modified phenol resins, polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, aniline, phenylenediamine, toluidine, and xylidine , diethyltoluenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenylketone, diaminodiphenylsulfide, diaminodiphenylsulfone, bis(aminophenyl)fluorene , diaminodiethyldimethyldiphenylmethane, diaminodiphenyl ether, diaminobenzanilide, diaminobiphenyl, dimethyldiaminobiphenyl, biphenyltetraamine, bisaminophenylanthracene, bisaminophenoxybenzene, bisamino and amine compounds such as phenoxyphenyl ether, bisaminophenoxybiphenyl, bisaminophenoxyphenylsulfone, bisaminophenoxyphenylpropane, and diaminonaphthalene, but are not limited thereto, and these epoxy resin modifiers alone may be used, or two or more types may be used in combination.

Moreover, you may use a non-reactive solvent as needed. Specifically, various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethyl ether, isopropyl ether, butyl ether, diiso Ethers such as amyl ether, methyl phenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methyl furan, tetrahydrofuran, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, dimethyl sulfoxide, etc., but are not limited thereto, and these non-reactive solvents include You may use individually and may mix and use 2 or more types.

The absorbance spectrum in the range of 1650 to 1800 cm ^-1 when the oxazolidone ring-containing epoxy resin is analyzed by the total reflection measurement method (ATR method) of the infrared spectrophotometer is shown in Figs. 4 (Example 1) and Fig. 5 (Comparative Example 2) is shown in

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

In the absorbance spectrum of Fig. 5, the peak A derived from 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 overlaps the peak of the ^oxazolidone ring and does not show a clear peak top. do.

The maximum value of the peak included in 1745 to 1760 cm ^-1 derived from stretching vibration of the carbonyl group of the oxazolidone ring is expressed as absorbance Ox. Let absorbance Ur be the maximum value of the peak contained in 1730-1740 cm< ^-1 > derived from expansion-contraction vibration of the carbonyl group of a urethane bond. At this time, the ratio of the presence of the oxazolidone ring and the urethane bond was expressed as the absorbance ratio Ox/Ur.

When an oxazolidone ring-containing epoxy resin is produced by the reaction of the epoxy resin (a) and the isocyanate compound (b), the alcoholic hydroxyl group contained in the epoxy resin (a) reacts with the isocyanate group of the isocyanate compound (b), the reaction formula Not the reaction to form the oxazolidone ring of (5), but the reaction to form a urethane bond by reaction formula (6) takes place. When the density|concentration of the urethane bond contained in an oxazolidone ring containing epoxy resin becomes high, there exists a possibility of reducing the heat resistance of the epoxy resin hardened|cured material obtained by hardening|curing an epoxy resin composition. Therefore, the ratio between the oxazolidone ring and the urethane bond contained in the oxazolidone ring-containing epoxy resin is defined as the absorbance ratio Ox/Ur. 1.35 or more are preferable and, as for the absorbance ratio Ox/Ur, 2.0 or more are more preferable. When the absorbance ratio Ox/Ur is less than 1.35, there is a fear that the heat resistance of the cured epoxy resin containing an oxazolidone ring is reduced.

Further, the softening point of the oxazolidone ring-containing epoxy resin of the present invention is preferably 50°C to 150°C, more preferably 65°C to 135°C, and more preferably 70°C to 110°C when used for a prepreg or film material. more preferably. When a softening point is low, since a viscosity is low when making it heat-dry in oven after glass cross impregnation with a resin varnish, there exists a possibility that the adhesion amount of resin may decrease. When the softening point is high, the resin viscosity increases, the impregnation property to the prepreg deteriorates, the solvent solubility deteriorates, and the dilution solvent remains in the resin without volatilization during heating and drying. There is a possibility that it may become a big problem in use.

The epoxy equivalent of the oxazolidone ring-containing epoxy resin of the present invention is 200 g/eq. more than 550 g/eq. 215 g/eq. more than 500 g/eq. The following ranges are preferred, 230 g/eq. more than 450 g/eq. The following ranges are more preferable, 250 g/eq. more than 350 g/eq. The following ranges are more preferable. When the epoxy equivalent is low, the content of the oxazolidone ring decreases and the concentration of hydroxyl groups in the cured product increases, so that there is a fear that the dielectric constant becomes high. Moreover, when an epoxy equivalent is high, content of an oxazolidone ring increases more than necessary, and there exists a possibility that adverse effects, such as deterioration of solvent solubility and increase of resin viscosity, may increase rather than the improvement effect of a dielectric property. Moreover, since the crosslinking density of hardened|cured material becomes low, there exists a possibility that it may become a big problem on use, such as an elasticity modulus falling in solder reflow temperature.

The oxazolidone ring containing epoxy resin of this invention can be made into a curable epoxy resin composition by mix|blending a hardening|curing agent. As the curing agent, commonly used curing agents for epoxy resins, such as various phenol resins, acid anhydrides, amines, hydrazides, and acidic polyesters, can be used. These hardening|curing agents may be used independently and may use 2 or more types together. Of these, dicyandiamide or a phenol-based 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 mol or more and 1.5 mol or less of the active hydrogen groups of the curing agent with respect to 1 mol of the epoxy groups of all epoxy resins containing the oxazolidone ring-containing epoxy resin. When the active hydrogen groups are less than 0.2 mol or more than 1.5 mol with respect to 1 mol of the epoxy group, curing may be incomplete and good cured physical properties may not be obtained. A preferable range is 0.3 mol or more and 1.5 mol or less, A more preferable range is 0.5 mol or more and 1.5 mol or less, A more preferable range is 0.8 mol or more and 1.2 mol or less. For example, when a phenol-based curing agent or an amine-based curing agent is used, an active hydrogen group is blended in substantially equimolar amounts with respect to the epoxy group, and when an acid anhydride-based curing agent is used, 0.5 to 1.2 moles of an acid anhydride group with respect to 1 mole of the epoxy group, preferably 0.6-1.0 mol is mix|blended.

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

Specific examples of the phenol resin curing agent include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydride Bisphenols such as hydroxydiphenyl sulfide and 4,4'-thiobis(3-methyl-6-tert-butylphenol); catechol, resorcinol, methylresorcin, hydroquinone, monomethylhydroquinone; Dihydroxybenzenes such as dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, trihydroxy Hydroxynaphthalenes such as naphthalene, phenol novolac resin, cresol novolac resin, RegTop (registered trademark) TPM-100 (product name, manufactured by Gunei Chemical Industry Co., Ltd.) Trishydroxyphenylmethane type novolac resin, naphthol Condensates of phenols and/or naphthols and aldehydes such as novolac resins, condensates of phenols and/or naphthols and xylylene glycol, for example, SN-160, SN-395, SN-485 (above, Product name, manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.), a condensate of phenols and/or naphthols and isopropenylacetophenone, a reaction product of phenols and/or naphthols and dicyclopentadiene, phenols and/or naphthols and biphenyl Phenolic compounds, such as a condensate of a system condensing agent, etc. are mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

A cured epoxy resin product can be obtained by curing the epoxy resin composition. As a method for obtaining a cured product, the same method as that of a known epoxy resin composition can be taken, and the method unique to the epoxy resin composition of the present invention is not required, and casting, pouring, potting, dipping, drip coating, transfer molding, Compression molding or the like, or a method such as forming a resin sheet, copper foil with resin, prepreg, or the like and laminating it and curing it by heating and pressurization to obtain a laminated sheet is preferably used. The curing temperature in that case is normally in the range of 100 degreeC - 300 degreeC, and hardening time is about 1 hour - about 5 hours normally.

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

As a result of preparing an epoxy resin composition and evaluating the cured epoxy resin product of the laminate by heat curing, the oxazolidone ring-containing epoxy resin of the present invention has a low dielectric property compared with a conventionally known epoxy resin, and has a low viscosity It was possible not only to have good workability, but also to have high heat resistance and high adhesiveness, and it was also possible to improve solvent solubility.

Example

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

· Epoxy equivalent: according to JIS K7236 standard.

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

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

- Solvent solubility: The state when it diluted to 50% of non-volatile matter with methyl ethyl ketone was judged visually. A completely dissolved and transparent thing was denoted by ○, a cloudy or separated thing was denoted by ×, and a slightly cloudy thing was denoted by Δ.

Absorbance ratio Ox/Ur: 1745 to 1760 by measuring the absorbance of 1650 to 1800 cm ^-1 by the total reflection measurement method (ATR method) of a Fourier transform infrared spectrophotometer (manufactured by PerkinEler Precisely, Spectrum One FT-IR Spectrometer 1760X) The maximum value of absorbance within the range of cm ^-1 was defined as Ox, and the maximum value of absorbance within the range of 1730-1740 cm ^-1 was defined as Ur, and the absorbance ratio Ox/Ur was calculated by calculation.

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

・Glass transition temperature (DSC method): When measurement was performed under a temperature rise condition of 20°C/min with a differential scanning calorimetry device (Exstar6000 DSC6200, manufactured by Hitachi Hitech Science, Inc.) in accordance with IPC-TM-650 2.4.25.c was expressed as the DSC·Tgm (intermediate temperature of the transition curve for the tangent between the glass state and the rubber state).

・Glass transition temperature (TMA method): When the measurement was carried out under a temperature increase condition of 10°C/min with a thermomechanical analyzer (manufactured by Hitachi Hitech Science, EXSTAR6000 TMA/SS120U) in accordance with IPC-TM-650 2.4.24.1 It was expressed as the temperature of the TMA extrapolated value.

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

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

-GPC: A body (manufactured by Tosoh Corporation, HLC-8220GPC) having a column (manufactured by Tosoh Corporation, TSKgel (registered trademark) G4000HXL, TSKgelG3000HXL, TSKgelG2000HXL) in series was used, and the column temperature was set to 40°C. In addition, tetrahydrofuran was used as an eluent, it was set as the flow rate of 1 ml/min, and the detector used the RI (differential refractometer) detector. It converted from the calibration curve calculated|required from standard monodisperse polystyrene.

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

-NMR: The ^13C liquid was measured using _CDCL3 as a solvent with a Fourier transform nuclear magnetic resonance apparatus (made by JEOL, JNM-ECA400).

Synthesis Example 1

In a glass separable flask, 100 parts of 4,4'-(3,3,5-trimethylcyclohexylidene)diphenol (manufactured by Honshu Chemical Industry Co., Ltd., BisP-TMC), 358 parts of epichlorohydrin, and ions 4 parts of exchange water were injected|threw-in, and it heated up to 50 degreeC, stirring. After uniformly melt|dissolving, 5.3 parts of 49% sodium hydroxide aqueous solution were injected|thrown-in, and reaction was performed for 3 hours. Next, after raising the temperature to 64°C, the pressure was reduced to the extent that reflux of water occurred, and 48 parts of a 49% aqueous sodium hydroxide solution were added dropwise over 3 hours, and the water and epichlorohydrin discharged under reflux during this dropwise addition were separated in a separation tank. After separation, epichlorohydrin was returned to the reaction vessel, and water was removed from the system to react. After completion of the reaction, the temperature was raised to 70°C to perform dehydration, and the temperature was adjusted to 135°C to recover the remaining epichlorohydrin. It returned to normal pressure, and 204 parts of methyl isobutyl ketone (MIBK) were added and dissolved. 127 parts of ion-exchange water was added, it stirred and left still, and the salt produced by it was dissolved in water and removed. Next, 2.9 parts of 49% sodium hydroxide aqueous solution was poured in, and it was made to react with stirring at 80 degreeC for 90 minutes, and purification reaction was performed. MIBK was added and washed several times to remove ionic impurities. The solvent was collect|recovered and the epoxy resin (epoxy resin A) represented by the said Formula (4) was obtained. The obtained epoxy resin A had an epoxy equivalent of 219 g/eq. and an alcoholic hydroxyl group equivalent of 5510 g/eq. , and m (average value) is 0.04.

Synthesis Example 2

282 parts of phenol and 14.8 parts of 98% sulfuric acid were poured into the apparatus similar to the synthesis example 1, and it heated up to 80 degreeC. After stirring for 1 hour at the same temperature, 33.6 parts of 4-methylcyclohexanone and 6 parts of n-dodecylmercaptan were added at 60°C, and the residual amount of 4-methylcyclohexanone was initially adjusted while removing water at 65°C and 1.3 kPa. It was made to react until it became 50% of the input amount. After returning the pressure to normal pressure with nitrogen gas, it was cooled to room temperature and left still for 3 days. Thereafter, toluene and ion-exchanged water were added to the solidified reaction product for dissolution, 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, filtered, and dried. This operation was repeated twice to obtain 4,4'-(4-methylcyclohexylidene)diphenol.

Next, the same operation was performed using the same apparatus as in Synthesis Example 1, except that 100 parts of BisP-TMC was replaced with 91 parts of the obtained 4,4'-(4-methylcyclohexylidene)diphenol, the following formula (8) An epoxy resin (epoxy resin B) represented by was obtained. The obtained epoxy resin B had an epoxy equivalent of 206 g/eq. and an alcoholic hydroxyl group equivalent of 5480 g/eq. , and m is 0.05.

[Formula 8]

Synthesis Example 3

Except for replacing 100 parts of BisP-TMC with 86.5 parts of 4,4'-cyclohexylidenebisphenol (manufactured by Honshu Chemical Industry Co., Ltd., Bis-Z), the same operation was carried out using the same apparatus as in Synthesis Example 1, and the following formula ( An epoxy resin (epoxy resin F) represented by 9) was obtained. The obtained epoxy resin F had an epoxy equivalent of 200 g/eq. and an alcoholic hydroxyl equivalent of 5500 g/eq. , and m is 0.06.

[Formula 9]

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

(epoxy resin)

Epoxy resin A: Epoxy resin obtained in Synthesis Example 1

Epoxy resin B: Epoxy resin obtained in Synthesis Example 2

Epoxy resin C: bisphenol A liquid epoxy resin (manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., EPOTOT YD-128, epoxy equivalent 186 g/eq., alcoholic hydroxyl group equivalent 2000 g/eq.)

Epoxy resin D: dicyclopentadiene type epoxy resin (manufactured by Kokuto Chemical Co., Ltd., KDCP-130, epoxy equivalent of 254 g/eq., alcoholic hydroxyl equivalent of 2500 g/eq.)

Epoxy resin E: Styrenated phenol novolac-type epoxy resin (manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., TX-1210, epoxy equivalent 257 g/eq., alcoholic hydroxyl equivalent 2800 g/eq.)

Epoxy resin F: Epoxy resin obtained in Synthesis Example 3

(isocyanate)

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

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

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

(catalyst)

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

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

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: Phenolic novolac resin (manufactured by Showa Denko Co., Ltd., Shounol (registered trademark) BRG-557, softening point 80°C)

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

(curing accelerator)

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

(flame retardant)

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

Example 1

In the same apparatus as in Synthesis Example 1, 100 parts of epoxy resin A as an epoxy resin (a) and 0.11 parts of catalyst A as a catalyst were injected, and the temperature was increased while introducing nitrogen gas, and the temperature was maintained at 120 ° C. Moisture was removed. Next, while maintaining the reaction temperature of 130°C to 140°C, 11.5 parts of isocyanate A as the isocyanate compound (b) (molar ratio of the isocyanate group of the isocyanate compound (b) to 1 mol of the epoxy group of the epoxy resin (a) [( b)/(a)] = 0.20) was added dropwise over 3 hours as a 50% toluene solution. After completion of the dropwise addition, stirring was continued for an additional 60 minutes while maintaining the same temperature. After completion of the reaction, the solvent was removed at 150°C, 1.33 kPa, and 30 minutes of recovery conditions to obtain an oxazolidone ring-containing epoxy resin (resin 1). With the obtained oxazolidone ring-containing epoxy resin, the epoxy equivalent, softening point, solvent solubility, and absorbance ratio were measured. Table 1 shows the measurement results. Moreover, a GPC chart is shown in FIG. (In the figure, the abscissa represents the elution time (minutes), and the left vertical axis represents the signal intensity (mV). The right vertical axis represents the number average molecular weight M as a common logarithm (log). Number of standard substances used The measured value of the average molecular weight was plotted as a white circle as a calibration curve.) An IR chart is shown in FIG. 2 . (In the figure, the horizontal axis indicates the wave number (cm ⁻¹ ), and the vertical axis indicates the transmittance (%T)) FIG. 3 shows a ¹³ C-NMR spectrum NMR chart. The absorbance spectrum in the range of 1650-1800 cm< ^-1 > at the time of analyzing by the total reflection measurement method (ATR method) of an infrared spectrophotometer in FIG. 4 is shown.

Examples 2 to 18

According to the injection amounts (parts) of each raw material shown in Table 1 or Table 2, an oxazolidone ring-containing epoxy resin was synthesized by the same operation as in Example 1 using the same apparatus. In addition, reaction temperature maintained the temperature range of reaction temperature +/-5 degreeC shown in Table 1 or Table 2, and the isocyanate compound was dripped at the dripping time shown in Table 1 or Table 2. Similarly to Example 1, the epoxy equivalent, softening point, solvent solubility, and absorbance ratio of the obtained oxazolidone ring containing epoxy resin were measured, and a measurement result is shown in Table 1 or Table 2.

Comparative Examples 1 to 5

According to the injection amount (part) of each raw material shown in Table 3, an oxazolidone ring-containing epoxy resin was synthesized by the same operation as in Example 1 using the same apparatus. In addition, reaction temperature maintained the temperature range of reaction temperature +/-5 degreeC shown in Table 3, and the isocyanate compound was dripped at the dripping time shown in Table 3. Similarly to Example 1, the epoxy equivalent, softening point, solvent solubility, and absorbance ratio of the obtained oxazolidone ring containing epoxy resin were measured, and the measurement result is shown in Table 3. Moreover, about the oxazolidone ring containing epoxy resin obtained in Comparative Example 2, the absorbance spectrum in the range of 1650-1800 cm ^-1 when analyzed by the total reflection measurement method (ATR method) of an infrared spectrophotometer in FIG. 5 is shown.

The oxazolidone ring-containing epoxy resin obtained in Example 1 was referred to as Resin 1, and was referred to as Resins 2 to 18 in the same manner below. The oxazolidone ring-containing epoxy resin obtained in Comparative Example 1 was referred to as Comparative Resin 1, and was referred to as Comparative Resins 2 to 5 in the same manner below.

Example 19

A mixed solvent prepared by blending 100 parts of 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, and adjusted with MEK, propylene glycol monomethyl ether, and N,N-dimethylformamide to obtain an epoxy resin composition varnish.

The obtained epoxy resin composition varnish was impregnated in the glass cloth (The Nitto Spinning Co., Ltd. make, WEA116E106S136, thickness 0.1mm). The impregnated glass cloth was dried for 11 minutes in 150 degreeC hot-air circulation oven, and the prepreg was obtained. 8 sheets of obtained prepreg and copper foil (manufactured by Mitsui Metals Mining Co., Ltd., 3EC-III, thickness 35 µm) were superimposed on top and bottom, and a vacuum press of 2 MPa was performed at a temperature of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes. It carried out and obtained the laminated board of 1 mm thickness. Table 4 shows the results of the copper foil peel strength of the laminate, the interlayer adhesion, the glass transition temperature (DSC method) (Tg·DSC), and the glass transition temperature (TMA method) (Tg·TMA).

Moreover, the obtained prepreg was unwound, and it was set as the powdery prepreg powder of 100 mesh pass through a sieve. The obtained prepreg powder was put in a mold made of a fluororesin, vacuum pressed at 2 MPa under a temperature condition of 130° C. × 15 minutes + 190° C. × 80 minutes, and a test piece with a thickness of 50 mm × 2 mm got Table 4 shows the results of the relative dielectric constant and dielectric loss tangent of the test piece.

Examples 20 to 36

Examples 2 to 18 Resins 2 to 18, PN, and 2E4MZ were blended in the compounding amounts (parts) of Table 4 or Table 5, using the same apparatus as in Example 19, the same operation was performed, and the laminate was and test pieces were obtained. The test similar to Example 19 was implemented, and the result is shown in Table 4 or Table 5. In addition, "-" in a table|surface shows that it is not used.

Comparative Example 6 to Comparative Example 13

Comparative resins 1 to 5 of Comparative Examples 1 to 5, Epoxy resin A, Epoxy resin D, Epoxy resin E, PN, and 2E4MZ were blended in the amounts (parts) shown in Table 6, and the same apparatus as in Example 19 Using , the same operation was performed to obtain a laminate and a test piece. The same test as in Example 19 was implemented, and the result is shown in Table 6. In addition, "-" in a table|surface represents 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, Comparative Resin 1, Comparative Resin 2, Comparative Resin 4, DICY, and 2E4MZ were blended in the amount (parts) of the formulation shown in Table 7, and the same as in Example 19. Using the apparatus, a laminated plate and a test piece were obtained by the same operation. The test similar to Example 19 was implemented, and the result is shown in Table 7. In addition, "-" in a table|surface shows 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 blended in the amounts (parts) of the formulation shown in Table 8, and the same apparatus as in Example 19 was used. Using and the same operation, the same test as Example 19 which obtained the laminated board and the test piece was done, and the result is shown in Table 8. Moreover, the test piece for a flame retardance measurement was obtained by etching both surfaces of a laminated board. In addition, "-" in a table|surface represents that it is not used.

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

Claims (18)

Alcoholic hydroxyl equivalent of 3000 g/eq. It is obtained from the epoxy resin (a) and the isocyanate compound (b) containing 50 mass % or more of the epoxy resin (a1) represented by the above following formula (1), and an epoxy equivalent is 200-550 g/eq. and, 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 derived from the absorbance Ox, the stretching vibration peak of the carbonyl group of the urethane bond structure An oxazolidone ring-containing epoxy resin having an absorbance ratio Ox/Ur of 1.35 or more, when the maximum value of the peak included in 1730-1740 cm ^-1 is taken as absorbance Ur.
[Formula 1]

(Wherein, X represents a cycloalkylidene group having 5 to 8 ring atoms 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 each independently represents 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 is a glycidyl group. represents repetition, and the average value is 0 to 5.) The method of claim 1,
Together with the epoxy resin (a1), the alcoholic hydroxyl equivalent was 1000 g/eq. The oxazolidone ring containing epoxy resin which contains 50-0 mass % of other epoxy resins (a2) above in an epoxy resin (a). The method of claim 1,
The epoxy equivalent of the epoxy resin (a) is 100-500 g/eq. Epoxy resin containing phosphorus oxazolidone ring. The method of claim 1,
Isocyanate compound (b) An oxazolidone ring-containing epoxy resin having an average of 1.8 or more isocyanate groups in the molecule. The method of claim 1,
Isocyanate compound (b) 1 selected from tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate Epoxy resins containing more than one species of oxazolidone ring. The method of claim 1,
An oxazolidone ring-containing epoxy resin having a softening point of 50 to 150°C. The epoxy resin (a) containing 50 mass % or more of the epoxy resin (a1) represented by following formula (1), and the isocyanate compound (b) with respect to 1 mol of the epoxy groups of the epoxy resin (a) of the isocyanate compound (b) An oxazolidone ring-containing epoxy resin, characterized in that an isocyanate group is used in the range of 0.02 mol or more and less than 0.45 mol, and the moisture in the system is removed in the presence of a catalyst, and then reacted at a reaction temperature of 100°C or more and 160°C or less manufacturing method.
[Formula 2]

(Wherein, X represents a cycloalkylidene group having 5 to 8 ring atoms 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 each independently represents 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 is a glycidyl group. represents repetition, and the average value is 0 to 5.) 8. The method of claim 7,
Isocyanate compound (b) A method for producing an oxazolidone ring-containing epoxy resin having an average of 1.8 or more isocyanate groups in the molecule. 9. The method according to claim 7 or 8,
Isocyanate compound (b) 1 selected from tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate A method for producing an epoxy resin containing more than one species of oxazolidone ring. 9. The method according to claim 7 or 8,
A method for producing an oxazolidone ring-containing epoxy resin in which the catalyst is a basic catalyst. An epoxy resin composition comprising the oxazolidone ring-containing epoxy resin according to any one of claims 1 to 6 and a curing agent as essential. 12. The method of claim 11,
The epoxy resin composition in which the active hydrogen groups of a hardening|curing agent are 0.2-1.5 mol with respect to 1 mol of the epoxy groups of all the epoxy resins in an epoxy resin composition. An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 11 . The prepreg characterized by using the epoxy resin composition of Claim 11. The epoxy resin laminated board characterized by using the epoxy resin composition of Claim 11. delete delete delete

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