KR20180108512A - Oxazolidone ring-containing epoxy resin composition, method for producing the same, curable resin composition and cured product - Google Patents

Abstract

The present invention provides an oxazolidone ring-containing epoxy resin composition capable of having excellent bonding force, dielectric properties, and flame retardancy and being useful as an epoxy resin material for an electronic circuit board. The oxazolidone ring-containing epoxy resin composition is obtained from epoxy resin (a) and an isocyanate compound (b), and contains bisphenol type epoxy resin (a1) indicated in the formula (1) and biphenyl type epoxy resin (a2) indicated in formula (2) below. The epoxy resin (a1) is 5-50 mass%, and the sum of the epoxy resin (a1) and the epoxy resin (a2) is 55-100 mass%. In the formulas, X is a cycloalkylidene group with 5-8 ring atoms which has an alkyl group, an aryl group, or an aralkyl group as a substituent.

Description

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

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

Epoxy resins are used in various fields such as paints, civil engineering adhesives, casting molds, electrical and electronic materials, and film materials in view of excellent adhesiveness, flexibility, heat resistance, chemical resistance, insulation and curing reactivity. Particularly, in the use of a printed wiring board which is one of electric and electronic materials, it is widely used by imparting flame retardancy to an epoxy resin.

BACKGROUND ART Infrastructure devices such as a portable device, which is one of applications of a printed wiring board, and a base station connecting the same, have always been required to have high functionality along with the recent increase in the amount of dramatic information. In portable devices, a multi-layered or micro-wiring has been advanced for the purpose of miniaturization, a material having a lower dielectric constant is required to thin the substrate, and a bonding material is reduced by fine wiring, Is required. In order to suppress the attenuation of the signal due to the high frequency in the substrate for the base station, a material with lower dielectric loss tangent is required.

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

Regarding the lowering of the dielectric constant of the epoxy resin, Patent Document 1 discloses a method for producing a low dielectric constant epoxy resin which comprises reacting diglycidyl of 4,4 '- [1,3-phenylene bis (1-methylethylidene)] bis [2,6- Ethers. In Patent Document 2, the alcoholic hydroxyl equivalent is 1000 g / eq. (1.0 meq / g or less) and an isocyanate compound having two or more isocyanate groups in a molecule, and an epoxy resin polymerized by an oxazolidone ring has a low dielectric constant, a low dielectric constant And the glass transition temperature is also high.

Patent Document 3 discloses an epoxy resin containing an oxazolidone ring by reaction between an epoxy resin and an isocyanate. As a raw epoxy resin, a compound obtained by glycidylating a dihydric phenol such as bisphenol A, a tris (glycidyloxy Phenyl) alkanols, aminophenols, and the like, and compounds obtained by glycidylating novolacs such as phenol novolak.

Patent Document 4 discloses a method of reacting a compound obtained by glycidylating a divalent phenol obtained by reacting a cyclic aliphatic ketone with a phenol and a isocyanate compound having two or more isocyanate groups in the molecule as a raw material epoxy resin And an oxazolidone ring-containing epoxy resin.

Patent Document 5 discloses an epoxy resin obtained by reacting a tetramethylbiphenol type epoxy resin as a starting epoxy resin with an isocyanate compound having two or more isocyanate groups in a molecule.

However, the epoxy resin disclosed in any of the literatures does not sufficiently satisfy the requirements of the dielectric properties based on recent high-performance, and the flame retardancy and adhesiveness are also insufficient.

Japanese Patent Application Laid-Open No. 5-293929 Japanese Patent Application Laid-Open No. 9-278867 Japanese Unexamined Patent Publication No. 5-43655 Japanese Laid-Open Patent Publication No. 2016-169362 Japanese Laid-Open Patent Publication No. 2016-69563

Accordingly, an object of the present invention is to provide an epoxy resin composition which is excellent in low dielectric constant, high heat resistance and high adhesiveness and is useful for applications such as lamination, molding, casting, and bonding, and an epoxy resin composition And a cured product of the curable resin composition.

In order to solve the above problems, the present inventors have intensively studied low dielectric constant and low dielectric loss tangent materials. As a result, they have found that a mixture of an epoxy resin containing two specific types of epoxy resins and an oxazolidone The present inventors have found that the ring-containing epoxy resin composition achieves both low dielectric constant, low dielectric loss tangent, and high flame retardancy which are not conventionally available, and that the adhesive strength is also good.

Specifically, the present invention provides an oxazolidone ring-containing epoxy resin composition obtained from an epoxy resin (a) and an isocyanate compound (b), wherein the epoxy resin (a) comprises an epoxy resin (a1) represented by the following formula (1) Wherein the epoxy resin (a1) is contained in an amount of 5 to 50 mass%, the total amount of the epoxy resin (a1) and the epoxy resin (a2) is 55 to 100 mass% . The epoxy resin composition according to claim 1, wherein the oxazolidone ring-containing epoxy resin composition is an oxazolidone ring-containing epoxy resin composition.

[Chemical Formula 1]

X is a cycloalkyl group having 5 to 8 ring atoms and having at least one substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms It is Denji. R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms , k1 and k2 are each independently an integer of 0 to 4. G is a glycidyl group. m and n represent the number of repeats, and the average value is 0 to 2.

The present invention also provides an epoxy resin composition comprising 5 to 50 mass% of the epoxy resin (a1) represented by the above formula (1), 55 to 100 mass% of a total of the epoxy resin (a1) and the epoxy resin (a2) Containing epoxy resin (a) and an isocyanate compound (b) in the presence of a catalyst in the presence of a catalyst.

In the epoxy resin composition containing an oxazolidone ring, or a method for producing the same, it is preferable that one or two or more of the following requirements are satisfied.

1) The alcoholic hydroxyl equivalent of the epoxy resin (a) is 1000 g / eq. Or more.

2) The isocyanate compound (b) has an average of at least 1.8 isocyanate groups in the molecule.

3) epoxy equivalent weight of the oxazolidone ring-containing epoxy resin composition is 200 to 600 g / eq. .

4) The epoxy resin composition containing oxazolidone ring has a softening point of 50 to 150 ° C.

5) A compound having an isocyanate group of the isocyanate compound (b) in an amount of 0.02 mol or more and less than 0.5 mol based on 1 mol of the epoxy group of the epoxy resin (a).

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

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

Further, the present invention is a cured product obtained by curing the above-mentioned curable resin composition. Further, the present invention is a prepreg and laminate obtained from the curable resin composition.

The epoxy resin composition of the present invention and a cured product of the curable resin composition containing the epoxy resin composition exhibit a cured product having high flame retardancy while maintaining an adhesive force. And exhibits good characteristics in a laminated board and an electronic circuit board which are excellent in dielectric characteristics and require low dielectric constant and low dielectric loss tangent.

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

The oxazolidone ring-containing epoxy resin composition of the present invention is obtained by reacting an epoxy resin (a) with an isocyanate compound (b). Here, the epoxy resin (a) is a mixture containing the epoxy resin (a1) represented by the formula (1) and the epoxy resin (a2) represented by the formula (2) as essential components.

The oxazolidone ring-containing epoxy resin composition comprises an oxazolidone ring-containing epoxy resin (A1) in which an epoxy resin (a1) is reacted with an isocyanate compound (b) alone and an epoxy resin (a2) (A12) containing an oxazolidone ring-containing epoxy resin (A2) in which both an epoxy resin (a1) and an epoxy resin (a2) are reacted with an isocyanate compound (b) , And further contains an unreacted epoxy resin (a1) and an epoxy resin (a2).

The epoxy resin (a) may contain an epoxy resin (a3) other than the epoxy resin (a1) and the epoxy resin (a2). In this case, the oxazolidone ring-containing epoxy resin (A3) in which the epoxy resin (a3) alone is reacted with the isocyanate compound (b), and the epoxy resin (a1) and the epoxy resin (a3) (A23) in which both of the epoxy resin (a2) and the epoxy resin (a3) are reacted with the isocyanate compound (b) and the oxazolidone ring-containing epoxy resin , An oxazolidone ring-containing epoxy resin (A123) in which an epoxy resin (a1), an epoxy resin (a2) and an isocyanate compound (b3) of the epoxy resin (a3) are reacted and an unreacted epoxy resin (a3) . The epoxy resin (a3) may be composed of two or more different epoxy resins. In this case, the epoxy resin containing the oxazolidone ring-containing epoxy resin and the unreacted epoxy resin contained in the oxazolidone ring- The number of kinds of the epoxy resin (a) increases, but it is preferable that the epoxy resin in the epoxy resin (a) is two or three kinds.

Further, the epoxy resin composition containing an oxazolidone ring further contains, as a by-product, an epoxy resin having a urethane structure or the like.

As a method for isolating or concentrating each of the epoxy resins (for example, A1, A2, A12, a1, a2, A3, A13, A23, A123, a3, etc.) from the epoxy resin composition containing an oxazolidone ring, There is no specific method, and since each has a molecular weight distribution, it is difficult to isolate or concentrate by a conventional isolation method. Furthermore, since the epoxy resin containing oxazolidone ring contained is similar in structure, it is also difficult to obtain the content by NMR or infrared spectroscopic analysis. In the present invention, since specific effects have been found in these mixtures, they are expressed not by the " oxazolidone ring-containing epoxy resin " but by the " oxazolidone ring-containing epoxy resin composition ". The physical properties of the oxazolidone ring-containing epoxy resin composition of the present invention can be measured by the same operation as the conventional epoxy resin. Therefore, in the epoxy resin composition containing an oxazolidone ring of the present invention, it is not necessary to isolate each epoxy resin from the reactant, but it is also possible to remove a part of the epoxy resin as necessary.

The epoxy equivalent (g / eq.) Of the epoxy resin composition containing an oxazolidone ring is preferably 200 to 600, more preferably 215 to 550, still more preferably 220 to 500. If the epoxy equivalent is too low, the molecular length may be shortened and the adhesion may be deteriorated. In addition, the content of the oxazolidone ring is decreased and the hydroxyl group concentration in the cured product is increased, which may increase the dielectric constant. If the epoxy equivalent is high, the molecular length becomes longer than necessary, and the adverse effects such as deterioration of solvent solubility and increase in resin viscosity may increase. Further, since the crosslinking density of the cured product is lowered, the elastic modulus at the temperature of the solder reflow is lowered, which may cause a serious problem in use.

The softening point is preferably 50 to 150 占 폚, more preferably 55 to 135 占 폚, and even more preferably 60 to 120 占 폚 in the case of being used for a prepreg or a film material. In this case, there is no concern that the softening point will be too low, so there is no need to worry about the lower limit value. When the softening point is high, the resin viscosity is high, and the impregnation property of the prepreg deteriorates, the solubility of the solvent deteriorates, and the diluting solvent remains in the resin without volatilization when heated and dried, There is a concern that it will become a big problem.

The epoxy resin (a) used for obtaining the oxazolidone ring-containing epoxy resin composition of the present invention contains the epoxy resin (a1) and the epoxy resin (a2) as essential components, and the epoxy resin (a1) and the epoxy resin (a2) is 55 to 100 mass% in the epoxy resin (a), the epoxy resin (a1) is 5 to 50 mass% in the epoxy resin (a), and the total of the epoxy resin (a1) and the epoxy resin (a2) Of the epoxy resin (a3) in an amount of less than 45 mass%.

The epoxy equivalent of the epoxy resin (a) is preferably 100 to 500, more preferably 150 to 300. The epoxy equivalent is obtained by carrying out measurement after mixing the whole epoxy resin containing the epoxy resin (a1) and the epoxy resin (a2). When the epoxy equivalent of the epoxy resin to be used is already known, it may be obtained by calculation.

The alcoholic hydroxyl group of the epoxy resin (a) reacts with the isocyanate to form a urethane bond, which may lower the heat resistance (glass transition point) of the cured product. In addition, since the concentration of hydroxyl groups in the cured product increases, there is a risk of increasing the dielectric constant of the cured product. Therefore, the alcoholic hydroxyl group equivalent (g / eq.) In the epoxy resin (a) is preferably 1,000 or more, more preferably 3,000 or more, and still more preferably 5,000 or more. The alcoholic hydroxyl equivalent is determined by carrying out measurement after mixing the whole epoxy resin containing the epoxy resin (a1) and the epoxy resin (a2). The larger the alcoholic hydroxyl group equivalent, the smaller the alcoholic hydroxyl group. For example, when m in the formula (1) and n in the formula (2) are 0, the alcoholic hydroxyl group is eliminated and the alcoholic hydroxyl group equivalent is theoretically infinite.

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

In the above formula (1), X represents a cycloalkylidene group having 5 to 8 ring atoms having a substituent. The substituent is an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms, and has at least one of them. The number of substituents may be one or two or more.

The cycloalkane ring constituting the cycloalkylidene group having 5 to 8 ring atoms is preferably a cyclopentane ring, a cyclohexane ring, a cycloheptane ring or a cyclooctane ring, and is preferably a cyclopentane ring or a cyclohexane ring.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl. Examples of the aryl group having 6 to 10 carbon atoms or the aralkyl group having 7 to 11 carbon atoms include a phenyl group, a benzyl group, a tolyl group and an o-xylyl group, but not limited thereto, And may be different. A preferable substituent is a methyl group or a phenyl group from the viewpoints of ease of obtaining and physical properties such as adhesiveness in laminate.

Further, the cycloalkylidene group is preferably a 1,1-cycloalkylidene group, and the above-mentioned substituent is preferably a cyclic alkylidene group in which the cyclic alkylidene group is substituted by a cycloalkylidene group, The object of the present invention is to improve the dielectric properties and improve the heat resistance by restricting the mobility of the alkane ring. This substitution position may be bonded at any position as far as it can restrict motility, but it is preferable that the substitution position is bonded to a carbon atom close to the 1-position of the cycloalkylidene group. The position of a preferable substituent is a carbon atom at the 2-position or 5-position in the cyclopentane ring. Is a carbon atom at the 2-position, 3-position, 5-position or 6-position in the cyclohexane ring, more preferably a carbon atom at the 2- or 6-position. In the cycloheptane ring, the carbon atom at the 2-position, the 3-position, the 6-position, or the 7-position is more preferable the carbon atom at the 2- or 7-position. In the cyclooctane ring, the carbon atom at the 2-position, the 3-position, the 4-position, the 6-position, the 7-position or the 8-position is more preferable the carbon atom at the 2-, 3-, Is a carbon atom at the 2-position or the 8-position.

The number of substituents is required to be at least one for the above-mentioned reasons, but from the viewpoint of heat resistance when a cured product is formed, three or more is preferable, and three is more preferable.

In the formula (1), the -O- group (ether bond) is preferably an ortho or para position with respect to the carbon atom bonded to X, and more preferably a para position.

In formula (1), each R ¹ independently represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, ≪ / RTI > Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group and a hexyl group, and a cycloalkyl group having 5 to 8 carbon atoms Examples of the alkenyl group having 1 to 4 carbon atoms include a 1-propenyl group and a 2-propenyl group. Examples of the alkenyl group having 1 to 4 carbon atoms include an aryl group having 6 to 10 carbon atoms or an aryl group having 7 to 10 carbon atoms Examples of the alkyl group include a phenyl group, a benzyl group, a phenethyl group, a 1-phenylethyl group, and a naphthyl group, but are not limited thereto and may be the same or different. Preferable R ¹ is a 1-phenylethyl group or a methyl group from the viewpoints of ease of availability and physical properties such as heat resistance when made into a cured product. The substitution position of R < ¹ > is preferably an ortho or meta position with respect to the carbon atom bonded to X, and more preferably an ortho position. K1 is independently 0, 1, 2, 3, or 4, preferably 0, 1 or 2;

In the formula (1), m is a repeating number, and the average value (number average) is 0 to 2, preferably 0 to 1, more preferably 0 to 0.5, and more preferably 0 to 0.3 . It is preferable that the number of repetitions (integer) is usually in the range of 0 to 2. Or may be a single compound in which the number of repeats is any one of 0 to 2, and m is a multiple of 0 to 2. In the epoxidation of an ordinary polyhydric hydroxy resin with epichlorohydrin or the like, it is obtained as a mixture, so that it is advantageous that the mixture can be used as it is.

In the formula (2), R ² , k ² and n have the same meanings as R ¹ , k ¹ and m in the formula (1), respectively, but they can be changed independently of each other.

The substitution position of R ² is preferably an ortho or meta position with respect to the carbon atom of the biphenyl bond, and more preferably an ortho position. The -O- group is preferably an ortho or para position with respect to the carbon atom of the biphenyl bond, more preferably a para position.

The epoxy resin (a1) can be obtained by a method in which a phenol compound containing a cycloalkylidene group represented by the following formula (3) is reacted with epihalohydrin in the presence of an alkali such as sodium hydroxide or a method in which a cycloalkylidene A method in which a phenol compound containing an allyl group is allyl etherified with an allyl ether compound and then an allyl group is oxidized with an oxidizing agent such as a peroxide to effect epoxidation.

(2)

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

The epoxy equivalent of the epoxy resin (a1) is preferably 100 to 500, more preferably 150 to 300. The alcoholic hydroxyl group equivalent is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 5,000 or more.

The phenol compounds represented by the formula (3) are obtained by reacting corresponding cyclic aliphatic ketones and phenols, respectively. Specifically, phenolic compounds containing a cycloalkylidene group as shown below can be mentioned, but the present invention is not limited thereto.

(3)

The phenol compounds containing these exemplified cycloalkylidene groups can be prepared, for example, by the method disclosed in Japanese Unexamined Patent Application Publication No. 4-282334 or Japanese Unexamined Patent Publication No. 201-5-51935, but they are also available as commercial products, BisP-nBZ and BisOEP-2HBP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), bisphenol-A- And the like.

Examples of the epoxy resin (a1) include 4,4'- (2-methylcyclohexylidene) diphenol glycidyl ether, 4,4 '- (3-methylcyclohexylidene) diphenol glycidyl 4,4'- (3,3,5-trimethylcyclohexylidene) diphenol glycidyl ether, 4,4 '- (4-methylcyclohexylidene) diphenol glycidyl ether, , 4 '- (3,3,5-trimethylcyclohexylidene) -bis-phenylphenol glycidyl ether, 4,4' - (3,3,5-trimethylcyclohexylidene) Glycidyl ether, 4,4 '- (3,3,5-trimethylcyclohexylidene) -bis-dimethylphenol glycidyl ether, 4,4' - (3,3,5-trimethylcyclohexylidene ) -Bis-t-butylphenol glycidyl ether. However, the epoxy resin is not limited thereto, and these epoxy resins may be used alone or in combination of two or more.

The epoxy resin (a1) is preferably a compound represented by the following formula (4) obtained from 4,4 '- (3,3,5-trimethylcyclohexylidene) diphenol and epihalohydrin in terms of ease of availability and good physical properties of the cured product ) Is suitable.

[Chemical Formula 4]

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

The epoxy resin (a2) can be obtained by a method in which a biphenol compound represented by the following formula (5) and epihalohydrin are reacted in the presence of an alkali such as sodium hydroxide or a method in which a biphenol compound represented by the formula (5) , Followed by epoxidation by oxidizing an allyl group with an oxidizing agent such as a peroxide or the like.

[Chemical Formula 5]

In the formula, R ^2, and k2 are respectively the same meaning as R ² and k2 of equation (2).

The epoxy equivalent of the epoxy resin (a2) is preferably 100 to 500, more preferably 150 to 300. The alcoholic hydroxyl group equivalent is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 5,000 or more.

Examples of the biphenol compound represented by the formula (5) include 4,4'-biphenol, 2,4'-biphenol, 2,2'-biphenol, 3,3'- Dimethyl-4,4'-biphenol, 3,3'-dimethyl-4,4'-biphenol, 2,2 ', 6,6'-tetramethyl- , 2 ', 5,5'-tetramethyl-4,4'-biphenol, 2,2', 3,3 ', 6,6'-hexamethyl-4,4'- Diethyl-4,4'-biphenol, 3,3'-diethyl-4,4'-biphenol, 2,2 ', 6,6'-tetraethyl- , 2 ', 5,5'-tetraethyl-4,4'-biphenol, 2,2'-diallyl-4,4'-biphenol, 3,3'-diallyl- Phenol, 2,2 ', 6,6'-tetraallyl-4,4'-biphenol, 2,2', 5,5'-tetraallyl-4,4'-biphenol, 2,2 ', 5 , 5'-tetra-t-butyl-4,4'-biphenol, 2,2 ', 6,6'-tetra- 4,4'-biphenol, 2,2 ', 3,3', 5,5'-hexamethylbiphenyl-4,4'-diol But are not limited to these. These biphenol compounds may be used alone or in combination of two or more. Particularly, when 4,4'-biphenol is used, it is preferably used in combination with other biphenol compounds.

These exemplified phenol compounds are also available as a commercial product and are commercially available under the trade names BP, 26X-BP, TTB-BP, DM-BP, PCR-BP, TMP-BP and 24B- And the like.

Examples of the epoxy resin (a2) include 4,4'-bis (glycidyloxy) biphenyl, 2,2'-bis (glycidyloxy) biphenyl, 3,3 ' (Glycidyloxy) biphenyl, 3,3'-dimethyl-4,4'-bis (glycidyloxy) biphenyl, 3,3 ', 5,5' Tetrabutyl-4,4'-bis (glycidyloxy) biphenyl, 3,3'-cyclohexyl-4,4'-bis (glycidyloxy) biphenyl, Diphenyl-4,4'-bis (glycidyloxy) biphenyl, and the like. However, the epoxy resins may be used alone or in combination of two or more.

The epoxy resin (a2) is preferably an epoxy resin (a2) which is obtained from 2,2 ', 6,6'-tetramethyl-4,4'-biphenol and epihalohydrin obtained from the following formula ) Is suitable.

[Chemical Formula 6]

In the formula, n has the same meaning as n in the formula (2).

The mixing ratio of the epoxy resin (a1) to the epoxy resin (a2) is 1/9 to 9/1 in mass ratio, but the epoxy resin (a1) needs to be contained in the epoxy resin (a) in an amount of 5 to 50 mass% have. When the amount of the epoxy resin (a1) is more than 50% by mass, heat resistance and adhesiveness may not be sufficiently exhibited, and flame retardancy may be insufficient in a flame retardant formulation using a phosphorus flame retardant. The amount of the epoxy resin (a2) to be used varies depending on the amount of the epoxy resin (a1) to be used, and the total amount of the epoxy resin (a1) and the epoxy resin (a2) to be used is required to be 55 mass% or more. That is, the amount of the epoxy resin (a2) to be used is in the range of 50 to 95 mass% when the epoxy resin (a1) is 5 mass%, and is used in the range of 5 to 50 mass% .

If the total amount is less than 55 mass%, there is a fear that the dielectric properties become insufficient.

The blend ratio (a1 / a2) of the epoxy resin (a1) and the epoxy resin (a2) in the epoxy resin (a) is preferably 5 to 50/95 to 50, more preferably 25 to 40/75 to 55 , And more preferably 40 to 45/60 to 55.

As the epoxy resin (a), an epoxy resin (a3) other than the epoxy resin (a1) and the epoxy resin (a2) may be used in an amount of 45 mass% or less in combination, so long as the effect of the present invention is not impaired. In this case, the mixing ratio of the epoxy resin (a1) to the epoxy resin (a2) is preferably 4/6 to 5/5 by mass ratio. The purpose of using the epoxy resin (a3) in combination is to impart other properties such as, for example, further improvement in solvent solubility. Therefore, the use amount of the epoxy resin (a3) is preferably as small as possible, more preferably 35 mass% or less, still more preferably 20 mass% or less, and particularly preferably 10 mass% or less.

The epoxy equivalent of the epoxy resin (a3) is preferably 100 to 500, more preferably 170 to 300. The alcoholic hydroxyl group equivalent is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 5,000 or more.

Examples of the epoxy resin (a3) which can be used in combination include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, bisphenol fluorene type epoxy resin, naphthalene diol type epoxy resin, bisphenol S type epoxy resin Cresol novolak type epoxy resin, alkyl novolak type epoxy resin, styrenated phenol novolak type epoxy resin, phenol novolak type epoxy resin, Polyglycidyl ether compounds such as naphthol novolak type epoxy resin,? -Naphthol aralkyl type epoxy resin, dinaphthol aralkyl type epoxy resin,? -Naphthol aralkyl type epoxy resin and biphenyl aralkyl phenol type epoxy resin, diamino Diphenylmethane tetraglycidyl ether, N, N, N ', N'-tetraglycidyl-1,3-benzene di (methanamine) Polyglycidyl ester compounds such as lycidyl amine compounds and dimeric acid type epoxy resins, and alicyclic epoxy compounds such as alicyclic epoxy resins. However, the epoxy resin is not limited to these, and these epoxy resins may be used alone , Or two or more types may be used in combination.

Of the epoxy resin (a3) that can be used in combination, bisphenol AF type epoxy resin having an epoxy resin or a fluorine atom containing an aliphatic substituent group in the molecule is preferable for the purpose of lowering the dielectric constant. For the purpose of further improving the heat resistance, An adult phenol novolak type epoxy resin and a cresol novolak type epoxy resin are preferable. For the purpose of raising the refractive index and further improving the heat resistance, bisphenol S type epoxy resin or bisphenol fluorene type epoxy resin is preferable, and for the purpose of enhancing thermal conductivity A diphenyl ether type epoxy resin or a benzophenone type epoxy resin is preferable, and for the purpose of decreasing the viscosity, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin is preferable, but not limited thereto.

To prepare the epoxy resin composition containing an oxazolidone ring of the present invention, an isocyanate compound (b) is used together with the epoxy resin (a). By the reaction of the epoxy resin (a) and the isocyanate compound (b), an epoxy resin composition containing a desired oxazolidone ring can be obtained. The isocyanate compound (b) may be an isocyanate compound having an average of not less than 1.8 isocyanate groups (-N = C = O) in the molecule, and may be an isocyanate compound for known purpose. Although the monofunctional isocyanate compound may be contained in a small amount, it is effective for the purpose of lowering the degree of polymerization because it becomes a terminal group, but is not preferable for the purpose of the present invention because the degree of polymerization is not increased.

Specific examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,5-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethyl xylylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, (Methylene) diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, naphthalene-1,4-diylbis Isocyanate, p-phenylenediisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbisphenyl-4,4'-diisocyanate, 2,3'-dimethoxybisphenyl- - diisocyanate, diphenylmethane-4,4'-diisocyanate Dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfide-4,4'- Diisocyanate, diphenylsulfone-4,4'-diisocyanate, bicyclo [2.2.1] heptane-2,5-diylbis methylene diisocyanate, bicyclo [2.2.1] heptane-2,6- Diisocyanate, isophorone diisocyanate, 4,4'-methylenebiscyclohexyldiisocyanate, lysine diisocyanate, 1,1-bis (isocyanatomethyl) cyclohexane, 1,2-bis (isocyanatomethyl) Cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4-methyl-1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, Cyclohexylene diisocyanate, 2-methyl-1,3-cyclohexylene diisocyanate, 1-methylbenzene-2,4-diisocyanate Methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl Diisocyanate, butane-1,1-diisocyanate, butane-1,1-diisocyanate, butane-1,1-diisocyanate, isobutylene diisocyanate, Butene-1,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methylbutane- , Pentane-1,5-diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, , Nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate , And trifunctional isocyanate compounds such as triphenylmethane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bicycloheptane triisocyanate, tris Phenyl) thiophosphate, lysine ester triisocyanate, undecane triisocyanate, tris (4-phenylisocyanate thiophosphate) -3,3 ', 4,4'-diphenylmethane tetraisocyanate, and polymethylene polyphenyl isocyanate. Isocyanate compounds, block-type isocyanates masked by blocking agents such as alcohols and phenols, bis-urethane compounds, etc., but not limited thereto, and these isocyanates The compounds may be used alone or in combination of two or more. It is.

Of these isocyanate compounds, bifunctional isocyanate compounds or trifunctional isocyanate compounds are preferable, and bifunctional isocyanate compounds are more preferable. If the number of functional groups of the isocyanate compound is large, there is a fear that the storage stability is lowered, and if it is small, heat resistance and dielectric properties may not be improved.

Particularly preferred isocyanate compounds (b) are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,5-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, Phenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-xylylenediisocyanate, p-xylylene diisocyanate, tetramethyl xylylene diisocyanate, 1,4-naphthalenediyl diisocyanate, 1,5- Naphthalene diisocyanate, 2,7-naphthalene diisocyanate, 3,3'-dimethylbisphenyl-4,4'-diisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, Cyclohexane-1,3-diylbis methylene diisocyanate, cyclohexane-1,4-diylbis methylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 4,4'-methylenebiscyclohexyl diisocyanate, bicyclo [2.2.1] heptane-2,5-diyl At least one selected from the group consisting of bismethylene diisocyanate, bicyclo [2.2.1] heptane-2,6-diylbis methylene diisocyanate, and isophorone diisocyanate.

The reaction of the epoxy resin (a) and the isocyanate compound (b) can be carried out by a known method. Specific reaction methods include: 1) removing the water in the epoxy resin by melting the epoxy resin (a) and drying gas purging or reducing the pressure in the system, and then adding the isocyanate compound (b) (2) a method in which the epoxy resin (a) and the catalyst are mixed in advance and the moisture in the epoxy resin is removed by a method such as dry gas purge or depressurization in the system, and then the isocyanate compound And the reaction is carried out. The water content in the system at this time is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less. In any of these methods, a non-reactive solvent may be used if necessary, for example, when the resin viscosity is high and stirring is difficult.

The amount of the epoxy resin (a) and the isocyanate compound (b) to be used is preferably in the range of from 0.02 mol or more to less than 0.5 mol, and more preferably, 0.1 mol or more per 1 mol of the epoxy group of the epoxy resin (a) More preferably in the range of 0.15 mol or more and 0.4 mol or less, and particularly preferably in the range of 0.2 mol or more and 0.35 mol or less. When the ratio of the isocyanate groups is low, the amount of the oxazolidone ring to be formed is lowered, and the effect of improving the dielectric properties and heat resistance of the cured product may not be obtained. When the proportion of the isocyanate group is large, not only the amount of the epoxy group remaining is reduced but also the increase in viscosity during the reaction is intense and the reaction becomes difficult. In addition, even if it is obtained, the solvent solubility and the impregnation property with the glass cloth deteriorate, making it difficult to use in laminate applications.

The reaction mechanism for forming an oxazolidone ring is as described in Patent Document 4. The epoxy group of the epoxy resin (a) and the isocyanate group of the isocyanate compound (b) react with each other to form an oxazolidone ring by adding a catalyst to the epoxy resin (a) and the isocyanate compound (b). When the epoxy resin (a) contains an alcoholic hydroxyl group, the isocyanate group of the isocyanate compound (b) undergoes an addition reaction with an alcoholic hydroxyl group to form a urethane bond. The addition temperature of the catalyst is preferably from room temperature to 150 ° C, more preferably from room temperature to 100 ° C.

Examples of the catalyst that can be used include lithium compounds, complex salts of boron trifluoride, quaternary ammonium salts, tertiary amines, phosphines, phosphonium salts, a combination of triphenylantimony and iodine, and alkali metal hydroxide And the like. However, the catalysts are not limited to these catalysts. These catalysts may be used alone, or two or more catalysts may be used in combination. Alternatively, it may be divided into several circuits and used. Of these catalysts, quaternary ammonium salts, tertiary amines, phosphines or phosphonium salts are preferred, and tetramethylammonium iodide is more preferred in terms of reaction activity and selectivity of the reaction. In the case of a catalyst having a low reaction activity, the reaction time may be prolonged and the productivity may be lowered. On the other hand, in the catalyst having low selectivity for the reaction, polymerization reaction between the epoxy groups proceeds and the desired properties may not be obtained.

The amount of the catalyst is not particularly limited, but is preferably from 0.0001 to 5 mass%, more preferably from 0.0005 to 1 mass%, still more preferably from 0.001 to 0.5 mass%, based on the total mass of the epoxy resin (a) and the isocyanate compound (b) , Still more preferably from 0.002 to 0.2 mass%. If the amount of the catalyst is large, the autocopolymerization reaction of the epoxy group proceeds in some cases, which may increase the resin viscosity. Further, the self-polymerization reaction of the isocyanate is promoted, which may inhibit the formation of the oxazolidone ring. In addition, it remains as an impurity in the resulting resin, and when used as a material for various applications, particularly a laminate or an encapsulating material, there is a fear of lowering the insulating property and lowering the moisture resistance. If the amount of the catalyst is small, there is a fear that the efficiency is lowered in order to obtain the epoxy resin composition containing the oxazolidone ring.

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

The reaction time is preferably 15 minutes to 10 hours from the end of the addition of the isocyanate compound (b), more preferably 30 minutes to 8 hours, further preferably 1 to 5 hours. If the reaction time is short, a large amount of isocyanate group may remain in the product. If the reaction time is long, there is a possibility that the productivity is remarkably lowered.

Further, when the reaction between the epoxy resin (a) and the isocyanate compound (b) is carried out, various modifiers may be further used within the range not affecting the action effect of the epoxy resin composition of the present invention. By using the modifier, it becomes easy to adjust the molecular weight (epoxy equivalent) and the like. The amount to be used is preferably 80 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the epoxy resin (a).

Examples of the modifier that can be used include various phenol compounds such as bisphenols such as bisphenol A and bisphenol F, monopotassium bifunctional phenols such as biphenols, resorcin and hydroquinone, dihydroxynaphthalenes, novolac resins, Phenol resins and polyhydric phenol resins obtained by the condensation reaction of various phenols with various aldehydes and amine compounds, but not limited to these, and these modifiers may be used alone or in combination of two or more. When these modifiers have an aromatic ring, the aromatic ring may be substituted with a substituent having no adverse effects such as an alkyl group and an aryl group.

If necessary, a non-reactive solvent may be used. Examples of the solvent include various hydrocarbons such as hexane, heptane, octane, dimethylbutane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and ethylbenzene, ethers such as dibutyl ether, dioxane, and tetrahydrofuran, Methyl cellosolve, ethyl cellosolve and the like, and glycol ethers such as ethylene glycol dimethyl ether. However, the solvent is not limited to these solvents. These solvents may be used alone or in combination of two or more kinds. They may be mixed and used. The amount of these solvents to be used is preferably 1 to 900 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the epoxy resin (a).

The reaction product obtained as described above is directly or after the removal of a solvent or a catalyst, or a part of unreacted materials or by-products, to obtain an oxazolidone ring-containing epoxy resin composition of the present invention.

Next, the curable resin composition of the present invention will be described.

The curable resin composition of the present invention contains the oxazolidone ring-containing epoxy resin composition of the present invention and a curing agent.

The curing agent is not particularly limited as long as it hardens the epoxy resin, and a curing agent for an epoxy resin such as a phenol curing agent, an acid anhydride curing agent, an amine curing agent, a hydrazide curing agent, an active ester curing agent, have. These curing agents may be used alone or in combination of two or more. Among these, dicyandiamide, a phenol-based curing agent or an active ester-based curing agent is preferable, and a phenol-based curing agent or an active ester-based curing agent is more preferable.

The amount of the curing agent to be used is preferably 0.2 to 1.5 moles, more preferably 0.3 to 1.5 moles, and more preferably 0.5 to 1.5 moles, of the active hydrogen group of the curing agent per mole of the epoxy group of the whole epoxy resin containing the oxazolidone ring- More preferably 1.5 to 1.5 moles, and particularly preferably 0.8 to 1.2 moles. If the active hydrogen group of the curing agent does not fall within this range, the curing will be incomplete and good curing properties may not be obtained. For example, when a phenol-based curing agent or an amine-based curing agent is used, the active hydrogen group is almost equimolarly added to the epoxy group, and when an acid anhydride-based curing agent is used, the acid anhydride group is used in an amount of 0.5 to 1.2 moles, , And 0.6 to 1.0 moles of the compound.

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

Specific examples of the phenol resin-based curing agent include bisphenols such as bisphenol A and bisphenol F, dihydroxybenzenes such as resorcin, hydroquinone and di-t-butylhydroquinone, dihydroxy naphthalene, trihydroxy Naphthalene, phenols such as phenol novolac resin, cresol novolak resin, trishydroxyphenylmethane novolac resin, naphthol novolak resin, and / or naphthol and condensation products of aldehydes and / or condensation products Water and the like.

In this case, examples of the phenol include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol and the like. Examples of the naphthols include 1-naphthol, 2-naphthol, and the like. Examples of the aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, maronaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde, Aldehyde, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like. Examples of the condensing agent include xylylene glycol, bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, bis (chloromethyl) biphenyl and the like.

Further, a benzoxazine photographic compound which is opened to form a phenol compound upon heating is also useful as a curing agent. For example, a benzoxazine compound of bisphenol F type or bisphenol S type, but the present invention is not limited thereto.

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

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

Examples of the active ester-based curing agent include reaction products of a polyfunctional phenolic compound and an aromatic carboxylic acid described in Japanese Patent No. 5152445. Epiclon HPC-8000-65T (product name, manufactured by DIC Co., Ltd.) .

As the other curing agent, for example, a phosphine compound such as triphenylphosphine, a phosphonium salt such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl- Imidazoles such as imidazole, trimellitic acid, isocyanuric acid, boric acid and the like, imidazole salts such as imidazole, Salts with diazabicyclo compounds and phenols and phenol novolak resins, complexes with boron trifluoride and amines or ether compounds, aromatic phosphonium salts, or iodonium salts such as iodonium salts And the like.

If necessary, a curing accelerator may be used. 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 , Tertiary amines such as 1,8-diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine and triphenylphosphine triphenylborane , Tin octylate, and the like. The curing accelerator is used in an amount of 0.02 parts by mass to 5 parts by mass based on 100 parts by mass of the epoxy resin component in the epoxy resin composition of the present invention. By using the curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

If necessary, an epoxy resin other than the oxazolidone ring-containing epoxy resin composition of the present invention may be used as long as the physical properties of the curable resin composition are not impaired. Examples of the epoxy resin that can be used include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, hydroquinone type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol S type epoxy resin , Bistiooether type epoxy resin, resorcinol type epoxy resin, biphenylaralkylphenol type epoxy resin, naphthalene diol type epoxy resin, phenol novolak type epoxy resin, styrenated phenol novolak type epoxy resin, cresol novolak type epoxy A naphthol novolak type epoxy resin, a? -Naphthol aralkyl type epoxy resin, a dinaphthol aralkyl type epoxy resin, an? -Naphthol aralkyl type epoxy resin, a tris Phenyl methane type epoxy resin, tetrahydroxyphenyl ethane type epoxy resin, dicyclopentadiene type A polyglycidyl ether compound of an aliphatic cyclic epoxy resin, a diaminodiphenylmethane type epoxy resin, a meta-xylene diamine type epoxy resin, a 1,3-bisaminomethylcyclohexane A polyglycidylamine compound such as an epoxy resin, an isocyanurate type epoxy resin, an aniline type epoxy resin, a hydantoin type epoxy resin and an aminophenol type epoxy resin, a dimer acid type epoxy resin, a hexahydrophthalic acid type epoxy resin, etc. Polyglycidyl ester compounds, and alicyclic epoxy compounds. Other examples include urethane-modified epoxy resins (for example, AER4152 (product name, manufactured by Asahi Chemical Industry Co., Ltd.) and the like), oxazolidone ring-containing epoxy resins other than the oxazolidone ring- Butadiene rubber derivatives such as PB-3600 (product name, manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resin [for example, EOTOTO YR-102 and EOTOTO YR- (Manufactured by Tetsu Sumikin Chemical Co., Ltd.)], and the like, but the present invention is not limited thereto. These epoxy resins may be used alone or in combination of two or more.

An organic solvent and / or a reactive diluent may be used in the epoxy resin composition and the curable resin composition of the present invention for adjusting the viscosity. These organic solvents and / or reactive diluents may be used alone or in combination of two or more.

Examples of the organic solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, 1-methoxy-ethyl alcohol, Propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyldiglycol and pine oil, and alcohols such as ethyl acetate, butyl acetate, methoxybutyl acetate, methylcellosolve acetate, Acetic acid esters such as cellosolve acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate and benzyl alcohol acetate, Benzoic acid esters such as methyl benzoate and ethyl benzoate, cellosolves such as methyl cellosolve, cellosolve and butyl cellosolve, carbitols such as methyl carbitol, carbitol and butyl carbitol, benzoic acid esters such as benzene, toluene, Aromatic hydrocarbons such as benzene, toluene and xylene, aromatic hydrocarbons such as benzene, toluene, and the like, sulfoxides such as dimethylsulfoxide, alkanes such as hexane and cyclohexane, acetonitrile and N-methylpyrrolidone.

Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and tolyl glycidyl ether; , Resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether , And propylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylol propane polyglycidyl ether, trimethylol ethane polyglycidyl ether, pentaerythritol polyglycidyl ether, Glycidyl esters such as polyfunctional glycidyl ethers such as glycidyl ethers and ether, and glycidyl esters such as neodecanoic acid, and glycidyl amines such as phenyl diglycidyl amine and tolyldiglycidyl amine.

These organic solvents and / or reactive diluents are preferably used in an amount of 90% by mass or less as non-volatile components, and the appropriate kinds and amounts thereof to be used are appropriately selected depending on the application. For example, in the case of a printed wiring board, it is preferably a polar solvent having a boiling point of 160 캜 or less such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, and the amount thereof is preferably 40 to 80% Do. It is preferable to use, for example, a ketone, an ester of an ester, a carbitol, an aromatic hydrocarbon, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., It is preferably 30 to 60 mass% as nonvolatile matter.

The curable resin composition may be blended with other thermosetting resin or thermoplastic resin to the extent that the properties are not impaired. Examples of the resin include phenol resin, acrylic resin, petroleum resin, indene resin, coumarone resin, phenoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, polyetherimide resin , A polyphenylene ether resin, a modified polyphenylene ether resin, a polyether sulfone resin, a polysulfone resin, a polyether ether ketone resin, a polyphenylene sulfide resin, a polyvinyl formal resin and the like. no.

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

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

Examples of the phosphorus-containing epoxy resin include EPOTOT FX-305, EPOTOT FX-289B, TX-1320A and EPOTOT TX-1328 (trade name, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.) But the present invention is not limited thereto. The epoxy equivalent of the phosphorus-containing epoxy resin is preferably 200 to 800, more preferably 300 to 780, and even more preferably 400 to 760. The phosphorus content of the phosphorus-containing epoxy resin is preferably 0.5 to 6% by mass, more preferably 2 to 5.5% by mass, and still more preferably 3 to 5% by mass.

Examples of phosphorus-containing curing agents include, in addition to phosphorus-containing phenols such as DOPO-HQ, DOPO-NQ and diphenylphosphinylhydroquinone, DOPO and aldehydes With a phenol compound to obtain a phosphorus-containing phenol compound. In this case, DOPO is introduced into the molecule through condensation through an aldehyde in the aromatic ring of the phenolic compound. The phosphorus-containing active ester compound can be obtained from the phosphorus-containing phenol compound having DOPO as a unit structure by further reacting with an aromatic carboxylic acid by the production method shown in Japanese Patent Application Laid-Open No. 2013-185002. In addition, a phosphorus-containing benzooxazine compound having a unit structure of DOPO can be obtained by the production method described in the re-publication patent publication WO2008 / 010429. The phosphorus content of the phosphorus-containing curing agent is preferably 0.5 to 12% by mass, more preferably 2 to 11% by mass, and still more preferably 4 to 10% by mass.

The blending amount of the flame retardant is appropriately selected depending on the kind of the phosphorus-based flame retardant, the component of the curable resin composition, and the degree of desired flame retardancy. For example, the phosphorus content in the organic component (excluding the organic solvent) in the curable resin composition is preferably 0.2 to 6 mass%, more preferably 0.4 to 4 mass%, further preferably 0.5 to 3.5 mass% , And particularly preferably from 0.6 to 3 mass%. When the phosphorus content is low, there is a fear that the flame retardancy can not be ensured, and if it is too much, the heat resistance may be adversely affected. When a phosphorus flame retardant is used, a flame retardant auxiliary such as magnesium hydroxide may be used in combination.

The phosphorus-containing epoxy resin is regarded as being equivalent to both of the phosphorus-based flame retardant and the epoxy resin, and the phosphorus-containing curing agent is deemed to correspond to both of the phosphorus-based flame retarder and the curing agent. Therefore, when a phosphorus-containing epoxy resin is used, another phosphorus flame retardant may not be required. Similarly, when a phosphorus-containing curing agent is used, other curing agent and / or phosphorus-containing flame retardant may not be required.

If necessary, a filler may be used in the curable resin composition. Specific examples of the filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, A fiber, a glass fiber, an alumina fiber, a silica alumina fiber, a silicon carbide fiber, a polyester fiber, a cellulose fiber, an aramid fiber, a ceramic fiber, a particulate rubber, a thermoplastic elastomer and a pigment. Generally, the reason for using the filler is to improve the impact resistance. In addition, when a metal hydroxide such as aluminum hydroxide, boehmite, or magnesium hydroxide is used, it acts as a flame retardant adjuvant and has an effect of improving the flame retardancy. The blending amount of these fillers is preferably 1 to 150 parts by mass, more preferably 10 to 70 parts by mass, per 100 parts by mass of the organic component (excluding organic solvent) in the curable resin composition. If the compounding amount is large, there is a fear that the adhesiveness required for laminated board applications is lowered, and furthermore, the cured product is discarded and sufficient mechanical properties can not be obtained. If the compounding amount is too small, there is a possibility that the effect of compounding the filler may not be exhibited, such as the improvement of the impact resistance of the cured product.

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

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

The curable resin composition of the present invention is obtained by uniformly mixing the above components. By curing the curable resin composition, a cured product such as a laminate, a mold, a molded product, an adhesive layer, an insulating layer, and a film can be obtained. As a method for obtaining the cured product, the same method as the known epoxy resin composition can be employed, and a method inherent to the curable resin composition of the present invention is not required, and a mold, injection, potting, dipping, drip coating, Compression molding, etc., a resin sheet, a resin-coated copper foil, a prepreg, or the like, followed by heating and pressure-curing to form a laminated board. The curing temperature at that time is usually in the range of 100 to 300 占 폚, and the curing time is usually about 10 minutes to 5 hours.

Examples of applications in which the curable resin composition is used include insulating materials for circuit boards such as printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up substrates, semiconductor encapsulating materials, conductive pastes, conductive films, , A resin mold material, an adhesive, and the like. Among these various applications, in the use of a printed wiring board material, an insulating material for a circuit board, and an adhesive film for a build-up, a so-called insulating material for a board for incorporating electronic components, in which passive components such as capacitors, . Among them, a material for a circuit board (laminate) such as a printed wiring board material, a resin composition for a flexible wiring board, an interlayer insulating material for a build-up substrate, and a semiconductor It is preferable to use it for an encapsulating material.

When the curable resin composition is in the form of a plate such as a laminate, the filler to be used is preferably fibrous in view of dimensional stability and bending strength, and is more preferable than a glass fiber cloth in which glass fibers are woven into a mesh.

The prepreg of the present invention used in a printed wiring board or the like can be prepared by impregnating the curable resin composition with a fibrous reinforcing base material. As the fibrous reinforcing base material, inorganic fibers such as glass, woven or nonwoven fabric of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, aromatic polyamide resin and the like can be used, no. The method for producing the prepreg from the epoxy resin composition is not particularly limited. For example, the epoxy resin composition on the varnish containing the organic solvent may be further mixed with an organic solvent to adjust the viscosity of the resin varnish , Impregnating the resinous varnish with the fibrous substrate, and then heating and drying the resin to make the resin component semi-cured (B-staged). The heating temperature is preferably 50 to 200 占 폚, more preferably 100 to 170 占 폚, depending on the kind of the organic solvent used. The heating time is preferably from 1 to 40 minutes, and more preferably from 3 to 20 minutes, depending on the kind of the organic solvent used and the curing property of the prepreg. At this time, the mass ratio of the epoxy resin composition to the reinforcing base material to be used is not particularly limited, but it is usually preferable to adjust the resin content in the prepreg to be 20 to 80 mass%.

The curable resin composition of the present invention can be molded into a sheet or a film. In this case, it is possible to form a sheet or a film using a conventionally known method. The method for producing the adhesive sheet is not particularly limited. For example, a resin varnish is coated on a support base film which is not dissolved in the resin varnish by using a coater such as a reverse roll coater, a comma coater, a die coater Followed by heating and drying to make the resin component B-staged. If necessary, another support base film is laminated on the application side (adhesive layer) as a protective film and dried, whereby an adhesive sheet having a release layer on both sides of the adhesive layer is obtained. Examples of the support base film include a metal foil such as a copper foil, a polyolefin film such as a polyethylene film and a polypropylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, a silicon film and a polyimide film. Is preferably a polyethylene terephthalate film free from defects such as particles and excellent in dimensional accuracy and cost-effective. Further, a metal foil, particularly a copper foil, which is easily laminated, is preferable. The thickness of the support base film is not particularly limited, but is preferably from 10 to 150 占 퐉, more preferably from 25 to 50 占 퐉, in view of strength as a support and difficulty in causing lamination failure. The thickness of the protective film is not particularly limited, but is generally from 5 to 50 탆. Further, in order to easily peel off the formed adhesive sheet, it is preferable to carry out surface treatment with a release agent in advance. The thickness of the resin varnish to be applied is preferably 5 to 200 占 퐉, more preferably 5 to 100 占 퐉 in terms of the thickness after drying. The heating temperature is preferably 50 to 200 占 폚, more preferably 100 to 170 占 폚, depending on the kind of the organic solvent used. The heating time is preferably from 1 to 40 minutes, and more preferably from 3 to 20 minutes, depending on the kind of the organic solvent used and the curing property of the prepreg. The thus-obtained adhesive sheet is usually an insulating adhesive sheet having insulating properties, but a conductive adhesive sheet can also be obtained by mixing metal or metal-coated microparticles having conductivity with the epoxy resin composition. Further, the support base film is peeled off after lamination to a circuit board or after heat-curing to form an insulating layer. When the support base film is peeled off after the adhesive sheet is heated and cured, adhesion of dust or the like in the curing process can be prevented. Here, the insulating adhesive sheet is also an insulating sheet.

A method for producing the laminate of the present invention using the prepreg of the present invention or the above-mentioned insulating adhesive sheet will be described. For example, when a laminate is formed using a prepreg, a laminate is formed by laminating one or a plurality of prepregs and arranging a metal foil on one or both sides of the laminate. By pressurizing and heating the laminate, Are cured and integrated to obtain a laminated board. As the metal foil, copper, aluminum, brass, nickel, or the like alone, an alloy, or a composite metal foil can be used. The conditions under which the laminate is heated and pressed can be appropriately adjusted under the condition that the epoxy resin composition is cured and then heated and pressed. However, if the amount of pressure applied is too low, bubbles remain in the resulting laminate, It is preferable to pressurize under the condition that the moldability is satisfied. The heating temperature is preferably 160 to 250 占 폚, more preferably 170 to 220 占 폚. The pressing pressure is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. Further, the multi-layered plate can be produced by using the thus obtained single-layered laminate as an inner layer material. In this case, a circuit is first formed on the laminate by the additive method or the subtractive method, and the surface of the formed circuit is treated with an acid solution and subjected to a blackening treatment to obtain an inner layer material. An insulating layer is formed of a prepreg or an insulating adhesive sheet on one surface or both circuit forming surfaces of the inner layer material and a conductor layer is formed on the surface of the insulating layer to form a multilayer plate.

In the case of forming an insulating layer with an insulating adhesive sheet, an insulating adhesive sheet is disposed on the circuit forming surface of a plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is disposed between the circuit formation surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressed to be integrally formed, thereby forming a cured product of the insulating adhesive sheet as an insulating layer and forming a multilayer of the inner layer material. Alternatively, a metal foil, which is an inner layer material and a conductor layer, is formed as a cured product of an insulating adhesive sheet as an insulating layer. Here, as the metal foil, the same materials as those used for the laminate used as the inner layer material can be used. The heat press molding can be carried out under the same conditions as the molding of the inner layer material.

In the case of forming the insulating layer by using the prepreg, one laminate of prepregs or a plurality of laminated prepregs is disposed on the circuit formation surface of the inner laminate, and a metal foil is further arranged on the outer side of the laminate. . Then, the laminate is heated and pressed to integrally form a cured product of the prepreg as an insulating layer, and the metal foil on the outside of the prepreg is formed as a conductor layer. Here, as the metal foil, the same materials as those used for the laminate used as the inner laminate can be used. The heat press molding can be carried out under the same conditions as the molding of the inner layer material. A printed circuit board can be formed by performing via hole formation or circuit formation on the surface of the multilayer laminate thus formed by the additive method or the subtractive method. Further, by repeating the above-described method using the printed wiring board as an inner layer material, a multilayered multilayer plate can be further formed.

When the curable resin composition is applied to the laminate to form the insulating layer, the curable resin composition is applied preferably to a thickness of 5 to 100 占 퐉, and then dried at 100 to 200 占 폚, preferably at 150 to 200 占 폚 For 1 to 120 minutes, preferably 30 to 90 minutes, to form a sheet. It is usually formed by a method called casting method. The thickness after drying is preferably 5 to 150 占 퐉, preferably 5 to 80 占 퐉. The viscosity of the curable resin composition is preferably in the range of 10 to 40,000 mPa · s at 25 ° C, more preferably in the range of 200 to 40000 mPa · s, 30000 mPa 占 퐏. A printed wiring board can be formed by performing a via hole formation or a circuit formation on the surface of the multilayered laminate thus formed by the additive method or the subtractive method. Further, by repeating the above-mentioned method using the printed wiring board as an inner layer material, a multilayer laminate can be further formed.

As the encapsulating material obtained by using the curable resin composition of the present invention, there can be used for a semiconductor chip on a tape, a potting liquid encapsulating, an underfill, an interlayer insulating film of a semiconductor, and the like. For example, in the semiconductor package molding, there can be mentioned a method in which an epoxy resin composition is molded using a mold, a transfer molding machine, an injection molding machine or the like, and heated at 50 to 200 DEG C for 2 to 10 hours to obtain a molded product .

In order to prepare the curable resin composition for the semiconductor encapsulating material, it is preferable to mix the curable resin composition with a compounding agent such as an inorganic filler, an additive such as a coupling agent and a releasing agent, And the mixture is thoroughly melted and mixed until homogeneous. In that case, silica is usually used as the inorganic filler. In that case, it is preferable to blend the inorganic filler in a proportion of 70 to 95% by mass in the curable resin composition. When the curable resin composition thus obtained is used as an encapsulating material on a tape, it is heated to produce a semi-cured sheet, and the encapsulating material tape is placed on a semiconductor chip. Deg.] C, softening and molding, and completely curing at 170 to 250 [deg.] C. When used as a potting liquid encapsulant, the resulting curable resin composition may be dissolved in a solvent as required, and then applied to a semiconductor chip or an electronic component and directly cured.

Further, the curable resin composition of the present invention may be further used as a resist ink. In this case, a composition for a resist ink is prepared by blending a vinyl-based monomer having an ethylenically unsaturated double bond and a cation polymerization catalyst as a curing agent, further adding a pigment, a talc and a filler to the epoxy resin composition, A method in which a resist ink is cured after being applied on a printed substrate by a screen printing method. The curing temperature at this time is preferably in the range of about 20 to 250 캜.

The cured product of the present invention can take the form of a laminate, a molded product, an adhesive, a coating film, a film and the like. As a result of evaluating the epoxy resin cured product of the laminate by heat curing, the oxazolidone ring-containing epoxy resin composition of the present invention obtained by reacting the specific epoxy resin (a) with the isocyanate compound (b) , It has a low dielectric property as compared with a conventionally known epoxy resin and has not only a good workability at a low point but also a high flame retardancy and a high adhesive property and can also improve solvent solubility.

Example

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise stated, " part " represents the mass part, and "% " The measurement methods were respectively measured by the following methods. The unit of equivalent is "g / eq.".

(1) Epoxy equivalent:

And measured according to JIS K7236 standard. Specifically, a potentiometric titration apparatus was used, methyl ethyl ketone was used as a solvent, a tetraethylammonium acetic acid bromide solution was added, and a 0.1 mol / l perchloric acid-acetic acid solution was used.

(2) Softening point:

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

(3) Number average molecular weight (Mn), weight average molecular weight (Mw), and dispersion degree (Mw / Mn):

A column (TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL, manufactured by Toso Co., Ltd.) in series was used in the main body (HLC-8220GPC manufactured by Tosoh Corporation), and the column temperature was 40 占 폚. Further, tetrahydrofuran was used as the eluent, the flow rate was 1 ml / min, and a differential refraction detector was used as the detector. Mn, Mw and Mw / Mn were calculated from the calibration curve obtained from standard monodisperse polystyrene.

(4) Solvent Solubility:

The state of dilution with toluene to nonvolatile content of 50% was visually determined. ?, Whitened or separated?, And lightly turbid?

(5) Glass transition temperature:

Measured according to JIS K7121 standard, differential scanning calorimetry. Was measured at a temperature raising rate of 10 占 폚 / min at 20 占 폚 using EXTERDSC6200 manufactured by SII, and was determined from the extrapolated glass transition temperature (Tig) of the DSC chart obtained on the second cycle.

(6) Copper peel strength and interlayer adhesion:

Measured according to JIS C6481. The interlaminar adhesive strength was measured by peeling between the 7th layer and the 8th layer.

(7) Specific dielectric constant and dielectric tangent:

Using a material analyzer (AGILENT Technologies) according to IPC-TM-6502.5.5.9, dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured by a capacitance method.

(8) Flammability:

The evaluation was carried out by the vertical method in accordance with UL94 (Safety Certification Standard of Underwriters Laboratories Inc.), and the sum of the five test piece's afterglow time (second) was shown. The smaller the time of the residual salt, the more preferable is the flame retardancy.

Synthesis Example 1

4,4 '- (3,3,5-trimethylcyclohexylidene) diphenol (manufactured by Honshu Chemical Industry Co., Ltd.) was added to a reaction apparatus equipped with a stirrer, a thermometer, a nitrogen gas introducing apparatus, a cooling tube and a water separator at room temperature , Bisp-TMC), 358 parts of epichlorohydrin and 4 parts of ion-exchanged water were charged, and the mixture was heated to 50 캜 with stirring. After uniformly dissolving, 5.3 parts of a 49% sodium hydroxide aqueous solution was injected and reacted for 3 hours. Next, the temperature was raised to 64 占 폚, the pressure was reduced to such an extent that reflux of water occurred, and 48 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours. Then, water and epichlorohydrin, Separately, epichlorohydrin was returned to the reaction vessel, and water was removed out of the system and reacted. After completion of the reaction, the temperature was raised to 70 캜 and dehydration was carried out, and the temperature was raised to 135 캜 to recover the remaining epichlorohydrin. The pressure was returned to normal pressure, and 204 parts of methyl isobutyl ketone (MIBK) was added and dissolved. 127 parts of ion-exchanged water was added, and the mixture was allowed to stand to dissolve the by-produced salt in water. Next, 2.9 parts of a 49% sodium hydroxide aqueous solution was injected, and the mixture was reacted with stirring at 80 캜 for 90 minutes to carry out a purification reaction. MIBK was added and washed several times to remove ionic impurities. The solvent was recovered to obtain an epoxy resin (epoxy resin a) represented by the above formula (1). The obtained epoxy resin a had an epoxy equivalent of 216, an alcoholic hydroxyl equivalent of 5510, and an average value of m of 0.04.

(Epoxy resin)

Epoxy resin a: Epoxy resin obtained in Synthesis Example 1

Epoxy resin b: biphenyl-type epoxy resin (YX-4000, epoxy equivalent 196, alcoholic hydroxyl equivalent of 5000, manufactured by Mitsubishi Chemical Corporation)

Epoxy resin c: biphenylaralkyl type epoxy resin (NC-3000, epoxy equivalent 275, alcoholic hydroxyl equivalent 4520, manufactured by Nippon Yakusho Co., Ltd.)

(Isocyanate compound)

Isocyanate A: A mixture of 2,4-tolylene diisocyanate (65%) and 2,6-tolylene diisocyanate (35%) (COSMONATE (registered trademark) T-65 manufactured by Mitsui Chemicals SKC Polyurethane Co., %)

Isocyanate B: A mixture of 2,4'-diphenylmethane diisocyanate (50%) and 4,4'-diphenylmethane diisocyanate (50%) (BASF INOAC Polyurethane Co., NCO concentration 33%)

Isocyanate C: Polymethylene polyphenyl polyisocyanate (BASF INOAC Polyurethane Co., Looplanate (registered trademark) M20S, NCO concentration: 31%)

(catalyst)

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

(Hardener)

PN: phenol novolak resin (Shonol (registered trademark) BRG-557, manufactured by Showa Denko K.K., softening point 80 ° C, phenolic hydroxyl group equivalent 105)

DCPD: dicyclopentadiene / phenol cocondensation resin (GDP9140, phenolic hydroxyl equivalent 196, manufactured by Guyi Chemical Co., Ltd.)

DICY: Dicyandiamide (DIHARD, active hydrogen equivalent 21, manufactured by Nippon Carbide Industries Co., Ltd.)

SMA: styrene / maleic acid copolymer resin (SMA2000, acid anhydride equivalent 316, manufactured by Cray Valley)

(Hardening accelerator)

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

(Flame retardant)

LC-950: phosphorus-containing phenol curing agent (LC-950PM60, phenolic hydroxyl equivalent 341, phosphorus content 9.3%, propylene glycol monomethyl ether solution, nonvolatile content 60%

SPB-100: phosphazene-based flame retardant (SPB-100 manufactured by Otsuka Chemical Co., Ltd., phosphorus content: 13%)

Example 1

40 parts of epoxy resin a as the epoxy resin (a1), 60 parts of the epoxy resin b as the epoxy resin (a2) and 0.1 part of TMAI as a catalyst were charged in the same apparatus as in Synthesis Example 1, and the temperature was raised while nitrogen gas was supplied , And the temperature was maintained at 120 캜 for 30 minutes to remove water in the system. Next, 8.6 parts (modification ratio: 20 mol%) of isocyanate A as an isocyanate compound (b) was added dropwise over 3 hours while maintaining the reaction temperature at 130 캜 to 140 캜. After completion of the dropwise addition, stirring was further continued for 3 hours while maintaining the same temperature, to obtain an oxazolidone ring-containing epoxy resin composition (Resin 1).

The epoxy equivalent, the softening point, the molecular weight distribution, and the solvent solubility of the resulting oxazolidone ring-containing epoxy resin composition were measured. The modifying rate represents the percentage of modification of the isocyanate compound (b) by the isocyanate group with respect to 1 equivalent of the epoxy group of the epoxy resin (a) [(b) / (a) x 100]. Here, (a) and (b) represent the number of moles of the epoxy group of the epoxy resin (a) and the number of moles of the isocyanate group of the isocyanate compound (b).

The measurement results are shown in Table 1.

Examples 2 to 8

An epoxy resin composition containing an oxazolidone ring was synthesized by the same operation using the same apparatus as in Example 1, in accordance with the injection amount (parts) of each raw material shown in Table 1. The epoxy equivalent, softening point, molecular weight distribution and solvent solubility of the obtained epoxy resin composition containing an oxazolidone ring were measured in the same manner as in Example 1, and the measurement results are shown in Table 1. The oxazolidone ring-containing epoxy resin compositions obtained in Examples 2 to 8 were referred to Resin 2 to 8.

Comparative Examples 1 to 7

An epoxy resin composition containing an oxazolidone ring was synthesized by the same operation using the same apparatus as in Example 1, with the injection amount (parts) of each raw material shown in Table 2. The epoxy equivalent, softening point, molecular weight distribution, and solvent solubility of the resulting epoxy resin composition containing oxazolidone ring were measured in the same manner as in Example 1, and the measurement results are shown in Table 2. The epoxy resin compositions containing oxazolidone rings obtained in Comparative Examples 1 to 7 were referred to Resin H1 to H7.

Example 9

100 parts of Resin 1 as an epoxy resin, 38 parts of PN as a curing agent, and 0.12 parts of 2E4MZ as a curing accelerator were mixed and dissolved in a mixed solvent adjusted with MEK, propylene glycol monomethyl ether and N, N-dimethylformamide, To obtain a resin composition varnish.

The obtained curable resin composition varnish was impregnated with glass cloth (WEA116E106S136, thickness: 0.1 mm, manufactured by Nitto Denki Co., Ltd.). The impregnated glass cloth was dried in a hot air circulating oven at 150 캜 for 11 minutes to obtain a prepreg. The obtained prepregs were superposed with copper foils (3EC-III, thickness: 35 占 퐉, manufactured by Mitsui Mining & Mining Co., Ltd.), and subjected to vacuum press at 2 MPa at a temperature of 130 占 폚 for 15 minutes + 190 占 폚 for 80 minutes To obtain a 1.0 mm thick laminated plate. The results of the glass transition temperature, the peeling strength of the copper foil, and the interlayer adhesion force of the laminate are shown in Table 3.

The obtained prepreg was loosened and sieved to prepare a 100-mesh-pass powdery prepreg powder. The resulting prepreg powder was placed in a mold made of a fluororesin and subjected to a vacuum press at 2 MPa at a temperature condition of 130 占 폚 for 15 minutes and 190 占 폚 for 80 minutes to prepare a test piece having a thickness of 50 mm x 2 mm ≪ / RTI > The results of the dielectric constant and dielectric tangent of the test pieces are shown in Table 3.

Examples 10 to 20

Resins 2 to 8 of Examples 2 to 8, epoxy resins c, PN, and 2E4MZ were compounded in the blend amounts (parts) shown in Tables 3 and 4, and the same apparatus was used as in Example 9, Laminates and test pieces were obtained. The same tests as in Example 9 were carried out, and the results are shown in Tables 3 and 4.

Comparative Examples 8 to 13

The same operations as in Example 9 were carried out using the resins H1 to H7 of Comparative Examples 1 to 7 and other epoxy resins c, PN and 2E4MZ in the compounding amounts (parts) shown in Table 5, And a test piece. The same test as in Example 9 was carried out, and the results are shown in Table 5.

Examples 21 to 26

The resin 1, 6, 7, 8, PN, 2E4MZ, and the flame retardant of Examples 1 to 8 were blended in the blending amount (parts) of the formulations shown in Table 6 and the same apparatus as in Example 9 was used. And a test piece. The same tests as in Example 9 were carried out, and the results are shown in Table 6. Separately, a test piece for measurement of flame retardancy was prepared by etching both surfaces of the laminate thus obtained, and a flame resistance test was carried out.

Comparative Examples 16 to 19

Resins H1 to H7, PN, 2E4MZ, and flame retardants of Comparative Examples 1 to 7 were compounded in the blend amount (parts) of the formulations shown in Table 7, and the same apparatus as in Example 9 was used to obtain laminated plates and test pieces . The same tests as in Example 9 were carried out, and the results are shown in Table 7. Apart from this, both sides of the obtained laminate were etched to prepare a test piece for flame retardancy measurement, and a flame resistance test was carried out.

Claims (14)

1. An epoxy resin composition comprising an epoxy resin (a) and an isocyanate compound (b), wherein the epoxy resin (a) comprises an epoxy resin (a1) represented by the following formula (1) Wherein the epoxy resin (a1) is a mixture containing 5 to 50 mass% of an epoxy resin (a1), and the total amount of the epoxy resin (a1) and the epoxy resin (a2) is 55 to 100 mass% Epoxy resin composition containing a Jolidone ring.
[Chemical Formula 1]

Wherein X is a cycloalkyl having 5 to 8 ring atoms and having at least one substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms, R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 7 to 10 carbon atoms And k1 and k2 are each independently an integer of 0 to 4. G is a glycidyl group, and m and n are repeating numbers and the average value is 0 to 2.) The method according to claim 1,
When the alcoholic hydroxyl equivalent of the epoxy resin (a) is 1000 g / eq. Or more of an oxazoline ring-containing epoxy resin composition. 3. The method according to claim 1 or 2,
The isocyanate compound (b) is an oxazolidone ring-containing epoxy resin composition having an average of at least 1.8 isocyanate groups in the molecule. 4. The method according to any one of claims 1 to 3,
Epoxy equivalent of 200 to 600 g / eq. An epoxy resin composition containing an oxazolidone ring. 5. The method according to any one of claims 1 to 4,
And having a softening point of 50 to 150 DEG C. The oxazolidone ring- An epoxy resin containing 5 to 50 mass% of an epoxy resin (a1) represented by the following formula (1) and 55 to 100 mass% of a total of an epoxy resin (a1) and an epoxy resin (a2) represented by the following formula (2) (a) and an isocyanate compound (b) are reacted in the presence of a catalyst to produce an oxazolidone ring-containing epoxy resin composition.
(2)

Wherein X is a cycloalkylidene group having 5 to 8 ring atoms and having at least one substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms And k1 and k2 are each independently an integer of 0 to 4. G is a glycidyl group, and m and n are repeating numbers, and the average value is 0 to 2.) The method according to claim 6,
When the alcoholic hydroxyl equivalent of the epoxy resin (a) is 1000 g / eq. Wherein the oxazolidone ring-containing epoxy resin composition is an epoxy resin. 8. The method according to claim 6 or 7,
Wherein the isocyanate compound (b) has an oxazolidone ring having an average of not less than 1.8 isocyanate groups in the molecule. 9. The method according to any one of claims 6 to 8,
Wherein an isocyanate group of the isocyanate compound (b) is in the range of 0.02 mol or more and less than 0.5 mol based on 1 mol of the epoxy group of the epoxy resin (a). A curable resin composition characterized by comprising the epoxy resin composition containing an oxazolidone ring according to any one of claims 1 to 5 and a curing agent. 11. The method of claim 10,
Wherein the curing agent is an epoxy resin curing agent having an active hydrogen group and the active hydrogen group of the curing agent is 0.2 to 1.5 moles per mole of the epoxy group of the whole epoxy resin in the curable resin composition. A cured product obtained by curing the curable resin composition according to claim 10 or 11. 11. A prepreg obtained from the curable resin composition according to claim 10 or claim 11. A laminate obtained from the curable resin composition according to claim 10 or 11.