TW201835136A - Oxazolidone ring-containing epoxy resin, method for producing thereof, curable resin composition and cured product having excellent properties of high heat resistance, low dielectric constant, low dielectric loss tangent and high adhesion - Google Patents

Abstract

The present invention provides an epoxy resin composition containing an oxazolidone ring which is excellent in adhesion, dielectric properties, and flame retardancy, and is useful as an epoxy resin for electronic circuit boards. An epoxy resin composition, containing an oxazolidone ring, is obtained from an epoxy resin (a) and an isocyanate compound (b), and the epoxy resin (a) comprises a bisphenol type epoxy resin (a1) represented by the following formula (1) and a biphenyl type epoxy resin (a2) represented by the following formula (2); wherein the epoxy resin (a1) is 5% by mass to 50% by mass and the total amount of the epoxy resin (a1) and the epoxy resin (a2) is from 55% by mass to 100% by mass. In the formula, X is a cycloalkylene group having 5 to 8 ring members having an alkyl group, an aryl group or an aralkyl group as a substituent.

Description

An oxazolidone ring-containing epoxy resin composition, a method for producing the same, a curable resin composition, and a cured product

The present invention relates to an oxazolidone ring-containing epoxy resin composition, a method for producing an epoxy resin composition, and a method for producing an epoxy resin composition that provides a hardened product with excellent low dielectric properties, high heat resistance, and high adhesion. An oxygen resin composition is a curable resin composition as an essential component, a cured product obtained from the curable resin composition, a prepreg, and a laminated board.

Epoxy resins are used in coatings, civil bonding, casting, electrical and electronic materials, and film materials due to their excellent adhesion, flexibility, heat resistance, chemical resistance, insulation, and hardening reactivity. In particular, in the use of printed wiring boards as one of electrical and electronic materials, it is widely used by imparting flame retardancy to epoxy resins.

Infrastructure equipment such as portable devices or base stations connected to the printed wiring board is one of the uses of the printed wiring board. With the rapid increase in the amount of information in recent years, there has been a demand for high functionality. In portable devices, high-level multilayers or micro-wiring are used for the purpose of miniaturization. In order to make substrates thinner, materials with lower dielectric constants are required. The micro-wiring reduces the bonding surface. Higher bonding materials. In a substrate for a base station, in order to suppress attenuation of a high-frequency signal, a material having a lower dielectric loss tangent is required.

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

Regarding the lowering of the dielectric constant of epoxy resins, Patent Document 1 discloses 4,4 '-[1,3-phenylenebis (1-methylethylene)] bis [2,6-dimethyl ] A diglycidyl etherate of phenol. In addition, Patent Document 2 discloses an epoxy resin obtained by reacting an epoxy resin having an alcoholic hydroxyl equivalent of 1,000 g / eq. Or more (1.0 meq / g or less) with an isocyanate compound having two or more isocyanate groups in the molecule. Resin, it has been revealed that the epoxy resin polymerized by the oxazolidone ring has a low dielectric constant, a low dielectric loss tangent, and a high glass transition temperature.

An oxazolidone ring-containing epoxy resin obtained by reacting an epoxy resin with an isocyanate is also disclosed in Patent Document 3. As a raw material epoxy resin, there are the following examples: Compounds obtained by glycidization, compounds obtained by glycidation of tris (glycidyloxyphenyl) alkanes, aminophenols, etc., or glycidol of novolacs, such as phenol novolac A compound obtained by amination.

Regarding the reduction of the dielectric constant of an epoxy resin, Patent Document 4 discloses that as a raw material epoxy resin, glycidylation of a dihydric phenol obtained by reacting a cyclic aliphatic ketone with a phenol is disclosed. A compound and an oxazolidone ring-containing epoxy resin obtained by reacting an isocyanate compound having two or more isocyanate groups in a molecule.

Regarding the high heat resistance of epoxy resins, Patent Document 5 discloses that a raw material epoxy resin is obtained by reacting a tetramethylbiphenol-type epoxy resin with an isocyanate compound having two or more isocyanate groups in the molecule. Epoxy.

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

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 5-293929 [Patent Literature 2] Japanese Patent Laid-Open No. 9-278867 [Patent Literature 3] Japanese Patent Laid-Open No. 5-43655 [Patent Literature 4] ] Japanese Patent Laid-Open Publication No. 2016-169362 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2016-69563

[Problems to be Solved by the Invention] Therefore, the problem to be solved by the present invention is to provide properties that are excellent in low dielectric properties, high heat resistance, and high adhesion, and are useful in applications such as lamination, molding, casting, and adhesion. Epoxy resin composition, a curable resin composition using the epoxy resin composition as an essential component, and a cured product thereof. [Technical means to solve the problem]

In order to solve the above problems, the present inventors made intensive studies on materials having a low dielectric constant and a low dielectric loss tangent. As a result, they found that a mixture of an epoxy resin having two specific epoxy resins as essential components and an isocyanate compound were used. The oxazolidone ring-containing epoxy resin composition obtained by the reaction can simultaneously achieve the low dielectric constant, low dielectric loss tangent, and high flame retardancy that are not present, and the adhesion is also good. .

That is, the present invention is an oxazolidone ring-containing epoxy resin composition, which is an oxazolidone ring-containing epoxy resin composition obtained from an epoxy resin (a) and an isocyanate compound (b), and The epoxy resin (a) is a mixture of the epoxy resin (a1) represented by the following formula (1) and the epoxy resin (a2) represented by the following formula (2) as essential components. The epoxy resin (a1) is 5 mass% to 50 mass%, and the total amount of the epoxy resin (a1) and the epoxy resin (a2) is 55 mass% to 100 mass%.

[Chemical 1] In the formula, X is a ring member 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. 5 to 8 cycloalkylene. R ¹ and R ² are each independently 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 7 to 10 carbon atoms An aralkyl group of 10, k1 and k2 are each independently an integer of 0 to 4. G is glycidyl. m and n represent the number of repetitions, and the average value is 0 to 2.

In addition, the present invention is a method for producing an oxazolidone ring-containing epoxy resin composition, characterized in that, in the presence of a catalyst, 5% to 50% by mass of the formula (1) is included. Epoxy resin (a1), epoxy resin (a) containing epoxy resin (a1) and epoxy resin (a2) represented by the formula (2) in a total amount of 55 mass% to 100 mass%, Reacts with isocyanate compound (b).

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

1) The epoxy group (a) has an alcoholic hydroxyl equivalent of 1,000 g / eq. Or more. 2) The isocyanate compound (b) has an average of 1.8 or more isocyanate groups in the molecule. 3) The epoxy equivalent of the oxazolidone ring-containing epoxy resin composition is 200 g / eq. To 600 g / eq. 4) The softening point of the oxazolidone ring-containing epoxy resin composition is 50 ° C to 150 ° C. 5) The isocyanate group of the isocyanate compound (b) is in a range of 0.02 mol or more and less than 0.5 mol with respect to 1 mol earring oxy group of the epoxy resin (a).

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

The active hydrogen group of the hardener is preferably 0.2 moles with respect to 1 mole of the epoxy group of all epoxy resins including the oxazolidone ring-containing epoxy resin composition in the curable resin composition. Ears ~ 1.5 moles.

Furthermore, this invention is a hardened | cured material which hardened | cured the said curable resin composition. Moreover, this invention is a prepreg and a laminated board obtained from the said curable resin composition.

[Effects of the Invention] The cured product of the epoxy resin composition and the curable resin composition containing the epoxy resin composition of the present invention exhibits hardened physical properties with high flame retardance while maintaining adhesion. Furthermore, it has excellent dielectric characteristics, and exhibits good characteristics in a multilayer board and an electronic circuit board that require a low dielectric constant and a low dielectric loss tangent.

Hereinafter, embodiments of the present invention will be described in detail. The 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 includes an oxazolidone ring-containing epoxy resin (A1) and an epoxy resin (a2) obtained by reacting an epoxy resin (a1) with an isocyanate compound (b) alone. An oxazolidone ring-containing epoxy resin (A2) obtained by reacting with an isocyanate compound (b) alone, and both an epoxy resin (a1) and an epoxy resin (a2) react with an isocyanate compound (b) The oxazolidone ring-containing epoxy resin (A12) further contains unreacted epoxy resin (a1) and epoxy resin (a2).

The epoxy resin (a) may include an epoxy resin (a1) and an epoxy resin (a3) other than the epoxy resin (a2). In this case, the oxazolidone ring-containing epoxy resin (A3), the epoxy resin (a1), and the epoxy resin (a3), which are obtained by reacting the epoxy resin (a3) with the isocyanate compound (b) alone, are further included. ) An oxazolidone ring-containing epoxy resin (A13), an epoxy resin (a2), and an epoxy resin (a3) obtained by reacting the two with an isocyanate compound (b), and The oxazolidinone-containing epoxy resin (A23), the epoxy resin (a1), and the isocyanate compound (b) of the epoxy resin (a2) and the epoxy resin (a3) are obtained by reaction Ketone ring epoxy resin (A123) and unreacted epoxy resin (a3). Furthermore, the epoxy resin (a3) may include two or more other epoxy resins. In this case, as described above, the oxazolidinone contained in the oxazolidone ring-containing epoxy resin composition is included. The number of ring epoxy resins and unreacted epoxy resins has increased, and the number of epoxy resins in the epoxy resin (a) is preferably two or three.

In addition, in addition to the oxazolidone ring-containing epoxy resin composition, an epoxy resin having a urethane structure or the like is also included as a by-product.

As an epoxy resin composition containing an oxazolidone ring, each epoxy resin (for example, the A1, A2, A12, a1, a2, A3, A13, A23, A123, a3, etc.) is isolated or concentrated. As the method, the method unique to the present invention is not special, and since each has a molecular weight distribution, it is difficult to perform separation or concentration using a conventional separation method. In addition, since the oxazolidone ring-containing epoxy resin is similar in structure, it is difficult to determine the content ratio by analysis such as nuclear magnetic resonance (NMR) or infrared spectrophotometer. In the present invention, since a specific effect is found in a mixture of these, it is not expressed as "the oxazolidone ring-containing epoxy resin" but as "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 that of a general epoxy resin. Therefore, the oxazolidone ring-containing epoxy resin composition of the present invention does not need to isolate each epoxy resin from the reactants, and may also remove a part of the epoxy resin as needed.

The epoxy equivalent (g / eq.) Of the oxazolidone ring-containing epoxy resin composition is preferably 200 to 600, more preferably 215 to 550, and still more preferably 220 to 500. If the epoxy equivalent is low, in addition to the fear of shortening the molecular length and deterioration of adhesion, there are also concerns that the content of the oxazolidone ring will decrease and the concentration of hydroxyl groups in the cured product will increase, so the dielectric constant Becomes high. If the epoxy equivalent is high, there is a concern that the molecular length becomes longer than necessary, and the adverse effects such as deterioration of solvent solubility and increase of resin viscosity increase. In addition, there is a concern that the crosslinked density of the hardened material becomes low, and therefore the elastic modulus decreases at the temperature of reflow soldering, etc., and there is a problem that it becomes large in use.

When the softening point is used in a prepreg or a film material, it is preferably 50 ° C to 150 ° C, more preferably 55 ° C to 135 ° C, and still more preferably 60 ° C to 120 ° C. In this case, there is no fear that the softening point is too low, so the lower limit value does not need to be paid special attention. If the softening point is high, there is a concern that the viscosity of the resin becomes high, the impregnation in the prepreg deteriorates, or the solubility of the solvent deteriorates, or the diluted solvent does not volatilize and remains in the resin during heating and drying. The occurrence of voids and the like when forming a laminated board is a big problem in use.

The epoxy resin (a) used to obtain 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 (a) The sum of a1) and epoxy resin (a2) is 55 mass% to 100 mass% in epoxy resin (a), and epoxy resin (a1) is 5 mass% to 50 mass% in epoxy resin (a). It may contain less than 45% by mass of epoxy resin (a1) and epoxy resin (a3) other than epoxy resin (a2).

The epoxy equivalent of the epoxy resin (a) is preferably 100 to 500, and more preferably 150 to 300. The epoxy equivalent is obtained by mixing and measuring all epoxy resins including epoxy resin (a1) and epoxy resin (a2). In addition, when the epoxy equivalent of the epoxy resin used is known, it can also be calculated | required by calculation.

Since the alcoholic hydroxyl group of the epoxy resin (a) reacts with an isocyanate to form a urethane bond, there is a concern that the heat resistance (glass transition point) of the cured product may be reduced. Moreover, since the hydroxyl group concentration in a hardened | cured material increases, there exists a possibility that the dielectric constant of a hardened | cured material may become high. Therefore, the alcoholic hydroxyl equivalent (g / eq.) In the epoxy resin (a) is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. The alcoholic hydroxyl equivalent is obtained by measuring and mixing all epoxy resins including epoxy resin (a1) and epoxy resin (a2). In addition, the larger the alcoholic hydroxyl equivalent, the smaller the alcoholic hydroxyl group. For example, when m in formula (1) and n in formula (2) are 0, the alcoholic hydroxyl group is absent, and the alcoholic hydroxyl equivalent is theoretically infinite. Therefore, it is not necessary to specify an upper limit value.

The alcoholic hydroxyl group of the epoxy resin (a) is an alcoholic hydroxyl group produced by a reaction between a phenol compound and an epihalohydrin. When epihalohydrin is epichlorohydrin, these alcoholic hydroxyl groups are alcoholic hydroxyl groups derived from 2-chloro-3-hydroxypropyl groups (α ), Alcoholic hydroxyl (β) derived from 1-chloromethyl-2-hydroxyethyl generated by addition of a phenol compound to the β-position of epichlorohydrin, by addition of a phenol compound to an epoxy resin The secondary alcoholic hydroxyl group (γ) produced, and α-glycol (δ) produced by the hydrolysis of the epoxy group of the epoxy resin. The alcoholic hydroxyl group in the present invention refers to all of (α), (β), (γ), and (δ). Therefore, the measurement target of the alcoholic hydroxyl equivalent is (α), (β), (γ), and (δ). ) All.

In the formula (1), X represents a cycloalkylene group having 5 to 8 ring members 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 these. The number of substituents may be one or two or more. The cycloalkane ring constituting the extended cycloalkyl group having 5 to 8 ring members is any of a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or a cyclooctane ring, and is preferably a cyclopentane ring. Or cyclohexane ring.

Examples of the substituent include, as the alkyl group having 1 to 4 carbon atoms, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl, and third butyl groups. 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, an o-xylyl group, and the like, but are not limited thereto. In the case of the same, they may be the same or different. From the viewpoints of easiness of obtaining and physical properties such as adhesiveness in a laminated board, a preferred substituent is a methyl group or a phenyl group.

Furthermore, the cycloalkyl group is preferably a 1,1-cycloalkyl group, and the purpose of the substituent is to use a three-dimensional structure that interacts with a benzene ring or a substituent bonded to the carbon at the 1-position of the cycloalkyl group. The repulsive effect restricts the mobility of the naphthene ring, thereby improving the dielectric properties and improving the heat resistance. As long as the substitution position is a position where the mobility can be restricted, it can be bonded to any position, and preferably is bonded to a carbon atom close to the 1-position of the cycloalkyl group. Preferred substituents have a carbon atom at the 2- or 5-position in the cyclopentane ring. In the cyclohexane ring, it is a carbon atom at the 2-, 3-, 5-, or 6-position, and more preferably a 2- or 6-position carbon atom. In the cycloheptane ring, it is a carbon atom at the 2-, 3-, 6-, or 7-position, and more preferably a 2- or 7-position carbon atom. In the cyclooctane ring, it is a carbon atom at the 2-, 3-, 4-, 6-, 7-, or 8-position, more preferably a 2-, 3-, 7-, or 8-position carbon atom, and further preferably 2 Or 8 carbon atoms.

In addition, at least one of the number of substituents is required for the reasons described above. From the viewpoint of heat resistance at the time of forming a cured product, it is preferably three or more, and more preferably three.

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

In formula (1), R ¹ each 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, or Aralkyl having 7 to 10 carbon atoms. For example, examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, third butyl, and hexyl. As the cycloalkyl group having 5 to 8 carbon atoms, Examples include cyclohexyl and the like. Examples of alkenyl having 1 to 4 carbon atoms include 1-propenyl or 2-propenyl. As the aryl group having 6 to 10 carbon atoms or the aralkyl group having 7 to 10 carbon atoms, Examples include phenyl, benzyl, phenethyl, 1-phenylethyl, and naphthyl, but are not limited to these, and may be the same or different. From the viewpoints of ease of availability and physical properties such as heat resistance at the time of forming a cured product, preferred R ¹ is 1-phenylethyl or methyl. The substitution position of R ¹ is preferably ortho or meta with respect to the carbon atom bonded to X, and more preferably ortho. In addition, k1 is independently 0, 1, 2, 3, or 4, and is preferably 0, 1, or 2.

In the formula (1), m is a repeating number, and an average value (quantity average) thereof is 0 to 2, 0 to 1 is a preferable range, 0 to 0.5 is a more preferable range, and 0 to 0.3 is a further preferable range. Moreover, the number of repetitions (integer) can usually be in the range of 0 to 2 integers. The repeating number may be a single compound having any integer of 0 to 2, or a mixture of a plurality of integers having m being 0 to 2. The epoxidation using epichlorohydrin or the like of a general polyhydric hydroxy resin is obtained as a mixture, and therefore has the advantage that it can be used directly as a mixture.

In the formula (2), R ² , k ² , and n have the same meanings as R ¹ , k ¹ , and m of the formula (1), and may be changed independently of each other. The substitution position of R ² is preferably ortho or meta with respect to the carbon atom of the biphenyl bond, and more preferably ortho. The -O- group is preferably ortho or para with respect to the carbon atom of the biphenyl bond, and more preferably is para.

The epoxy resin (a1) can be obtained by a known method in which a cycloalkylene group-containing phenol compound represented by the following formula (3) is reacted with epihalohydrin in the presence of a base such as sodium hydroxide. Or a method of performing epoxidation of an allyl group by oxidizing an allyl group with an oxidizing agent such as a peroxide, after allyl etherification of a phenolic compound containing a cycloalkyl group represented by formula (3) with allyl etherate Wait.

[Chemical 2] Wherein, R ^1, k1 and X, respectively R & lt formula (1) is ^1, k1 and X have the same meaning.

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

The phenol compound represented by the formula (3) can be obtained by reacting cyclic aliphatic ketones and phenols which are equivalent to each other. Specific examples include cyclic alkylene group-containing phenol compounds as shown below, but they are not limited to these.

[Chemical 3]

These exemplified cyclic alkyl group-containing phenol compounds can be produced, for example, by a method disclosed in Japanese Patent Laid-Open No. 4-282334 or Japanese Patent Laid-Open No. 2015-51935, and can also be obtained as a commercially available product. For example, BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, BisOCP-IPZ, BisP-nBZ, BisOEP-2HBP (the above are product names, Honshu Chemical Industry) and so on.

Examples of the epoxy resin (a1) include 4,4 '-(2-methylcyclohexylene) diphenol glycidyl ether, and 4,4'-(3-methylcyclohexylene) diphenol glycidyl ether. Ether, 4,4 '-(4-methylcyclohexylene) diphenol glycidyl ether, 4,4'-(3,3,5-trimethylcyclohexylene) diphenol glycidyl ether, 4,4 '-(3,3,5-trimethylcyclohexylene) -bis-phenylphenol glycidyl ether, 4,4'-(3,3,5-trimethylcyclohexylene) -bis-phenyl Phenol glycidyl ether, 4,4 '-(3,3,5-trimethylcyclohexylene) -bis-dimethylphenol glycidyl ether, 4,4'-(3,3,5-trimethyl Cyclohexylene) -bis-third-butylphenol glycidyl ether and the like are not limited to these, and these epoxy resins may be used alone or in combination of two or more.

As the epoxy resin (a1), in terms of ease of availability and good physical properties of the hardened material, it is suitable to use 4,4 '-(3,3,5-trimethylcyclohexylene) diphenol and a table An epoxy resin represented by the following formula (4) obtained by halo alcohol.

[Chemical 4] In the formula, m has the same meaning as that of the formula (1).

The epoxy resin (a2) can be obtained by a known method such as a method of reacting a biphenol compound represented by the following formula (5) with epihalohydrin in the presence of a base such as sodium hydroxide, or using allyl A method in which the biphenol compound represented by formula (5) is allyl etherified with an alkyl etherate, and then the allyl group is oxidized with an oxidizing agent such as a peroxide and epoxidized.

[Chemical 5] In the formula, R ² and k ^{2 have the} same meanings as R ² and k ^{2 in} formula (2), respectively.

The epoxy equivalent of the epoxy resin (a2) is preferably 100 to 500, and more preferably 150 to 300. The alcoholic hydroxyl equivalent is preferably 1,000 or more, more preferably 2,000 or more, and even 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'-biphenol, 2, 2'-dimethyl-4,4'-biphenol, 3,3'-dimethyl-4,4'-biphenol, 2,2 ', 6,6'-tetramethyl-4,4' -Biphenol, 2,2 ', 5,5'-tetramethyl-4,4'-biphenol, 2,2', 3,3 ', 6,6'-hexamethyl-4,4'- Biphenol, 2,2'-diethyl-4,4'-biphenol, 3,3'-diethyl-4,4'-biphenol, 2,2 ', 6,6'-tetraethyl -4,4'-biphenol, 2,2 ', 5,5'-tetraethyl-4,4'-biphenol, 2,2'-diallyl-4,4'-biphenol, 3 , 3'-diallyl-4,4'-biphenol, 2,2 ', 6,6'-tetraallyl-4,4'-biphenol, 2,2', 5,5'- Tetraallyl-4,4'-biphenol, 2,2 ', 5,5'-tetra-third-butyl-4,4'-biphenol, 2,2', 6,6'-tetra- Third butyl-4,4'-biphenol, 2,2'-cyclohexyl-4,4'-biphenol, 2,2'-diphenyl-4,4'-biphenol, 2,2 ' , 3,3 ', 5,5'-hexamethylbiphenyl-4,4'-diol and the like, but it is not limited to these. These biphenol compounds may be used alone or in combination of two or more. In particular, when 4,4'-biphenol is used, it is preferably used in combination with another biphenol compound.

These exemplified phenol compounds are also available as commercially available products, and examples thereof include BP, 26X-BP, TTB-BP, DM-BP, PCR-BP, TMP-BP, and 24B-BP (the above are the product names, Honshu) Chemical industry)).

Examples of the epoxy resin (a2) include 4,4'-bis (glycidyloxy) biphenyl, 2,2'-bis (glycidyloxy) biphenyl, 3,3 ', 5 , 5'-tetramethyl-4,4'-bis (glycidyloxy) biphenyl, 3,3'-dimethyl-4,4'-bis (glycidyloxy) biphenyl, 3 , 3 ', 5,5'-Tetra-third-butyl-4,4'-bis (glycidyloxy) biphenyl, 3,3'-cyclohexyl-4,4'-bis (glycidyl Oxy) biphenyl, 3,3'-diphenyl-4,4'-bis (glycidyloxy) biphenyl, etc., but are not limited to these, these epoxy resins can be used alone or in combination More than two.

As the epoxy resin (a2), in terms of easiness of obtaining and good physical properties of the hardened material, it is suitable to combine 2,2 ', 6,6'-tetramethyl-4,4'-biphenol with a table An epoxy resin represented by the following formula (6) obtained by halo alcohol.

[Chemical 6] In the formula, n has the same meaning as that of formula (2).

The blending ratio of the epoxy resin (a1) and the epoxy resin (a2) is 1/9 to 9/1 in terms of mass ratio. The epoxy resin (a1) must contain 5 mass% to 50% in the epoxy resin (a). quality%. When the epoxy resin (a1) exceeds 50% by mass, there is a concern that the heat resistance or adhesion cannot be sufficiently exhibited, and there is a concern that the flame retardancy is insufficient in a flame retardant formulation using a phosphorus-based flame retardant. The amount of the epoxy resin (a2) used varies depending on the amount of the epoxy resin (a1) used, and the total amount of the epoxy resin (a1) and the epoxy resin (a2) used must be 55% by mass or more. That is, it is understood that the amount of the epoxy resin (a2) is used in the range of 50 mass% to 95 mass% when the epoxy resin (a1) is 5 mass%, and the epoxy resin (a1) is used. ) When it is 50% by mass, use it in the range of 5 to 50% by mass. If the total is less than 55% by mass, there is a concern that the dielectric characteristics are insufficient. The blending ratio (a1 / a2) of the epoxy resin (a1) and the epoxy resin (a2) in the epoxy resin (a) is 5 to 50/95 to 50, and more preferably 25 to 50% by mass. 40/75 to 55, and more preferably 40 to 45/60 to 55.

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

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

Examples of the epoxy resin (a3) that can be used in combination include bisphenol A epoxy resin, bisphenol F epoxy resin, tetramethylbisphenol F epoxy resin, bisphenol fluorene epoxy resin, and naphthalene. Diphenol epoxy resin, bisphenol S epoxy resin, bissulfide epoxy resin, hydroquinone epoxy resin, resorcinol epoxy resin, phenol novolac epoxy resin, methyl alcohol Novolac epoxy resin, alkyl novolac epoxy resin, styrenated phenol novolac epoxy resin, naphthol novolac epoxy resin, β-naphthol aralkyl epoxy resin, two Polyglycidyl ether compounds such as naphthol aralkyl epoxy resin, α-naphthol aralkyl epoxy resin, biphenylaralkylphenol epoxy resin, diaminodiphenylmethane tetraglycidyl ether , Polyglycidylamine compounds such as N, N, N ', N'-tetraglycidyl-1,3-benzenedi (methylamine), polyglycidyl ester compounds such as dimer acid epoxy resins, fats Alicyclic epoxy compounds, such as family cyclic epoxy resins, and the like, are not limited to these, and these epoxy resins may be used alone or in combination. the above.

Among the epoxy resins (a3) that can be used in combination, an epoxy resin containing an aliphatic substituent or a bisphenol AF-type epoxy resin having a fluorine atom in the molecule is preferred for the purpose of further reducing the dielectric constant in order to make it heat resistant Multifunctional phenol novolak-type epoxy resins and cresol novolak-type epoxy resins are preferred for the purpose of further improving properties, and bisphenol S-type epoxy resins or A bisphenol fluorene type epoxy resin is preferably a diphenyl ether type epoxy resin or a benzophenone type epoxy resin for the purpose of improving thermal conductivity, and a bisphenol A type epoxy resin is preferably used for the purpose of reducing viscosity. Or bisphenol F-type epoxy resin, but it is not limited to these.

When producing the oxazolidone ring-containing epoxy resin composition of the present invention, an isocyanate compound (b) is used together with the epoxy resin (a). The reaction of the epoxy resin (a) and the isocyanate compound (b) can be used to obtain a desired oxazolidone ring-containing epoxy resin composition. As long as the said isocyanate compound (b) is an isocyanate compound which has an average of 1.8 or more isocyanate group (-N = C = O) in a molecule | numerator, a well-known and usual isocyanate compound can be used. The monofunctional isocyanate compound may be contained in a small amount, but since it is a terminal group, it is effective for the purpose of reducing the degree of polymerization, but the degree of polymerization is not high, so it is not preferable for the purpose of the present invention.

Specific examples include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,5-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 2,4'-diphenyl Methane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethylxylene diisocyanate, 1,4-naphthalene diyl diisocyanate, 1,5 -Naphthalene diyl diisocyanate, 2,6-naphthalene diyl diisocyanate, 2,7-naphthalene diyl diisocyanate, naphthalene-1,4-diyl bis (methylene) diisocyanate, naphthalene-1,5- Diyl bis (methylene) diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbisphenyl-4,4'-di Isocyanate, 2,3'-dimethoxybisphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane- 4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfite-4,4'-diisocyanate, diphenylfluorene-4 , 4'-diisocyanate, bicyclic [2.2.1] heptane-2,5-diylbismethylene diisocyanate Bicyclo [2.2.1] heptane-2,6-diylbismethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebiscyclohexyl diisocyanate, lysine diisocyanate, 1, 1-bis (isocyanate methyl) cyclohexane, 1,2-bis (isocyanate methyl) cyclohexane, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) Cyclohexane, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4-methyl-1,3-cyclohexylene diisocyanate, 2-methyl-1,3-cyclohexylene Hexyl diisocyanate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3 , 5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, methane diisocyanate, ethyl Alkan-1,2-diisocyanate, propane-1,3-diisocyanate, butane-1,1-diisocyanate, butane-1,2-diisocyanate, butane-1,4-diisocyanate, 2- Butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate Pentane-1,5-diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, octane- Bifunctional isocyanate compounds such as 1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, or triphenyl Methane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyano-4-isocyanate methyloctane, dicycloheptane triisocyanate, tris (isocyanatephenyl) thiophosphoric acid Ester, lysine triisocyanate, undecane triisocyanate, tris (4-phenylisocyanate thiophosphate) -3,3 ', 4,4'-diphenylmethane tetraisocyanate, polymethylene poly A polyfunctional isocyanate compound such as phenyl isocyanate, a polymer such as a dimer or trimer of the isocyanate compound, or a block-type isocyanate masked with a blocking agent such as an alcohol or phenol, or bisaminomethyl Ester compounds and the like are not limited to these, and these isocyanate compounds may be used alone or in combination of two or more.

Among these isocyanate compounds, a bifunctional isocyanate compound or a trifunctional isocyanate compound is preferable, and a bifunctional isocyanate compound is more preferable. When there are many functional groups of an isocyanate compound, there exists a possibility that storage stability may fall, and when there are few functional groups of an isocyanate compound, there exists a possibility that heat resistance or dielectric characteristics may not improve.

Particularly preferred isocyanate compound (b) is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,5-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4 '-Diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethylxylene diisocyanate, 1,4-naphthalene diisocyanate , 1,5-naphthalenediyl diisocyanate, 2,6-naphthalenediyl diisocyanate, 2,7-naphthalenediyl diisocyanate, 3,3'-dimethylbisphenyl-4,4'-diisocyanate , M-phenylene diisocyanate, terephthalic acid diisocyanate, cyclohexane-1,4-diyl diisocyanate, cyclohexane-1,3-diylbismethylene diisocyanate, cyclohexane-1,4-di Dibismethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 4,4 '-Methylene dicyclohexyl diisocyanate, bicyclo [2.2.1] heptane-2,5-diylbismethylene diisocyanate, bicyclo [2.2.1] heptane-2,6-diylbismethylene Diisocyanate, and isophor One diisocyanate group consisting of one or more.

The reaction of the epoxy resin (a) and the isocyanate compound (b) can be performed by a known method. The specific reaction methods are: 1) Melting the epoxy resin (a), removing the moisture in the epoxy resin by flushing with a dry gas or reducing the pressure in the system, and then adding an isocyanate compound (b) and a catalyst The reaction method; or 2) the epoxy resin (a) and the catalyst are mixed in advance, and the moisture in the epoxy resin is removed by flushing with a dry gas or reducing the pressure in the system, and then the isocyanate compound (b ) And the method of reaction. The amount of water in the system at this time is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.05% by mass or less. In addition, in any method, if the resin viscosity is high and it is difficult to stir, etc., if necessary, a non-reactive solvent may be used.

Regarding the usage amounts of the epoxy resin (a) and the isocyanate compound (b), the isocyanate group of the isocyanate compound (b) is preferably 0.02 mol or more and less than 1 mol earring oxy group of the epoxy resin (a). The range of 0.5 mol is more preferably a range of 0.1 mol or more and 0.45 mol or less, still more preferably a range of 0.15 mol or more and 0.4 mol or less, and particularly preferably a range of 0.2 mol or more and 0.35 mol or less. . If the ratio of the isocyanate group is low, there is a concern that the amount of oxazolidone ring formation is reduced, and the effect of improving the dielectric properties or heat resistance of the cured product may not be obtained. In addition, when the ratio of the isocyanate group is large, not only the remaining amount of the epoxy group decreases, but also the reaction becomes thicker during the reaction, which makes the reaction difficult. In addition, even if obtained, solvent solubility or impregnation in glass cloth is deteriorated, and it is difficult to use it for laminated board applications.

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

Examples of usable catalysts include lithium compounds, complex salts of boron trifluoride, quaternary ammonium salts, tertiary amines, phosphines, phosphonium salts, combinations of triphenyl antimony and iodine, and imidazole. And alkali metal hydroxides, but are not limited to these, and these catalysts may be used alone or in combination of two or more. In addition, it can be divided and used several times. Among these catalysts, quaternary ammonium salts, tertiary amines, phosphines, or phosphonium salts are preferred, and tetramethylammonium iodide is more preferred in terms of reactivity and selectivity of the reaction. In the case of a catalyst having a low reactivity, there is a concern that the reaction time becomes long and the productivity is lowered. In the case of a catalyst having a low selectivity of the reaction, there is a concern that the polymerization reaction of epoxy groups cannot proceed to obtain the target physical properties. .

The amount of catalyst is not particularly limited, and is preferably 0.0001 to 5 mass%, more preferably 0.0005 to 1 mass% with respect to the total mass of the epoxy resin (a) and the isocyanate compound (b), and more preferably 0.001% by mass to 0.5% by mass, and particularly preferably 0.002% by mass to 0.2% by mass. When the amount of the catalyst is large, there is a concern that the epoxy group undergoes a self-polymerization reaction depending on the case, and therefore the resin viscosity becomes high. In addition, there is a concern that the self-polymerization reaction of the isocyanate is promoted and the generation of the oxazolidone ring is suppressed. Furthermore, there is a concern that it may remain as an impurity in the produced resin, and when it is used as a material for a laminated board or a sealing material in various applications, it may cause a reduction in insulation or moisture resistance. If the amount of the catalyst is small, there is a concern that the efficiency for obtaining an oxazolidone ring-containing epoxy resin composition is reduced.

The reaction temperature is preferably 100 ° C to 250 ° C, more preferably 100 ° C to 200 ° C, and even more preferably 120 ° C to 160 ° C. If the reaction temperature is low, there is a concern that the formation of the oxazolidinone ring cannot proceed sufficiently, and the isocyanurate ring is formed due to the trimerization reaction of the isocyanate group. In addition, if the reaction temperature is high, there is a concern that a local high molecular weight is caused, and an insoluble gel component is generated more. Therefore, it is necessary to adjust the addition speed of the isocyanate compound (b). If the addition rate of the isocyanate compound (b) is high, there is a concern that it is not possible to cool it with respect to heat generation, so that a preferable reaction temperature cannot be maintained. In addition, if the addition rate is slow, there is a concern that productivity is significantly reduced.

The reaction time is preferably 15 minutes to 10 hours after the addition of the isocyanate compound (b) is completed, more preferably 30 minutes to 8 hours, and still more preferably 1 hour to 5 hours. If the reaction time is short, there is a concern that a large amount of isocyanate groups remain in the product. If the reaction time is long, there is a concern that productivity is significantly reduced.

In addition, when the reaction between the epoxy resin (a) and the isocyanate compound (b) is performed, various modifiers may be used for the epoxy resin composition of the present invention within a range that does not affect the effect. It is easy to adjust molecular weight (epoxy equivalent) and the like by using a modifier. The amount 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 usable modifiers include bisphenols such as bisphenol A, bisphenol F, biphenols, resorcinol, and hydroquinone, and monocyclic bifunctional phenols, dihydroxynaphthalenes, and novolacs. Various phenols such as resins and heavy oil modified phenol resins, or polyhydric phenol resins or amine compounds obtained by condensation reactions of various phenols and various aldehydes, but are not limited to these, and these modifiers may be It can be used alone or in combination of two or more. Moreover, when these modifiers have an aromatic ring, the said aromatic ring may be substituted by the substituent which does not have an adverse effect, such as an alkyl group and an aryl group.

Alternatively, a non-reactive solvent may be used if necessary. Examples include various hydrocarbons such as hexane, heptane, octane, dimethylbutane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, or dibutyl ether, Ethers such as dioxane and tetrahydrofuran, or cellosolvents such as methyl cellosolve and ethyl cellosolve, or glycol ethers such as ethylene glycol dimethyl ether, etc. are not particularly limited to these solvents They can be used alone or in combination of two or more. The usage-amount of these solvents is 1-900 mass parts with respect to 100 mass parts of epoxy resin (a), More preferably, it is 5-100 mass parts.

The reaction product obtained as described above can be used as the epoxy resin composition containing an oxazolidone ring of the present invention by removing a solvent or a catalyst, or a part of an unreacted product or a product directly or if necessary.

Next, the curable resin composition of the present invention will be described. The curable resin composition of this invention contains the oxazolidone ring containing epoxy resin composition of this invention, and a hardening | curing agent.

The hardener is not particularly limited as long as it can harden the epoxy resin, and phenol-based hardeners, acid anhydride-based hardeners, amine-based hardeners, hydrazine-based hardeners, active ester-based hardeners, and phosphorus-containing hardeners can be used. Hardener for epoxy resin. These hardeners may be used alone or in combination of two or more. Among these, dicyandiamine, a phenol-based hardener, or an active ester-based hardener is preferred, and a phenol-based hardener or an active ester-based hardener is more preferred.

The amount of the hardener used is preferably 0.2 mol to 1.5 mol per 1 mol of the epoxy resin of all epoxy resins containing the oxazolidone ring-containing epoxy resin composition. It is more preferably 0.3 mol to 1.5 mol, still more preferably 0.5 mol to 1.5 mol, and particularly preferably 0.8 mol to 1.2 mol. When the active hydrogen group of the hardener is not in the above range, there is a concern that hardening is not completed and good hardened physical properties cannot be obtained. For example, when a phenol-based hardener or an amine-based hardener is used, an active hydrogen group of approximately equal mole is prepared relative to an epoxy group, and when an acid anhydride-based hardener is used, it is compared with 1 mole of a ring. An acid anhydride group is prepared from 0.5 to 1.2 mol, preferably from 0.6 to 1.0 mol.

The active hydrogen group described in the present invention is a functional group having an active hydrogen that is reactive with an epoxy group (a functional group containing a potential active hydrogen that generates active hydrogen due to hydrolysis or the like, or equivalent) Specific functional groups for hardening) include acid anhydride groups, carboxyl groups, amine groups, and phenolic hydroxyl groups. In addition, as for the active hydrogen group, one mole of a carboxyl group or a phenolic hydroxyl group is calculated as one mole, and one mole of an amine group (NH ₂ ) is calculated as two moles. When the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, by reacting a single epoxy resin such as phenyl glycidyl ether with a known epoxy equivalent with a hardener whose active hydrogen equivalent is unknown, and measuring the amount of the single epoxy resin consumed, the Active hydrogen equivalent.

Specific examples of the phenol resin-based hardener include bisphenols such as bisphenol A and bisphenol F, or dihydroxybenzenes such as resorcinol, hydroquinone, and di-tert-butylhydroquinone. Type, or hydroxy naphthalenes such as dihydroxynaphthalene, trihydroxynaphthalene, or phenols such as phenol novolac resin, cresol novolac resin, trihydroxyphenylmethane novolac resin, naphthol novolac resin, and / or naphthol And condensates of aldehydes and / or condensation agents.

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

In addition, a benzoxazine compound that becomes a phenol compound by ring opening upon heating is also useful as a hardener. Examples include, but are not limited to, bisphenol F-type or bisphenol S-type benzoxazine compounds.

Examples of the acid anhydride-based hardener include methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, phthalic anhydride, trimellitic anhydride, and methylnadic acid. Acid etc.

Examples of the amine-based hardener include diethylenetriamine, triethylenetetramine, m-xylylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylphosphonium, and diamine. Condensates of amino diphenyl ethers, benzyl dimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, dicyandiamine, acids such as dimer acids, and polyamines Polyamine-amine and other amine compounds.

Examples of the active ester-based hardener include a reaction product of a polyfunctional phenol compound and an aromatic carboxylic acid described in Japanese Patent No. 5152445, and commercially available products include Epiclon HPC-8000-65T (product Name, manufactured by Disheng (DIC) Co., Ltd.).

Examples of other curing agents include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, Imidazoles such as 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, imidazole salts as salts of imidazoles with trimellitic acid, isocyanuric acid, boric acid, etc., trimethyl chloride Quaternary ammonium salts such as ammonium chloride, diazabicyclic compounds, salts of diazabicyclic compounds and phenols or phenol novolac resins, complex compounds of boron trifluoride and amines or ether compounds, Aromatic osmium, or osmium salt.

If necessary, a hardening accelerator is used. Examples of usable hardening accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, and 2- (dimethylaminomethyl) phenol. , Amines such as 1,8-diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane , Tin octoate and other metal compounds. A hardening 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 a hardening accelerator, the hardening temperature can be reduced, or the hardening time can be shortened.

In addition, an epoxy resin other than the oxazolidone ring-containing epoxy resin composition of the present invention may be used within a range that does not impair the physical properties of the curable resin composition, if necessary. Examples of usable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, hydroquinone type epoxy resin, and bisphenol.芴 type epoxy resin, bisphenol S type epoxy resin, bis sulfide type epoxy resin, resorcinol type epoxy resin, biphenylaralkylphenol type epoxy resin, naphthalene diphenol type epoxy resin, Phenolic novolac epoxy resin, styrenated phenol novolac epoxy resin, cresol novolac epoxy resin, alkyl novolac epoxy resin, bisphenol novolac epoxy resin, naphthol novolac Type epoxy resin, β-naphthol aralkyl type epoxy resin, dinaphthol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, triphenylmethane type epoxy resin, four Hydroxyphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, alkanediol type epoxy resin, polyglycidyl ether compound of aliphatic cyclic epoxy resin, or diaminodiphenylmethane Epoxy resin, m-xylylenediamine epoxy resin, 1,3-bisaminomethylcyclohexane epoxy resin, isocyanide Polyglycidylamine compounds such as ester type epoxy resin, aniline type epoxy resin, hydantoin type epoxy resin, aminophenol type epoxy resin, or dimer acid type epoxy resin, hexahydrophthalic acid Polyglycidyl ester compounds such as formic acid epoxy resins, or alicyclic epoxy compounds. Other examples include urethane-modified epoxy resins (eg, AER4152 (product name, manufactured by Asahi Kasei Electronic Materials Co., Ltd.), etc.), and other oxazolidone ring-containing epoxy resin compositions of the present invention. Oxazolidone ring-containing epoxy resin, epoxy modified polybutadiene rubber derivative [such as PB-3600 (product name, manufactured by Daicel Chemical Industry Co., Ltd.), etc.], CTBN modified epoxy resin [For example, Epotohto YR-102, Epotohto YR-450 (the above is the product name, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc.], etc., but it is not limited to these. The oxyresin may be used singly or in combination of two or more kinds.

In addition, the oxazolidone ring-containing epoxy resin composition and curable resin composition of the present invention can be used for adjusting viscosity by using an organic solvent and / or a reactive diluent. These organic solvents and / or reactive diluents may be used alone or in combination of two or more.

Examples of the organic solvent include amines such as N, N-dimethylformamide and N, N-dimethylacetamide, or dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, and dimethyl ether. Ethers such as oxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether, or acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Ketones, or alcohols such as methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl diethylene glycol, and pine oil Type, or ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyldiethylene glycol acetate, propylene glycol monomethyl ether acetate , Acetates such as carbitol acetate, benzyl alcohol acetate, or benzoates such as methyl benzoate, ethyl benzoate, or methyl cellosolve, cellosolve, butyl cellosolve, etc. Fibrinolytic agents, or carbitols such as methyl carbitol, carbitol, butyl carbitol, or aromatic hydrocarbons such as benzene, toluene, and xylene, or fluorenes such as dimethyl sulfene Alkane, such as hexane, cyclohexane, or acetonitrile 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. Or resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol Difunctional glycidyl ethers such as glycidyl ether, propylene glycol diglycidyl ether, or glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolethane polyglycidyl ether, pentaerythritol polyglycidyl ether Polyfunctional glycidyl ethers, glycidyl esters such as glycidyl neodecanoate, or glycidylamines such as phenyldiglycidylamine, tolyldiglycidylamine, and the like.

These organic solvents and / or reactive diluents are preferably used in an amount of 90% by mass or less of the non-volatile content, and the appropriate type or amount of use can be appropriately selected depending on the application. For example, in printed wiring board applications, a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, etc. is preferred, and the amount used is preferably 40 mass in terms of non-volatile components. % To 80% by mass. In addition, for adhesive film applications, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferably used. The use amount thereof is preferably 30% by mass to 60% by mass in terms of nonvolatile components.

The curable resin composition can be blended with other thermosetting resins or thermoplastic resins within a range that does not impair the characteristics. Examples include: phenol resin, acrylic resin, petroleum resin, indene resin, benzofuran-indene resin, phenoxy resin, polyurethane resin, polyester resin, polyamide resin, Polyimide resin, polyimide resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether resin, polyfluorene resin, polyether ether ketone resin, polybenzene A thioether resin, a polyvinyl formal resin, etc. are not limited to these.

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

As the phosphorus-based flame retardant, any of an inorganic phosphorus-based compound and an organic phosphorus-based compound can be used. Examples of the inorganic phosphorus-based compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphatidamine. Examples of the organic phosphorus-based compound include general organic compounds such as aliphatic phosphates, phosphate compounds, condensed phosphates, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, orthophosphine compounds, and organic nitrogen-containing phosphorus compounds. Examples of phosphorus compounds or metal salts of phosphinic acid include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10- (2,5- Dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), 10- (2,7-dihydroxynaphthyl) -10H-9-oxa-10- Phosphophenanthrene-10-oxide (DOPO-NQ) and other cyclic organic phosphorus compounds, or phosphorus-containing epoxy resins or phosphorus-containing epoxy resins as derivatives obtained by reacting these compounds with compounds such as epoxy resins or phenol resins Hardener, etc.

Examples of the phosphorus-containing epoxy resin include Epotohto FX-305, Epotohto FX-289B, TX-1320A, and Epotohto TX-1328 (the above are product names, (Nippon Steel & Sumitomo Chemical Co., Ltd.), but not limited to these. The epoxy equivalent of the phosphorus-containing epoxy resin may be 200 to 800, preferably 300 to 780, and more preferably 400 to 760. The phosphorus content of the phosphorus-containing epoxy resin may be 0.5% by mass to 6% by mass, preferably 2% by mass to 5.5% by mass, and more preferably 3% by mass to 5% by mass.

As the phosphorus-containing hardener, in addition to phosphorus-containing phenols such as DOPO-HQ, DOPO-NQ, and diphenylphosphinohydroquinone, Japanese Patent Publication No. 2008-501063 or Japanese Patent No. 4548547 can be used. The production method shown in Japanese Patent Publication No. 1 is obtained by reacting DOPO, aldehydes, and phenol compounds to obtain a phenol compound containing phosphorus. In this case, DOPO is incorporated into the molecule by condensation and addition to the aromatic ring of the phenol compound via aldehydes. In addition, a phosphorous-containing active ester compound can be obtained from a phosphorus-containing phenol compound having DOPO as a unit structure by using a production method shown in Japanese Patent Laid-Open No. 2013-185002 and further reacting with an aromatic carboxylic acid. . In addition, a phosphorus-containing benzoxazine compound having a DOPO unit structure can be obtained by a production method shown in Japanese Patent Application Publication No. WO2008 / 010429. The phosphorus content of the phosphorus-containing hardener may be 0.5% to 12% by mass, preferably 2% to 11% by mass, and more preferably 4% to 10% by mass.

The blending amount of the flame retardant is appropriately selected depending on the type of the phosphorus-based flame retardant, the components of the curable resin composition, and the degree of desired flame retardancy. For example, the phosphorus content in organic components (excluding organic solvents) in the curable resin composition is preferably 0.2% to 6% by mass, more preferably 0.4% to 4% by mass, and still more preferably 0.5% to 3.5%. The mass% is particularly preferably 0.6 to 3 mass%. If the phosphorus content is small, there is a concern that it is difficult to ensure flame retardancy, and if the phosphorus content is too large, there is a concern that heat resistance may be adversely affected. When a phosphorus-based flame retardant is used, a flame retardant auxiliary such as magnesium hydroxide may be used in combination.

The phosphorus-containing epoxy resin is treated as a compound equivalent to both a phosphorus-based flame retardant and an epoxy resin, and the phosphorus-containing hardener is a compound equivalent to both a phosphorus-based flame retardant and a hardener. While processing. Therefore, when a phosphorus-containing epoxy resin is used, another phosphorus-based flame retardant may not be required. Similarly, when a phosphorus-containing hardener is used, another hardener and / or a phosphorus-based flame retardant may not be required.

If necessary, a filler is used in the curable resin composition. Specific examples 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, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aromatic polyamide fiber, Ceramic fiber, micro rubber, thermoplastic elastomer, pigment, etc. The reason for using a filler generally includes the effect of improving impact resistance. In addition, when a metal hydroxide such as aluminum hydroxide, boehmite, or magnesium hydroxide is used, it has an effect of functioning as a flame retardant additive and improving flame retardancy. The blending amount of these fillers is preferably 1 to 150 parts by mass, and more preferably 10 to 70 parts by mass based on 100 parts by mass of the organic component (excluding the organic solvent) in the curable resin composition. When there are many formulation amounts, there exists a possibility that the adhesiveness required for a laminated board use may fall, and there exists a possibility that a hardened | cured material may become brittle and sufficient mechanical physical property may not be obtained. In addition, if the blending amount is small, there is a concern that the impact resistance of the cured product is improved, etc., and this is not the blending effect of the filler.

When the curable resin composition is made into a plate-like substrate or the like, a fibrous filler may be cited as a preferable filler in terms of dimensional stability, flexural strength, and the like. More preferable examples include a glass fiber substrate in which glass fibers are knitted into a mesh.

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

The curable resin composition of the present invention can be obtained by uniformly mixing the respective components. By hardening the curable resin composition, a hardened material such as a laminate, a cast, a molded article, an adhesive, an insulating layer, or a film can be obtained. As a method for obtaining a cured product, the same method as that of a known epoxy resin composition can be adopted, and the method inherent to the curable resin composition of the present invention is not required, and casting, pouring, pouring, dipping, and dropping can be preferably used Coating, transfer molding, compression molding, etc., or methods such as forming a resin sheet, a copper foil with a resin, a prepreg, etc., and laminating and heating and pressing to form a laminated board. The curing temperature at this time is usually in the range of 100 ° C to 300 ° C, and the curing time is usually about 10 minutes to 5 hours.

Examples of applications using a curable resin composition include printed circuit board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up substrates, and other circuit board insulating materials, semiconductor sealing materials, conductive pastes, conductive films, Build-up adhesive film, resin casting material, adhesive, etc. Among these various applications, printed wiring board materials, insulation materials for circuit substrates, and adhesive films for build-ups can be used to embed passive components such as capacitors or active components such as integrated circuit (IC) wafers in substrates. The so-called insulating material for a substrate for use in built-in electronic components is used. Among these applications, in terms of characteristics such as high flame retardancy, high heat resistance, low dielectric properties, and solvent solubility, it is preferable to use interlayer insulation for printed wiring board materials, resin compositions for flexible wiring substrates, and build-up substrates. Materials such as materials for circuit boards (multilayer boards) and semiconductor sealing materials.

When the curable resin composition is formed into a plate shape such as a laminated board, the filler used is preferably a fibrous filler in terms of dimensional stability and flexural strength, and more preferably glass The fibers are woven into a net-like glass fiber cloth.

The prepreg of the present invention used in a printed wiring board or the like can be prepared by impregnating a fibrous reinforcing substrate with a curable resin composition. As the fibrous reinforcing substrate, woven or non-woven fabrics such as inorganic fibers such as glass, or polyester resins, polyamine resins, polyacrylic resins, polyimide resins, and aromatic polyimide resins can be used. , But not limited to this. The method for producing a prepreg from an epoxy resin composition is not particularly limited, and it can be obtained, for example, by preparing a varnish-like epoxy resin composition containing the organic solvent, and then adjusting the composition with an organic solvent. It is a resin varnish with a suitable viscosity. After impregnating the fibrous substrate with the resin varnish, the resin varnish is heated and dried to semi-harden the resin component (B stage). The heating temperature is preferably 50 ° C to 200 ° C, and more preferably 100 ° C to 170 ° C, depending on the type of the organic solvent used. The heating time can be adjusted according to the type of the organic solvent used or the curability of the prepreg, and is preferably 1 minute to 40 minutes, and more preferably 3 minutes to 20 minutes. At this time, the mass ratio of the epoxy resin composition to the reinforcing substrate used is not particularly limited, and it is generally preferably adjusted so that the resin component in the prepreg becomes 20% by mass to 80% by mass.

The curable resin composition of the present invention can be formed into a sheet shape or a film shape and used. In such a case, a conventionally known method can be used to form the sheet or film. The method for manufacturing the adhesive sheet is not particularly limited, and it can be obtained, for example, by using a reverse roll coater, a notch wheel coater, and a mold on a supporting base film that is not dissolved in the resin varnish. A coater such as a coater applies a resin varnish, and then heat-dries to make the resin component B-stage. In addition, if necessary, another supporting base film is laminated on the coating surface (adhesive layer) as a protective film, and dried to obtain an adhesive sheet having release layers on both surfaces of the adhesive layer. Examples of the supporting base film include metal foils such as copper foil, polyolefin films such as polyethylene film and polypropylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, silicone film, and polyfluorene. Among these supporting base films, a polyethylene terephthalate film which is excellent in dimensional accuracy without defects such as chipping and is also excellent in cost is preferable. In addition, a metal foil, particularly a copper foil, which facilitates multilayering of a laminated board is preferred. The thickness of the supporting base film is not particularly limited, but it is preferably from 10 μm to 150 μm, and more preferably from 25 μm to 50 μm, from the viewpoint of having strength as a support and difficulty in causing poor lamination. The thickness of the protective film is not particularly limited, but is usually 5 μm to 50 μm. In addition, in order to facilitate peel-molding of the adhesive sheet, it is preferable to perform surface treatment with a release agent in advance. The thickness of the coated resin varnish is preferably 5 μm to 200 μm, and more preferably 5 μm to 100 μm, based on the thickness after drying. The heating temperature is preferably 50 ° C to 200 ° C, and more preferably 100 ° C to 170 ° C, depending on the type of the organic solvent used. The heating time can be adjusted according to the type of the organic solvent used or the curability of the prepreg, and is preferably 1 minute to 40 minutes, and more preferably 3 minutes to 20 minutes. The adhesive sheet obtained as described above is usually an insulating adhesive sheet, but conductive adhesive can also be obtained by mixing a conductive metal or metal-coated fine particles in an epoxy resin composition. sheet. Furthermore, the supporting base film is peeled after being laminated on a circuit board or after being heated and hardened to form an insulating layer. If the support base film is peeled off after the adhesive sheet is heat-hardened, dirt and the like can be prevented from being attached during the hardening step. Here, the insulating adhesive sheet is also an insulating sheet.

A method for manufacturing a laminated board of the present invention using the prepreg of the present invention or the insulating adhesive sheet will be described. For example, when a prepreg is used to form a laminated board, one or more prepregs are laminated, and metal foils are arranged on one or both sides to form a laminate, and the laminate is heated under pressure, thereby The prepreg is hardened and integrated to obtain a laminated board. Here, as the metal foil, a single, alloy, or composite metal foil such as copper, aluminum, brass, or nickel can be used. As a condition for applying heat and pressure to the laminate, the heat and pressure may be appropriately adjusted under the condition that the epoxy resin composition is hardened. However, if the pressure is too low, the laminate may be Air bubbles remain in the inside and the electrical characteristics are degraded. Therefore, it is desirable to pressurize under conditions that satisfy moldability. The heating temperature is preferably 160 ° C to 250 ° C, and more preferably 170 ° C to 220 ° C. The pressing pressure is preferably 0.5 MPa to 10 MPa, and more preferably 1 MPa to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, and more preferably 40 minutes to 3 hours. Furthermore, a multilayer board can be manufactured using the single-layer laminated board obtained as mentioned above as an inner-layer material. In such a case, first, an additive method or a subtractive method is used to form a circuit on the multilayer board, and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. A prepreg or an insulating adhesive sheet is used to form an insulating layer on one or both sides of the circuit forming surface of the inner layer material, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.

When an insulating layer is formed using an insulating adhesive sheet, an insulating adhesive sheet is arranged on a circuit formation surface of a plurality of inner layers to form a laminate. Alternatively, an insulating adhesive sheet is arranged between the circuit formation surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressurized to be integrally molded, thereby forming a cured product of the insulating adhesive sheet as an insulating layer, and forming a multilayered inner layer material. Alternatively, the inner layer material and the metal foil as the conductive layer may be formed as a cured product of an insulating adhesive sheet and used as an insulating layer. Here, as the metal foil, the same metal foil as the metal foil used in a laminated board used as an inner layer material can be used. The heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.

When the insulating layer is formed using the prepreg, one or a plurality of prepregs are laminated on the circuit formation surface of the inner layer material, and a metal foil is further arranged on the outer side to form a laminated body. Further, the laminated body is integrally molded by applying heat and pressure, thereby forming a hardened material of the prepreg as an insulating layer, and forming a metal foil on the outside thereof as a conductive layer. Here, as the metal foil, the same metal foil as the metal foil used in the laminated board used as the inner layer board can be used. The heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. The printed wiring board can be formed by forming via holes or circuits on the surface of the multilayer laminated board formed as described above by an addition method or a subtractive method. In addition, the printed wiring board is used as an inner layer material, and the above-mentioned method is repeated, whereby a multi-layered multilayer board can be formed.

In addition, when a curable resin composition is applied to the laminated board to form an insulating layer, the curable fat composition is applied to a thickness of preferably 5 μm to 100 μm, and then at 100 ° C. to 200 ° C., preferably The sheet is formed by heating and drying at 150 ° C to 200 ° C for 1 minute to 120 minutes, preferably 30 minutes to 90 minutes. It is usually formed by a method called a casting method. The thickness after drying is preferably 5 μm to 150 μm, and preferably 5 μm to 80 μm. Furthermore, in terms of obtaining a sufficient film thickness and making it difficult to cause uneven coating or streaks, the viscosity of the curable resin composition is preferably in the range of 10 mPa · s to 40,000 mPa · s at 25 ° C, and more preferably It is 200 mPa · s to 30,000 mPa · s. A printed wiring board can be formed by forming via holes or circuits on the surface of the multilayer laminated board formed as described above by an addition method or a subtractive method. In addition, the printed wiring board is used as an inner layer material, and the above-mentioned method is repeated to form a multilayer laminated board.

Sealing materials obtained by using the curable resin composition of the present invention include tape-shaped semiconductor wafers, infusion liquid seals, underfills, and semiconductor interlayer insulation films, and the like can be preferably used among these. For example, the molding of the semiconductor package may include casting an epoxy resin composition, or molding the epoxy resin composition using a transfer molding machine, an injection molding machine, or the like, and further heating at 50 ° C to 200 ° C for 2 hours to 10 hours. A method of obtaining a molded product in hours.

In order to prepare a curable resin composition for use as a semiconductor sealing material, an additive such as an inorganic filler, if necessary, or an additive such as a coupling agent and a release agent may be mixed in the curable resin composition in advance, and then extruded. Extruder, kneader, roll, etc. are fully melted and mixed until uniform. At this time, silicon dioxide is generally used as the inorganic filler. In this case, it is preferable to mix the inorganic filler in the curable resin composition at a ratio of 70% to 95% by mass. In the case where the curable resin composition obtained as described above is used as a tape-shaped sealing material, it may be heated to produce a semi-hardened sheet, and after forming a sealing material tape, the sealing material tape is placed on A method in which a semiconductor wafer is heated to 100 ° C. to 150 ° C. to be softened to be formed, and then completely cured at 170 ° C. to 250 ° C. Moreover, when using as a potting type liquid sealing material, what is necessary is just to melt | dissolve the obtained curable resin composition in a solvent as needed, apply to a semiconductor wafer or an electronic component, and harden it directly.

The curable resin composition of the present invention can also be used as a resist ink. In this case, a cationic polymerization catalyst having an ethylenically unsaturated double bond, a cationic polymerization catalyst as a hardener, and a pigment, talc, and a filler are added to the epoxy resin composition to prepare a resist. After the composition for ink is applied on a printed circuit board by a screen printing method, a method for forming a cured resist ink is made. The curing temperature at this time is preferably a temperature range of about 20 ° C to 250 ° C.

The cured product of the present invention can take the form of a laminate, a molded product, an adhesive, a coating film, a film, or the like. An oxazolidine-containing compound of the present invention is obtained by preparing a curable resin composition and evaluating the cured epoxy resin of the laminated board by heating and curing. As a result, a specific epoxy resin (a) and an isocyanate compound (b) are reacted. Compared with conventional epoxy resins, ketone ring epoxy resin compositions have not only low dielectric properties, but also low viscosity and good workability, and they can have both high flame retardancy and high adhesion. Furthermore, the solvent solubility is also improved. [Example]

Hereinafter, the present invention will be specifically described with examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, "part" means mass parts, and "%" means mass%. The measurement method can be measured by the following methods, respectively. The equivalent units are all "g / eq.".

(1) Epoxy equivalent: Measured in accordance with JIS K7236. Specifically, using a potentiometric titration device and using methyl ethyl ketone as a solvent, a tetraethylammonium bromide acetic acid solution was added, and a 0.1 mol / L perchloric acid-acetic acid solution was further used. (2) Softening point: Measured in accordance with JIS K7234 standard and ring and ball method. Specifically, an automatic softening point device (manufactured by Meitec Corporation, ASP-MG4) was used. (3) Number average molecular weight (Mn), weight average molecular weight (Mw), and dispersion (Mw / Mn): The body (manufactured by Tosoh Co., Ltd., HLC-8220GPC) is provided with a column (East TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL) were manufactured by Tosoh Co., Ltd. The column temperature was set to 40 ° C. In addition, tetrahydrofuran was used as the eluent, and a flow rate of 1 mL / min was used, and a differential refractive detector was used as the detector. The calibration curves obtained from standard monodisperse polystyrene were used to convert Mn, Mw, and Mw / Mn. (4) Solvent solubility: Visually judge the state when diluted with toluene to 50% of non-volatile content. A case where it is completely dissolved and transparent is regarded as "○", a case where it is white and cloudy or separated is regarded as "X", and a case where it is slightly cloudy is regarded as "△".

(5) Glass transition temperature: Measured in accordance with JIS K7121 and by differential scanning calorimetry. Using EXII DSC6200 manufactured by SII, the temperature was measured at a temperature increase rate of 10 ° C / min from 20 ° C, and the extrapolated glass transition start temperature (Tig) of the DSC chart obtained in the second cycle was used. ) And find it. (6) Peel strength and interlayer adhesion: measured in accordance with JIS C6481. The interlayer adhesion was measured by peeling between the seventh layer and the eighth layer. (7) Relative dielectric constant and dielectric loss tangent: According to IPC-TM-650 2.5.5.9, a material analyzer (manufactured by Agilent Technologies) was used to measure the dielectric constant and frequency of 1 GHz using a capacitance method. Dielectric loss tangent. (8) Flame retardancy: It was evaluated by the vertical method in accordance with UL94 (Underwriters Laboratories Inc.'s safety certification standard), and the total flame time (seconds) of five test pieces was shown. A small afterflame time indicates a more preferable flame retardancy.

Synthesis Example 1 In a reaction device including a stirring device, a thermometer, a nitrogen introduction device, a cooling pipe, and a water separator, 100 parts of 4,4 '-(3,3,5-trimethylamine) were charged at room temperature. (Cyclohexyl) diphenol (manufactured by Honshu Chemical Industry Co., Ltd., BisP-TMC), 358 parts of epichlorohydrin, 4 parts of ion-exchanged water, and the temperature was raised to 50 ° C while stirring. After uniform dissolution, 5.3 parts of a 49% aqueous sodium hydroxide solution was charged and reacted for 3 hours. Next, after raising the temperature to 64 ° C., the pressure was reduced to the extent that the reflux of water was generated, and 48 parts of a 49% aqueous solution of sodium hydroxide was added dropwise over 3 hours. During the dropwise addition, the reflux distilled water was separated from the surface with a separation tank. Chlorohydrin returns epichlorohydrin to the reaction vessel and removes water from the system to perform the reaction. After completion of the reaction, the temperature was raised to 70 ° C to perform dehydration, and the remaining epichlorohydrin was recovered by setting the temperature to 135 ° C. After returning to normal pressure, 204 parts of methyl isobutyl ketone (MIBK) was added and dissolved. 127 parts of ion-exchanged water was added, and the solution was stirred and left to dissolve by-product salt in water to remove it. Next, 2.9 parts of a 49% aqueous sodium hydroxide solution was charged, and the reaction was stirred at 80 ° C. for 90 minutes to perform a purification reaction. MIBK was added and washed several times to remove ionic impurities. The solvent was recovered to obtain the epoxy resin (epoxy resin a) represented by the formula (1). The epoxy equivalent of the obtained epoxy resin a was 216, the alcoholic hydroxyl equivalent was 5510, and the average value of m was 0.04.

(Epoxy resin) Epoxy resin a: Epoxy resin obtained in Synthesis Example 1 b: Biphenyl epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-4000, epoxy equivalent 196, alcoholic hydroxyl equivalent 5000 ) Epoxy resin c: Biphenylaralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 275, alcoholic hydroxyl equivalent 4520)

(Isocyanate compound) Isocyanate A: A mixture of 2,4-toluene diisocyanate (65%) and 2,6-toluene diisocyanate (35%) (Mitsui Chemical SKC Polyurethane Co., Ltd., Cosmo Cosmonate (registered trademark) T-65, NCO concentration 48%) Isocyanate B: 2,4'-diphenylmethane diisocyanate (50%) and 4,4'-diphenylmethane diisocyanate (50 %) Mixture (BASF INOAC Polyurethane Co., Ltd., Lupranate (registered trademark) MI, NCO concentration 33%) Isocyanate C: Polymethylene poly Phenyl polyisocyanate (BASF INOAC Polyurethane Co., Ltd., Lupranate (registered trademark) M20S, NCO concentration 31%)

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

(Hardener) PN: Phenol novolac resin (manufactured by Showa Denko Corporation, shonol (registered trademark) BRG-557, softening point 80 ° C, phenolic hydroxyl equivalent 105) DCPD: dicyclopentadiene / Phenol co-condensation resin (manufactured by Qunei Chemical Co., Ltd., GDP9140, phenolic hydroxyl equivalent 196) DICY: dicyandiamine (manufactured by Japan Carbide Industry Co., Ltd., DIHARD, active hydrogen equivalent 21) SMA: styrene / Maleic acid copolymer resin (manufactured by Cray Valley, SMA2000, anhydride equivalent 316)

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

(Flame retardant) LC-950: Phenol hardener containing phosphorus (manufactured by Shin-AT & C, LC-950PM60, phenolic hydroxyl equivalent 341, 9.3% phosphorus content, propylene glycol monomethyl ether solution, 60% non-volatile content) SPB-100: phosphazene flame retardant (manufactured by Otsuka Chemical Co., Ltd., SPB-100, 13% phosphorus content)

Example 1 In the same apparatus as in Synthesis Example 1, 40 parts of epoxy resin a as epoxy resin (a1), 60 parts of epoxy resin b as epoxy resin (a2), and 0.1 part of epoxy resin b TMAI as a catalyst was heated while nitrogen was introduced, and maintained at a temperature of 120 ° C. for 30 minutes to remove water in the system. Next, while maintaining a reaction temperature of 130 ° C to 140 ° C, 8.6 parts (modification rate 20 mol%) of isocyanate A as an isocyanate compound (b) was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for 3 hours while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin composition (resin 1). About the obtained oxazolidone ring containing epoxy resin composition, the epoxy equivalent, softening point, molecular weight distribution, and solvent solubility were measured. In addition, the modification rate is the percentage of the modification rate using the isocyanate group of the isocyanate compound (b) with respect to 1 equivalent of epoxy groups of the epoxy resin (a) [(b) / (a) × 100]. Here, (a) and (b) show the molar number of the epoxy group of the epoxy resin (a), and the molar number of the isocyanate group of the isocyanate compound (b). The measurement results are shown in Table 1.

Example 2 to Example 8 According to the loading amount (parts) of each raw material shown in Table 1, an epoxy resin composition containing an oxazolidone ring was synthesized using the same apparatus and the same operation as in Example 1. Thing. The epoxy equivalent, softening point, molecular weight distribution, and solvent solubility of the obtained oxazolidone ring-containing epoxy resin composition were measured in the same manner as in Example 1. Table 1 shows the measurement results. The oxazolidone ring-containing epoxy resin compositions obtained in Examples 2 to 8 were used as resins 2 to 8.

[Table 1]

Comparative Example 1 to Comparative Example 7 The loading amount (parts) of each raw material shown in Table 2 was set, and the same apparatus as in Example 1 was used to synthesize an oxazolidone ring-containing epoxy resin by the same operation.组合 物。 Composition. The epoxy equivalent, softening point, molecular weight distribution, and solvent solubility of the obtained oxazolidone ring-containing epoxy resin composition were measured in the same manner as in Example 1. Table 2 shows the measurement results. The oxazolidone ring-containing epoxy resin compositions obtained in these Comparative Examples 1 to 7 were used as resins H1 to H7.

[Table 2]

Example 9 100 parts of resin as an epoxy resin, 38 parts of PN as a hardener, and 0.12 parts of 2E4MZ as a hardening accelerator were prepared, and dissolved in MEK, propylene glycol monomethyl ether, N, N-di A hardening resin composition varnish was obtained in a mixed solvent prepared from methylformamide.

The obtained hardening resin composition varnish was impregnated into a glass cloth (manufactured by Nitto Textile Co., Ltd., WEA 116E106S136, thickness 0.1 mm). The impregnated glass cloth was dried in a hot air circulation oven at 150 ° C. for 11 minutes to obtain a prepreg. 8 pieces of the obtained prepreg were overlapped with copper foil (manufactured by Mitsui Metals Mining Co., Ltd., 3EC-III, thickness 35 μm), and the temperature was 130 ° C × 15 minutes + 190 ° C × 80 minutes for 2 Vacuum compression of MPa to obtain a 1.0 mm thick laminated board. Table 3 shows the results of the glass transition temperature, copper foil peeling strength, and interlayer adhesion of the laminated board.

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

Example 10 to Example 20 Resins 2 to 18, epoxy resins c, PN, and 2E4MZ of Examples 2 to 8 were blended at the blending amounts (parts) in Tables 3 and 4 and the same use as in Example 9 was used. The same operation was carried out to obtain a laminated board and a test piece. The same tests as in Example 9 were performed, and the results are shown in Tables 3 and 4.

[table 3]

[Table 4]

Comparative Example 8 to Comparative Example 13 The resins H1 to H7, other epoxy resins c, PN, and 2E4MZ of Comparative Example 1 to Comparative Example 7 were blended at the blending amounts (parts) in Table 5. Using the same device as in Example 9, The same operation was performed to obtain a laminated board and a test piece. The same test as in Example 9 was performed, and the results are shown in Table 5.

[table 5]

Example 21 to Example 26 Resin 1, Resin 6, Resin 7, Resin 8, PN, 2E4MZ, and flame retardant were blended in the blending amount (parts) of the formulation in Table 6 in Example 6 and used and implemented. The same apparatus as in Example 9 was used to obtain a laminated board and a test piece by the same operation. The same test as in Example 9 was performed, and the results are shown in Table 6. In addition, both sides of the obtained laminated board were etched to prepare a test piece for measuring the flame retardancy, and a flame retardance test was performed. The results are shown in Table 6.

[TABLE 6]

Comparative Example 16 to Comparative Example 19 Resins H1 to Resin H7, PN, 2E4MZ, and flame retardants of Comparative Example 1 to Comparative Example 7 were prepared at the compounding amount (parts) of the formulation in Table 7, using the same apparatus as in Example 9. With the same operation, a laminated board and a test piece were obtained. The same test as in Example 9 was performed, and the results are shown in Table 7. In addition, both sides of the obtained laminated board were etched to prepare a test piece for measuring the flame retardancy, and a flame retardance test was performed. The results are shown in Table 7.

[TABLE 7]

no.

no.

Claims (14)

An oxazolidone ring-containing epoxy resin composition is an oxazolidone ring-containing epoxy resin composition obtained from an epoxy resin (a) and an isocyanate compound (b), and is characterized in that: The epoxy resin (a) is a mixture of the epoxy resin (a1) represented by the following formula (1) and the epoxy resin (a2) represented by the following formula (2) as an essential component, and the epoxy resin (A1) is 5 mass% to 50 mass%, and the total amount of the epoxy resin (a1) and the epoxy resin (a2) is 55 mass% to 100 mass%; In the formula, X is a ring member 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. 5 to 8 cycloalkyl groups; R ¹ and R ² are each independently 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, and 6 carbon atoms An aryl group of 10 to 10 or an aralkyl group of 7 to 10 carbons, k1 and k2 are each independently an integer of 0 to 4; G is a glycidyl group; m and n represent repeating numbers, and the average value is 0 to 2. The oxazolidone ring-containing epoxy resin composition according to item 1 of the scope of the patent application, wherein the epoxy group (a) has an alcoholic hydroxyl equivalent of 1,000 g / eq. Or more. The oxazolidone ring-containing epoxy resin composition according to claim 1 or claim 2, wherein the isocyanate compound (b) has an average of 1.8 or more isocyanate groups in the molecule. The oxazolidone ring-containing epoxy resin composition according to any one of claims 1 to 3 in the patent application scope, wherein the epoxy equivalent is 200 g / eq. To 600 g / eq. The oxazolidone ring-containing epoxy resin composition according to any one of claims 1 to 4 in the scope of the patent application, which has a softening point of 50 ° C to 150 ° C. A method for producing an oxazolidone ring-containing epoxy resin composition, comprising: in the presence of a catalyst, containing 5% to 50% by mass of an epoxy resin represented by the following formula (1) ( a1), an epoxy resin (a) containing an epoxy resin (a1) and an epoxy resin (a2) represented by the following formula (2), and an isocyanate compound (b) in a total amount of 55% by mass to 100% by mass )reaction; In the formula, X is a group having 5 to 8 ring members having at least one substituent selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 11 carbon atoms. Cycloalkyl; R ¹ and R ² are each independently 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, and 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 repeating numbers, and the average value is 0 to 2. The method for producing an oxazolidone ring-containing epoxy resin composition according to item 6 of the scope of patent application, wherein the epoxy group (a) has an alcoholic hydroxyl equivalent of 1,000 g / eq. Or more. The method for producing an oxazolidone ring-containing epoxy resin composition according to item 6 or item 7 of the scope of patent application, wherein the isocyanate compound (b) has an average of 1.8 or more isocyanate groups in the molecule . The method for producing an oxazolidone ring-containing epoxy resin composition according to any one of claims 6 to 8 in the scope of the patent application, wherein the earrings are 1 mole to the epoxy resin (a). Oxygen, the isocyanate group of the isocyanate compound (b) is in a range of 0.02 mol or more and less than 0.5 mol. A curable resin composition, comprising: an oxazolidone ring-containing epoxy resin composition and a curing agent as described in any one of claims 1 to 5 of the scope of patent application, as essential components. The hardening resin composition according to item 10 of the scope of application for a patent, wherein the hardener is an epoxy resin hardener having an active hydrogen group, and is relative to all epoxy resins in the hardening resin composition. 1 mol earring oxy group, the active hydrogen group of the hardener is 0.2 mol to 1.5 mol. A hardened product, which is obtained by hardening the hardenable resin composition described in the tenth or eleventh scope of the patent application. A prepreg, characterized in that it is obtained from a hardening resin composition as described in item 10 or 11 of the scope of patent application. A laminated board, characterized in that it is obtained from the hardening resin composition described in item 10 or 11 of the scope of patent application.