Epoxy resins, curable compositions, cured products, and electrical and electronic components

Abstract

This provides an epoxy resin with an excellent balance of low dielectric properties and low storage modulus. [Solution] An epoxy resin represented by formula (1) contains a compound represented by formula (2), wherein the ratio of the peak area of ​​the compound represented by formula (2) in high-performance liquid chromatography measurement is 0.001 to 5.0 area%. TIFF2026095849000043.tif55170 (R: Hydrogen atom, or alkyl group with 1 to 5 carbon atoms. X: Divalent hydrocarbon group with 1 to 18 carbon atoms, -C(CF3)2-, or single bond. p is 0 or 1. n: An integer greater than or equal to 0. If p is 0, X excludes -C(CH3)2- and -CH2-.)

Description

[Technical Field]

[0001] The present invention relates to epoxy resins, curable compositions, cured products, and electrical and electronic components, and more particularly to epoxy resins with excellent low dielectric properties and low storage modulus, curable compositions containing the same and their cured products, and electrical and electronic components. [Background technology]

[0002] Epoxy resins, typified by diglycidyl ether, are used in a wide range of fields, including adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic components, due to their excellent adhesion, water resistance, mechanical strength, and electrical properties. In particular, they are widely used in the electrical and electronic fields for insulating casting, laminating materials, and sealing materials. In recent years, multilayer circuit boards used in electrical and electronic equipment have become smaller, lighter, and more functional, requiring further multilayering, higher density, thinner construction, lighter weight, and improved reliability and moldability.

[0003] Low dielectric properties are an important requirement for epoxy resins used as materials for electrical and electronic components such as laminates for electrical and electronic circuits. In recent years, communication frequencies have been increasing to improve the amount and speed of information transmission, and in this context, the increase in transmission loss (α) has become a major challenge. The lower the value of α, the less attenuation there is in the information signal, and the higher the reliability of the communication. Since α is proportional to the frequency (f), α becomes large in high-frequency communication, leading to a decrease in reliability. One method to suppress α is to reduce the dielectric loss tangent (tanδ), which, like f, is proportional to α. For high-speed transmission of communication signals, materials with low tanδ, that is, materials with low dielectric properties, are required.

[0004] Furthermore, electrical and electronic components such as laminates for electrical and electronic circuits require high reliability, and the epoxy resin used as the material must have a balance of various properties, including low dielectric properties, a low mean linear expansion coefficient, a low storage modulus, heat resistance, and flame retardancy. In particular, a low storage modulus is an essential property to ensure the relaxation of internal stresses.

[0005] Low molecular weight bisphenol A type epoxy resin (bisphenol A type diglycidyl ether) is generally widely known as an epoxy resin used as a material for electrical and electronic components such as laminates for electrical and electronic circuits. However, its heat resistance and dielectric properties were not sufficient. In recent years, diglycidyl ethers with various skeletons have been investigated, and Patent Document 1 discloses a bisphenol C type epoxy resin (bisphenol C type diglycidyl ether) that has excellent low dielectric properties. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2023-36020 [Overview of the project] [Problems that the invention aims to solve]

[0007] Currently, FC-BGA is the dominant package used for data center information processing devices, where each semiconductor chip is mounted on its own package substrate. In contrast, in recent years, packages have been proposed in which multiple semiconductor chips are mounted on a single interposer and housed within a single package. Since information is transmitted via the interposer, the distance between chips is shortened, enabling higher speeds. Consequently, the package substrate becomes larger, and the materials used require not only low dielectric loss tangent but also low modulus of elasticity to suppress warping.

[0008] Furthermore, for the reasons mentioned above, the composition of epoxy resins tends to become more complex, and the importance of low molecular weight epoxy resins, which have good solubility in solvents, compatibility with other resins, and dispersibility of fine particle fillers such as silica, as well as excellent handling properties, is increasing.

[0009] However, the bisphenol C type epoxy resin described in Patent Document 1 and the generally known bisphenol A type epoxy resin have the problem that the balance between low dielectric properties and low storage modulus in the cured product is not sufficiently satisfactory.

[0010] The object of the present invention is to provide an epoxy resin with an excellent balance of low dielectric properties and low storage modulus, a curable composition containing the epoxy resin and a curing agent, a cured product thereof, and electrical and electronic components using the curable composition. [Means for solving the problem]

[0011] As a result of diligent research, the inventors of the present invention have found that the above problem can be solved by including a 1,2-glycol compound in a specific epoxy resin.

[0012] In other words, the gist of the present invention lies in the following [1] to [9]. [1] An epoxy resin comprising the epoxy resin represented by the following formula (1) and the compound represented by the following formula (2), wherein the ratio of the peak area of ​​the compound represented by the following formula (2) in high-performance liquid chromatography measurement is 0.001 to 5.0 area%. [ka] (In formula (1) above, each of the substituents R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Each of the linking groups X is independently a divalent hydrocarbon group having 1 to 18 carbon atoms, -C(CF3)2-, or a single bond. p is 0 or 1. n represents the number of repetitions and is a non-negative integer. However, if p is 0, the linking groups X are not -C(CH3)2- and -CH2-.) [ka] (In formula (2) above, each of the substituents R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The linking group X is a divalent hydrocarbon group having 1 to 18 carbon atoms, -C(CF3)2-, or a single bond. p is 0 or 1. However, if p is 0, the linking group X is not -C(CH3)2- or -CH2-.) [2] The epoxy resin described in [1], wherein the epoxy equivalent is 150 to 500 g / equivalent. [3] The epoxy resin according to [1] or [2], wherein the ratio of peak areas of epoxy resins where n in formula (1) is 0 in the high-performance liquid chromatography measurement is 50 area % or more. [4] An epoxy resin according to any one of items [1] to [3], wherein the total chlorine content is 5,000 ppm or less. A curable composition comprising the epoxy resin and curing agent described in any one of the items [5] [1] to [4]. [6] The curable composition according to [5], comprising 0.1 to 100 parts by mass of the curing agent in terms of solid content per 100 parts by mass of the solid content of the epoxy resin. [7] The curable composition according to [5] or [6], wherein the curing agent is at least one selected from the group consisting of phenolic curing agents, amide curing agents, imidazoles, and active ester curing agents. A cured product obtained by curing the curable composition described in [8] [5] or [6]. Electrical and electronic components comprising the curable composition described in [9] [5] or [6]. [Effects of the Invention]

[0013] According to the present invention, an epoxy resin, a curable composition, and a cured product having an excellent balance between low dielectric properties and a low elastic modulus can be provided. Therefore, the epoxy resin and the curable composition of the present invention are applicable to various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic components, and are particularly useful as insulating casting, laminated materials, sealing materials, etc. in the electrical and electronic fields. The epoxy resin of the present invention and the curable composition containing the same are suitable for use in multilayer printed wiring boards, laminated boards for electrical and electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor sealing materials, underfill materials, interchip fills for 3D-LSI, insulating sheets, prepregs, heat dissipation substrates, and the like.

Embodiments for Carrying Out the Invention

[0014] Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to the description below as long as it does not exceed the gist thereof. In this specification, when the expression "~" is used, it shall be used as an expression including the numerical values or physical property values before and after it. Note that the epoxy resin of this embodiment includes those having a repeating structure and those having a single molecular structure. However, in the industry, any epoxy compound may be expressed as an "epoxy resin" or an "epoxy resin composition" and may be sold. In the industry, a mixture further containing an epoxy resin different from the epoxy resin of this embodiment may be expressed as an "epoxy resin composition", but may also be simply referred to as an "epoxy resin".

[0015] 〔Epoxy resin〕 An epoxy resin according to one embodiment of the present invention is an epoxy resin in which a compound represented by the following formula (1) (hereinafter, may be abbreviated as "compound (1)") contains a compound represented by the following formula (2) (hereinafter, may be abbreviated as "compound (2)").

[0016]

Chemical formula

[0017] In formula (1) above, each of the substituents R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Each of the linking groups X is independently a divalent hydrocarbon group having 1 to 18 carbon atoms, -C(CF3)2-, or a single bond. p is 0 or 1. n represents the number of repetitions and is a non-negative integer. However, if p is 0, the linking groups X are not -C(CH3)2- and -CH2-.

[0018] [ka]

[0019] In formula (2) above, each substituent R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The linking group X is a divalent hydrocarbon group having 1 to 18 carbon atoms, -C(CF3)2-, or a single bond. p is 0 or 1. However, if p is 0, the linking group X is not -C(CH3)2- or -CH2-.

[0020] The alkyl group R in formulas (1) and (2) may be linear or branched. Specifically, examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, and tert-pentyl group. R is preferably a methyl group, an ethyl group, or an isopropyl group, and most preferably a methyl group.

[0021] In formulas (1) and (2), X is preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, or -C(CF3)2-. Examples of divalent hydrocarbon groups having 1 to 18 carbon atoms include groups represented by the following formulas (3) to (7).

[0022] [ka]

[0023] In the formula (3), the plurality of R 1 may be the same as or different from each other, and is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, the total number of carbon atoms of each R 1 is 17 or less.

[0024]

Chemical formula

[0025] In the formula (4), the plurality of R 2 may be the same as or different from each other, and is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, the total number of carbon atoms of each R 2 is 10 or less.

[0026]

Chemical formula

[0027] In the formula (5), the plurality of R 3 may be the same as or different from each other, and is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. However, the total number of carbon atoms of each R 3 is 4 or less.

[0028]

Chemical formula

[0029] In the formula (6), R 4 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. m is an integer from 0 to 5. When m is 2 or more, the plurality of R 4 may be the same as or different from each other. However, the total number of carbon atoms of each R 4 is 12 or less. )

[0030]

Chemical formula

[0031] Specific examples of X include the base represented by the following equations (X-1) to (X-4).

[0032] [ka]

[0033] In equations (1) and (2), n is a non-negative integer. The upper limit of n is not particularly limited, but it is usually 20 or less, may be 15 or less, and is preferably 10 or less. n is preferably 0 to 5, more preferably 0 to 3, and most preferably 0 or 1.

[0034] [Content of compound (2) in epoxy resin] The content of compound (2) in the epoxy resin of this embodiment, that is, the percentage of the peak area of ​​compound (2) in high-performance liquid chromatography measurement, is preferably 0.001 to 5.0 area%, more preferably 0.02 to 4.0 area%, even more preferably 0.03 to 3.5 area%, and most preferably 0.1 to 3.0 area%. If the content of compound (2) is higher than the upper limit, the dielectric properties deteriorate due to the influence of hydroxyl groups, and if it is lower than the lower limit, the crosslinking density increases, so the storage modulus becomes large and stress relaxation does not occur sufficiently. On the other hand, if the content of compound (2) is within the above range, physical properties with an excellent balance between dielectric properties and storage modulus can be obtained.

[0035] There are no particular limitations on the method for incorporating compound (2) into the epoxy resin of this embodiment. For example, one method may involve manufacturing compound (1) and compound (2) separately and then mixing them in a predetermined ratio, or one method may involve generating compound (2) during the manufacturing process of compound (1).

[0036] In this embodiment, the epoxy resin preferably has a peak area ratio (content) of 50 area% or more and 99 area% or less for the epoxy resin where n in formula (1) is 0 (hereinafter sometimes abbreviated as "n=0"), and a peak area ratio (content) of 50 area% or less and 1 area% or more for the epoxy resin where n in formula (1) is 1 (hereinafter sometimes abbreviated as "n=1"), as measured by high-performance liquid chromatography. By controlling the content of n=0 and n=1 within the above ranges, it becomes easier to balance dielectric properties and heat resistance.

[0037] In the epoxy resin of this embodiment, the content of n=0 isomers, i.e., the percentage of the peak area of ​​n=0 isomers in high-performance liquid chromatography measurements, is preferably 60 area% or more, more preferably 70 area% or more, even more preferably 80 area% or more, and particularly preferably 90 area% or more, from the viewpoint of improving reactivity and maintaining good dielectric properties. On the other hand, as the amount of n=0 isomers increases, the burden on purification processes such as distillation when manufacturing the epoxy resin of this embodiment on an industrial scale may increase. Therefore, from the viewpoint of improving productivity, the content of n=0 isomers is preferably 98 area% or less, more preferably 97 area% or less, even more preferably 96 area% or less, and particularly preferably 95 area% or less. The lower and upper limits of the n=0 isomer content can be arbitrarily combined and may be, for example, 60-98 area%, 70-97 area%, 80-96 area%, or 90-95 area%.

[0038] In the epoxy resin of this embodiment, the content of n=1, i.e., the percentage of the peak area of ​​n=1 in high-performance liquid chromatography measurements, is preferably 30 area% or less, more preferably 20 area% or less, even more preferably 16 area% or less, and particularly preferably 12 area% or less, from the viewpoint of improving reactivity and maintaining good dielectric properties and heat resistance. On the other hand, from the viewpoint of improving productivity, the content of n=1 is preferably 2 area% or more, more preferably 4 area% or more, and even more preferably 6 area% or more. The lower and upper limits of the n=1 content can be arbitrarily combined and may be, for example, 2 to 30 area%, 4 to 20 area%, 6 to 16 area%, or 6 to 12 area%.

[0039] The epoxy resin of this embodiment can satisfy the above characteristics by the epoxy resin manufacturing method described later.

[0040] The epoxy resin of this embodiment preferably contains n=0 and n=1 as compound (1) as described above, but may also contain components with n=2 or more. When components with n=2 or more are included, their content is preferably 12 area% or less, more preferably 5 area% or less, and even more preferably 2 area% or less, as expressed as the percentage of peak area in high-performance liquid chromatography measurement.

[0041] As mentioned above, the content of compound (2) in the epoxy resin, as well as the content of components with n=0, n=1, and n=2 or more, can be determined by high-performance liquid chromatography. Specifically, this can be determined by measuring under the conditions shown in the section "Analysis of the Content of Constituent Components" in the Examples described below.

[0042] [Epoxy equivalent] The epoxy equivalent of the epoxy resin in this embodiment is preferably 150 to 500 g / equivalent. From the viewpoint of maintaining good heat resistance and dielectric properties, the epoxy equivalent is more preferably 400 g / equivalent or less, and even more preferably 300 g / equivalent or less. Furthermore, from the viewpoint of improving productivity, it is more preferably 160 g / equivalent or more, even more preferably 170 g / equivalent or more, and particularly preferably 180 g / equivalent or more. The epoxy equivalent can be controlled by the epoxy resin manufacturing method described later.

[0043] [Total chlorine content] The total chlorine content of the epoxy resin in this embodiment is preferably 5,000 ppm or less. Furthermore, from the viewpoint of improving reliability when used in electrical and electronic components, especially insulating materials, it is preferably 3,000 ppm or less, more preferably 2,000 ppm or less, and particularly preferably 1,500 ppm or less. The total chlorine content can be measured in accordance with JIS K 7243-3.

[0044] [Manufacturing method for epoxy resin] As described above, the epoxy resin manufacturing method of this embodiment may involve manufacturing compound (1) and compound (2) separately and then mixing them in a predetermined ratio, or manufacturing compound (1) by epoxidizing a bisphenol compound under conditions that produce compound (2) in a predetermined ratio during the manufacturing process of compound (1). The following describes a manufacturing method in which compound (2) is produced within compound (1).

[0045] <Method for producing compound (1) and compound (2)> Examples of methods for producing compound (1) and compound (2) include reacting a bisphenol compound, which is a raw material for compound (1), with an epihalohydrin in the presence of an alkali, or allyling the bisphenol compound, which is a raw material for compound (1), and then oxidizing the olefin portion to epoxidize it.

[0046] In the method for producing compound (1), the bisphenol compound used as the raw material is a bisphenol compound represented by the following formula (8).

[0047] [ka]

[0048] In formula (8) above, the substituent R, integer p, and linking group X are equivalent to those in formula (1).

[0049] The reaction step of reacting the bisphenol compound represented by formula (8) with an epihalohydrin in the presence of an alkali is not particularly limited, but a reaction step in which the bisphenol compound represented by formula (8) and the epihalohydrin are reacted in a single step is preferred. The following describes the reaction process using this one-step method in detail.

[0050] (One-step reaction process) A specific example of a one-step method for producing compound (1) is a method in which 1 mole of hydroxyl groups of the bisphenol compound represented by formula (8) is reacted with 1.00 to 20.0 moles, preferably 1.50 to 15.0 moles, more preferably 2.0 to 12.0 moles, and even more preferably 4.0 to 10.0 moles of epihalohydrin. If the amount of epihalohydrin used is too small, it will lead to an increase in viscosity in the formation of compound (1), as well as deterioration of dielectric properties and heat resistance. If the amount of epihalohydrin is too large, the economic efficiency will be poor.

[0051] More specifically, a bisphenol compound represented by formula (8) is mixed with an epihalohydrin such as epichlorohydrin and reacted in the presence of an alkali. It is preferable to use an alkali metal hydroxide in solid or aqueous form as the alkali. This reaction can be carried out under normal pressure or reduced pressure, with the reaction temperature being 20-150°C under normal pressure and 30-80°C under reduced pressure. The reaction is carried out while dehydrating by azeotropizing the reaction solution while maintaining a predetermined temperature as needed, cooling the volatile vapors to obtain a condensate, separating the oil / water, and returning the oil (from which the water has been removed) to the reaction system. To suppress a rapid reaction, it is preferable to add the alkali metal hydroxide to the reaction system in small amounts intermittently or continuously over 0.1-10 hours. The total reaction time between the bisphenol compound represented by formula (8) and the epihalohydrin can be 1-15 hours.

[0052] After the reaction is complete, the insoluble by-product salt is removed from the reaction solution containing the target product, compound (1), by filtration or by washing with water. Then, the unreacted epihalohydrin is removed by distillation under reduced pressure to obtain the target compound (1).

[0053] In this reaction, it is preferable to use epichlorohydrin or epibromohydrin as the epihalohydrin. As the alkali metal hydroxide, it is preferable to use sodium hydroxide or potassium hydroxide.

[0054] Furthermore, catalysts such as quaternary ammonium salts like tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines like benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; imidazoles like 2-ethyl-4-methylimidazole and 2-phenylimidazole; phosphonium salts like ethyltriphenylphosphonium iodide; and phosphines like triphenylphosphine may also be used in this reaction.

[0055] Furthermore, in this reaction, inert organic solvents such as alcohols like ethanol, isopropyl alcohol, and ethylene glycol; ketones like acetone and methyl ethyl ketone; ethers like dioxane; glycol ethers like methoxypropanol; and aprotic polar solvents like dimethyl sulfoxide and dimethylformamide may be used.

[0056] The compound (1) obtained as described above can also be reprocessed to obtain compound (1) with a sufficiently reduced amount of saponifiable halogen. For example, the crude compound (1) obtained by the reaction can be redissolved in an inert organic solvent, an alkali metal hydroxide can be added in solid or aqueous solution, and a re-cyclization reaction can be carried out at a temperature of about 20 to 120°C for 0.5 to 8 hours. After that, excess alkali metal hydroxide and by-product salts can be removed by washing with water or other methods, and the organic solvent can be removed by distillation under reduced pressure to obtain purified compound (1) in a single step. Examples of inert organic solvents include isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, and dimethyl sulfoxide.

[0057] When compound (1) is produced by a one-step method, at least a bisphenol compound represented by formula (8) is used as a raw material. However, other polyhydric hydroxy compounds (hereinafter sometimes referred to as "other polyhydric hydroxy compounds") may also be used in combination, and the compound (1) may be produced as a mixture of compound (1) and other epoxy resins. However, from the viewpoint of enhancing the effects of the present invention, the proportion of the bisphenol compound represented by formula (8) is preferably 72 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, based on the total amount of polyhydric hydroxy compounds used as raw materials. The upper limit is 100 mol%, and most preferably 100 mol%. In this specification, "polyhydric hydroxy compound" is a general term for dihydric or higher phenol compounds and dihydric or higher alcohols.

[0058] Other polyhydric hydroxy compounds include, for example, various polyhydric phenols such as bisphenol A, bisphenol AF, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolac resin, naphthol novolac resin, brominated bisphenol A, brominated phenol novolac resin, and various phenols mixed with benzaldehyde, hydroxybenzaldehyde, and crotonaldehyde. Examples include polyhydric phenolic resins obtained by condensation reactions with various aldehydes such as glyoxal, polyhydric phenolic resins obtained by condensation reactions between xylene resin and phenols, various phenolic resins such as co-condensation resins of heavy oil or pitch with phenols and formaldehydes, ethylene glycol, trimethylene glycol, propylene glycol, linear aliphatic diols such as 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, and 1,6-hexanediol; cyclic aliphatic diols such as cyclohexanediol and cyclodecanediol; and polyalkylene ether glycols such as polyethylene ether glycol, polyoxytrimethylene ether glycol, and polypropylene ether glycol.Preferred materials among these include phenol novolac resins, phenol aralkyl resins, polyhydric phenol resins obtained by the condensation reaction of phenol and hydroxybenzaldehyde, biphenyl aralkyl resins, naphthol aralkyl resins, ethylene glycol, trimethylene glycol, propylene glycol, linear aliphatic diols such as 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, and 1,6-hexanediol, cyclic aliphatic diols such as cyclohexanediol and cyclodecanediol, and polyalkylene ether glycols such as polyethylene ether glycol, polyoxytrimethylene ether glycol, and polypropylene ether glycol.

[0059] Methods for controlling the amounts of n=0 and n=1 compound (1) include, for example, adjusting the molar ratio of the bisphenol compound represented by formula (8) and the epihalohydrin used in the reaction step described above, adjusting the amount of alkali used, controlling the amount through purification or distillation, and combining these methods.

[0060] Specifically, increasing the amount of epihalohydrin used in the reaction can increase the proportion of the n=0 compound and decrease the proportion of the n=1 compound. Furthermore, using 1 mole or more of epihalohydrin per mole of phenolic hydroxyl groups of the bisphenol compound represented by formula (8) in the starting material can increase the proportion of the n=0 compound, while using less than 1 mole can increase the proportion of the n=1 compound or the proportion of components with 2 or more compounds.

[0061] Furthermore, by using more alkali than the reaction equivalent in the synthesis, the content of n=1 isomer or the content of components with n=2 or more isomers can be increased. In addition, there is a method in which the bisphenol compound represented by formula (8) is reacted with an epihalohydrin to obtain the product, and then distillation or column chromatography is performed to increase the content of n=0 isomer while decreasing the content of n=1 isomer. Depending on the conditions of the distillation or column chromatography operation, the reverse control is also possible.

[0062] (Method for producing compound (2)) Compound (2) is produced in the manufacturing reaction of compound (1) described above by the reaction of a glycidyl group with water. It is also produced by the addition of glycidol to a phenolic hydroxyl group. Since glycidol is produced by the addition of water to epihalohydrin and ring opening with alkali, it is usually present as an impurity in epihalohydrin. Therefore, the content of compound (2) in the epoxy resin can be adjusted by the amount of water in the reaction system and the amount of glycidol in the epihalohydrin. In this embodiment, it is necessary to adjust the amount of glycidol in the epihalohydrin used and the amount of water in the reaction system so that the content of compound (2) falls within a predetermined range.

[0063] The compound (2) content can be adjusted after the epoxy resin has been manufactured by extracting components rich in compound (2) using polar solvents such as alcohols, removing compound (2) by distillation or column chromatography, or conversely, extracting components with low levels of compound (2) using non-polar solvents such as hydrocarbons.

[0064] [Curable composition] One embodiment of the present invention is a curable composition comprising at least the epoxy resin of the embodiment of the present invention described above and a curing agent. Furthermore, the curable composition of this embodiment may optionally contain other epoxy resins, inorganic fillers, coupling agents, antioxidants, and other additives as needed. The curable composition of this embodiment offers improved handling properties through the incorporation of the epoxy resin of the embodiment of the present invention, thereby improving compatibility with other components, increasing the amount of filler that can be added, and improving impregnation into glass cloth. Moreover, its low storage modulus and low dielectric properties make it advantageous for the miniaturization, multilayering, high-density and high-frequency applications of electronic components.

[0065] [Hardening agent] In this specification, "curing agent" refers to a substance that contributes to the crosslinking reaction and / or chain length extension reaction between epoxy groups of an epoxy resin. In this specification, even substances referred to as "curing accelerators" will be considered curing agents if they contribute to the crosslinking reaction and / or chain length extension reaction between epoxy groups of an epoxy resin.

[0066] The curing agent content in the curable composition of this embodiment is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 90 parts by mass, and even more preferably 0.1 to 80 parts by mass, based on 100 parts by mass of solids of the epoxy resin of this embodiment.

[0067] When the curable composition of this embodiment contains other epoxy resins described later, the mass ratio of the solid content of the epoxy resin of this embodiment to the other epoxy resins is preferably 99 / 1 to 1 / 99. In this case, the content of the curing agent in the curable composition of this embodiment is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 90 parts by mass, and even more preferably 0.1 to 80 parts by mass, based on 100 parts by mass of the total solid content of the epoxy resin of this embodiment and other epoxy resins.

[0068] In this specification, "solid content" refers to the components excluding the solvent, and includes not only solid epoxy resins but also semi-solid and viscous liquid substances. Furthermore, "total epoxy resin components" refers to the sum of the epoxy resin of this embodiment and other epoxy resins described later.

[0069] There are no particular restrictions on the curing agent used in the curable composition of this embodiment; all commonly known epoxy resin curing agents can be used. From the viewpoint of improving heat resistance, preferred curing agents include phenolic curing agents, amide curing agents, imidazoles, and active ester curing agents. The curing agent may be used alone, or two or more may be mixed in any combination and ratio. The following are examples of phenolic curing agents, amide curing agents, imidazoles, active ester curing agents, and other usable curing agents.

[0070] <Phenol-based curing agent> As the curing agent used in the curable composition of this embodiment, a phenolic curing agent is preferred from the viewpoint of improving the handlingability of the resulting curable composition and the heat resistance after curing.

[0071] Specific examples of phenolic curing agents include, for example, bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxystyrene, hydroquinone, resorcinol, catechol, and t-butylcatechol. t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene Examples include 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allyl or polyallylated derivatives of the above dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, etc. The phenolic curing agent may be used alone, or two or more may be mixed in any combination and ratio.

[0072] When using a phenolic curing agent, it is preferable that the amount used be in the range of 0.8 to 1.5 in terms of the equivalent ratio of functional groups in the curing agent to epoxy groups in the total epoxy resin components of the curable composition. This range is preferable because it reduces the likelihood of unreacted epoxy groups or functional groups of the curing agent remaining in the mixture.

[0073] <Amid-based hardener> As the curing agent used in the curable composition of this embodiment, an amide-based curing agent is preferred from the viewpoint of improving the heat resistance of the resulting curable composition.

[0074] Examples of amide-based curing agents include dicyandiamide and its derivatives, and polyamide resins. The amide-based curing agent may be used alone, or two or more may be mixed in any combination and ratio. When using an amide-based curing agent, it is preferable that the amount used be in the range of 0.1 to 20% by mass of the total epoxy resin components and curing agent in the curable composition.

[0075] <Imidazoles> As a curing agent used in this embodiment of the curable composition, imidazoles (imidazole-based curing agents) are preferred from the viewpoint of allowing the curing reaction to proceed sufficiently and improving heat resistance.

[0076] Imidazoles include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6-[2'-methylimidazolyl- Examples include (1')-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins with the above imidazoles. Although imidazoles have catalytic activity and can generally be classified as curing accelerators as described later, in this invention they are classified as curing agents. Imidazoles may be used individually or mixed in any combination and ratio of two or more types.

[0077] When using imidazoles as a curing agent, the amount used is preferably in the range of 0.1 to 20% by mass relative to the total amount of the epoxy resin components and imidazoles as solids in the curable composition.

[0078] <Activated ester-based curing agent> As the curing agent used in the curable composition of this embodiment, an active ester-based curing agent is preferred from the viewpoint of exhibiting low water absorption and low dielectric properties in the resulting cured product.

[0079] There are no particular restrictions on the active ester-based curing agent, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred.

[0080] The above-mentioned active ester curing agents are preferably those obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester resins obtained from a carboxylic acid compound or its halide and a hydroxy compound are preferred, and active ester resins obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound are more preferred.

[0081] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc., or their halides. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-phenol addition resins, etc.

[0082] As the active ester resin, specifically, active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins that are acetylated phenol novolacs, and active ester resins that are benzoylated phenol novolacs are preferred, and among these, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred in that they are excellent at improving peel strength.

[0083] More specifically, examples of active ester resins containing a dicyclopentadiene-phenol addition structure include the compound represented by the following formula (I) and the compound represented by the following formula (II).

[0084] [ka]

[0085] In the above formula (I), multiple R 21 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group. Each of the multiple Zs is independently a phenyl group, a naphthyl group, or a phenyl or naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic core. l is 0 or 1, and k' is the average of the repeating units, ranging from 0.05 to 3.5. Each of the multiple B's is independently selected from the structural sites represented by the following formulas (B'-1) to (B'-6).

[0086] [ka]

[0087] In the above equations (B'-1) to (B'-6), R 22 Each of these is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and R 23Each of the following is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group; Y is a linear alkylene group having 2 to 6 carbon atoms, an ether linkage, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group; and o and p are integers from 1 to 4.

[0088] [ka]

[0089] In formula (II) above, W is a phenyl group or a naphthyl group. l' represents 0 or 1, and k'' is the average of the repeating units, ranging from 0.05 to 3.5.

[0090] In formula (II), from the viewpoint of reducing the dielectric loss tangent of the cured resin composition and improving heat resistance, W is preferably a naphthyl group, l' is preferably 0, and k'' is preferably 0.25 to 1.5. Furthermore, polyarylate can be used as a curing agent similar to the compounds represented by formulas (I) and (II).

[0091] Examples of commercially available active ester curing agents include HPC-8000-65T (active ester curing agent containing a dicyclopentadiene structure), HPC-8150-60T (active ester curing agent containing a naphthalene structure as its main backbone) (both manufactured by DIC Corporation), and W-575 and V-575 (both manufactured by Unitika Ltd., polyarylates having a bisphenol backbone).

[0092] The active ester-based curing agent may be used alone, or two or more may be mixed in any combination and ratio. When using an active ester-based curing agent, it is preferable that the amount used be in the range of 0.2 to 2.0 in terms of the equivalent ratio of the active ester groups in the curing agent to the epoxy groups in the total epoxy resin components in the curable composition.

[0093] <Other hardening agents> Other curing agents that can be used in the curable composition of this embodiment include, for example, amine-based curing agents (excluding tertiary amines), acid anhydride-based curing agents, tertiary amines, organophosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron-halogenated amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, carbodiimides, and the like. These other curing agents may be used individually or mixed in any combination and ratio of two or more types.

[0094] [Other epoxy resins] The curable composition of this embodiment may contain other epoxy resins. By using other epoxy resins, it is possible to compensate for any lacking physical properties or to improve various physical properties.

[0095] Other epoxy resins that have two or more epoxy groups in their molecule are preferred, and various epoxy resins such as bisphenol A type epoxy resin, bisphenol AF type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol Z type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, and dicyclopentadiene type epoxy resin can be used. These can be used individually or as a mixture of two or more types.

[0096] In the curable composition of this embodiment, when using the epoxy resin of this embodiment and other epoxy resins, the amount of other epoxy resin blended in 100% by mass of the total epoxy resin component as solid content is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, on the other hand, preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. By having a proportion of other epoxy resins above the lower limit, the effect of improving physical properties by blending other epoxy resins can be fully obtained. On the other hand, by having a proportion of other epoxy resins below the upper limit, the effect of the epoxy resin of this embodiment is fully exhibited, which is preferable from the viewpoint of obtaining physical property improvement effects such as low storage modulus and low dielectric properties.

[0097] [solvent] The curable composition of this embodiment may be diluted with a solvent to appropriately adjust its viscosity during handling when forming a coating film. In the curable composition of this embodiment, the solvent is used to ensure the handling and workability of the curable composition during molding, and there are no particular restrictions on the amount used. In this invention, the terms "solvent" and "solvent" as described above are used to distinguish them according to their form of use, but they may be used independently as the same type or as different types.

[0098] The solvents that may be included in the curable composition of this embodiment include, for example, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; ethers such as ethylene glycol monomethyl ether; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; alcohols such as methanol and ethanol; alkanes such as hexane and cyclohexane; and aromatics such as toluene and xylene. These solvents may be used individually or mixed in any combination and ratio of two or more.

[0099] [Other ingredients] The curable composition of this embodiment may contain other components besides those listed above for the purpose of further improving its functionality. Examples of other components include thermosetting resins other than epoxy resins, photocurable resins, curing accelerators (excluding those included in the "curing agent"), UV inhibitors, antioxidants, coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, emulsifiers, deelasticizers, diluents, defoamers, ion trappers, inorganic fillers, organic fillers, and the like.

[0100] [Cured product] One embodiment of the present invention is a cured product, which is obtained by curing a curable composition that is one embodiment of the present invention. The cured product of this embodiment, obtained by curing the epoxy resin of this embodiment with a curing agent, has excellent handling properties for the curable composition, which allows for an increase in the amount of filler added and improved impregnation into glass cloth. Furthermore, it has excellent heat resistance and low dielectric properties, providing a cured product that is advantageous for the miniaturization, multilayering, high density, and high frequency of electronic components. Here, "curing" means intentionally curing the curable composition with heat and / or light, and the degree of curing can be controlled according to the desired physical properties and application. The degree of progress of the curing reaction may be fully cured or partially cured, and is not particularly limited, but the reaction rate of the curing reaction between the epoxy group and the curing agent may be 5 to 95%.

[0101] The curing method for the curable composition of this embodiment, when curing the curable composition to obtain the cured product of this embodiment, varies depending on the components and their amounts in the curable composition, but for example, heating conditions of 80 to 280°C for 60 to 360 minutes can be used. This heating is preferably a two-stage process consisting of primary heating at 80 to 160°C for 10 to 90 minutes and secondary heating at 120 to 200°C for 60 to 150 minutes. Furthermore, in formulations where the glass transition temperature (Tg) exceeds the secondary heating temperature, it is preferable to perform a tertiary heating of 150 to 280°C for 60 to 120 minutes. Performing secondary and tertiary heating in this manner is preferable from the viewpoint of reducing curing defects and solvent residue.

[0102] When preparing a semi-cured resin product, it is preferable to allow the curing reaction of the curable composition to progress to the extent that its shape can be maintained by heating or other means. If the curable composition contains a solvent, most of the solvent is usually removed by methods such as heating, reduced pressure, or air drying, but it is also acceptable to leave 5% by mass or less of the solvent in the semi-cured resin product.

[0103] [Application] The epoxy resin of this embodiment offers excellent productivity and handling properties, as well as superior heat resistance, low dielectric properties, and stress relaxation. Furthermore, it allows for improved handling of its curable composition, enabling increased filler addition, improved compatibility with other resin components, and enhanced impregnation into glass cloth. For these reasons, it can be applied to various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic components. In particular, it is useful as an insulating casting material, laminating material, and sealing material in the electrical and electronic fields.

[0104] Examples of applications for epoxy resins and curable compositions containing the same, which are embodiments of the present invention, include, but are not limited to, electrical and electronic components such as multilayer printed circuit boards and laminates for electrical and electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor encapsulation materials, underfill materials, interchip fills for 3D-LSIs, insulating sheets, prepregs, and heat dissipation substrates.

[0105] [Electrical and Electronic Components] One embodiment of the present invention is an electrical / electronic component, which is made using a curable composition that is an embodiment of the present invention. In the present invention, "laminated board for electrical / electronic circuits" refers to a laminate in which a layer containing a curable composition that is an embodiment of the present invention and a conductive metal layer are laminated together, and the concept is used to include not only electrical / electronic circuits but also, for example, capacitors, as long as a layer containing a curable composition and a conductive metal layer are laminated together. In addition, layers made of two or more types of curable compositions may be formed in the laminate for electrical / electronic circuits, and it is sufficient that a curable composition that is an embodiment of the present invention is used in at least one layer. Furthermore, two or more types of conductive metal layers may be formed.

[0106] In laminates for electrical and electronic circuits, the thickness of the layer made of a curable composition, which is one embodiment of the present invention, is typically about 10 to 200 μm. The thickness of the conductive metal layer is typically about 0.2 to 70 μm.

[0107] [Conductive metals] Examples of conductive metals in laminates for electrical and electronic circuits include metals such as copper and aluminum, and alloys containing these metals. In this embodiment, the conductive metal layer of the laminate for electrical and electronic circuits can be made of metal foil made of these metals, or a metal layer formed by plating or sputtering.

[0108] [Manufacturing method for laminated boards for electrical and electronic circuits] Examples of methods for manufacturing laminates for electrical and electronic circuits include the following: (1) A prepreg is formed by impregnating a nonwoven fabric or cloth made of inorganic and / or organic fiber materials such as glass fiber, polyester fiber, aramid fiber, cellulose, nanofiber cellulose, etc. with the curable composition of the present invention. A conductive metal layer is then provided by conductive metal foil and / or plating, and then a circuit is formed using a photoresist or the like. The required number of these layers are stacked to form a laminate. (2) Using the prepreg described in (1) above as a core material, a layer made of the curable composition of the present invention and a conductive metal layer are laminated on it (one side or both sides) (build-up method). The layer made of the curable composition may contain organic and / or inorganic fillers. (3) Without using a core material, a laminate for electrical and electronic circuits is made by alternately laminating only layers made of the curable composition of the present invention and conductive metal layers. [Examples]

[0109] The present invention will be described more specifically below based on examples, but the present invention is not limited in any way by the following examples. The various manufacturing conditions and evaluation result values ​​in the following examples are meant to represent preferred upper or lower limits in embodiments of the present invention, and the preferred range may be defined by a combination of the aforementioned upper or lower limits and the values ​​of the following examples or the values ​​of different examples.

[0110] [Raw materials used, etc.] The structural formulas of the raw materials and reaction products used in the examples and comparative examples are as follows.

[0111] • Bisphenol M (a compound represented by the following formula (8-1). Hereinafter, it will be abbreviated as "compound (8-1).")

[0112] [ka]

[0113] • BiOC-M (a compound represented by the following formula (8-2). Hereafter, it will be abbreviated as "compound (8-2).")

[0114] [ka]

[0115] • BIOC-F (a compound represented by the following formula (8-3). Hereafter, it will be abbreviated as "compound (8-3).")

[0116] [ka]

[0117] • Bisphenol C (a compound represented by the following formula (8-4). Hereinafter, it will be abbreviated as "compound (8-4).")

[0118] [ka]

[0119] • Bisphenol AF (a compound represented by the following formula (8-5). Hereafter, it will be abbreviated as "compound (8-5).")

[0120] [ka]

[0121] • BisOC-TMC (a compound represented by the following formula (8-6). Hereafter, it will be abbreviated as "compound (8-6).")

[0122] [ka]

[0123] • Bisphenol M-type diglycidyl ether (a compound represented by the following formula (1-1). Hereinafter, it will be abbreviated as "compound (1-1).")

[0124] [ka]

[0125] • BiOC-M type diglycidyl ether (a compound represented by the following formula (1-2). Hereinafter, it will be abbreviated as "compound (1-2).")

[0126] [ka]

[0127] • BIOC-F type diglycidyl ether (a compound represented by the following formula (1-3). Hereinafter, it will be abbreviated as "compound (1-3).")

[0128] [ka]

[0129] • Bisphenol C-type diglycidyl ether (a compound represented by the following formula (1-4). Hereinafter, it will be abbreviated as "compound (1-4).")

[0130] [ka]

[0131] • Bisphenol AF-type diglycidyl ether (a compound represented by the following formula (1-5). Hereinafter, it will be abbreviated as "compound (1-5).")

[0132] [ka]

[0133] • BisOC-TMC type diglycidyl ether (compound represented by the following formulas (1-6). Hereinafter abbreviated as "compound (1-6).")

[0134] [ka]

[0135] • BPA-type diglycidyl ether (Trade name: jER828US (manufactured by Mitsubishi Chemical). A compound represented by the following formula (1'-1). Hereafter, it will be abbreviated as "compound (1'-1).")

[0136] [ka]

[0137] • BPF-type diglycidyl ether (Trade name: jER1750 (manufactured by Mitsubishi Chemical). A compound represented by the following formula (1'-2). Hereafter, it will be abbreviated as "compound (1'-2).")

[0138] [ka]

[0139] • Commercially available orthocresol novolac type epoxy resin (a compound represented by the following formula (1'-3). Hereafter, it will be abbreviated as "compound (1'-3).")

[0140] [ka]

[0141] • 1,2-glycol derivative of compound (1-1) (the compound represented by formula (2-1) below; hereinafter abbreviated as "compound (2-1)").

[0142] [ka]

[0143] • 1,2-glycol derivative of compound (1-2) (the compound represented by formula (2-2) below; hereinafter abbreviated as "compound (2-2)").

[0144] [ka]

[0145] • 1,2-glycol derivative of compound (1-3) (the compound represented by formula (2-3) below; hereinafter abbreviated as "compound (2-3)").

[0146] [ka]

[0147] • 1,2-glycol derivative of compound (1-4) (the compound represented by formula (2-4) below; hereinafter abbreviated as "compound (2-4)").

[0148] [ka]

[0149] • 1,2-glycol derivative of compound (1-5) (the compound represented by formula (2-5) below; hereinafter abbreviated as "compound (2-5)").

[0150] [ka]

[0151] • 1,2-glycol derivative of compound (1-6) (the compound represented by formula (2-6) below; hereinafter abbreviated as "compound (2-6)").

[0152] [ka]

[0153] • 1,2-glycol derivative of compound (1'-1) (the compound represented by formula (2'-1) below; hereinafter abbreviated as "compound (2'-1)").

[0154] [ka]

[0155] • The 1,2-glycol derivative of compound (1'-2) (the compound represented by formula (2'-2) below; hereinafter abbreviated as "compound (2'-2)").

[0156] [ka]

[0157] [Methods for evaluating physical properties and characteristics] The methods for measuring and evaluating the physical properties of the epoxy resin and its cured product obtained in the following examples and comparative examples are as follows.

[0158] <Analysis of the content of constituent components> Using a JASCO Corporation "Pump: PU-4185-Binary", "PDA detector: MD-41010", "Column heater: CO-4060", "Autosampler: AS-4150", "Interface box: LC-NetII / ADC", "Valve unit: RV-2080-02", and "Unifinepak C18 3.0mmΦ×150mm 3μm", high-performance liquid chromatography measurements were performed on the epoxy resins (A-1) to (A-12) and (E-1) to (E-2) of Examples 1 to 12 and Comparative Examples 1 and 2, described below, under the following conditions to separate compound (1) and compound (2). • Eluent: Gradient analysis using acetonitrile / water = 30 / 70 for 60 minutes to achieve 100 / 0. ·Flow rate: 0.5mL / min • Detection: UV ·Temperature: 40℃ • Sample concentration: 0.1-0.2% by mass Injection volume: 10 μL The content of compound (1) and compound (2) was calculated as the ratio of the respective peak areas of compound (1) and compound (2) to the sum of the peak areas of compound (1) and compound (2). Furthermore, the content of the n=0 entity in the epoxy resin was calculated as the ratio (area %) of the peak area of ​​the n=0 entity to the sum of the peak areas of the n=0 entity and the peak areas of components other than the n=0 entity. Similarly, for the epoxy resins (E-3) to (E-5) of Comparative Examples 3 to 5 described later, the content of compounds (1'-1) to (1'-3), their 1,2-glycol derivatives (compounds (2'-1), (2'-2), (2'-3)), and the component n=0 in formulas (1'-1) to (1'-3) was calculated.

[0159] <Epoxy equivalent> Measurements were taken in accordance with JIS K 7236 and expressed as solid content equivalent values.

[0160] <Total Chlorine Amount> The total chlorine content was measured in accordance with JIS K 7243-3.

[0161] <Dielectric properties> A test specimen measuring 2 mm in width and 80 mm in length was cut from a film of cured epoxy resin. The dielectric properties (dielectric constant: Dk, dielectric loss tangent: Df) of this specimen were measured at a measurement frequency (10 GHz) using a network analyzer and the cavity resonance perturbation method. Details of the equipment and measurement environment are described below. Note that specialized measurement software provided by the cavity resonator manufacturer was used to calculate the dielectric properties. (Equipment used) • Network analyzer: Agilent Technologies E8361A • Cavity resonator: CP184 (10GHz), manufactured by Kanto Electronics Applied Development Co., Ltd. (Measurement environment) ·Temperature: 23℃ • Relative humidity: 50%RH

[0162] <Storage modulus E'> Using test specimens obtained by cutting the cured material (film) into 5 cm x 1 cm sections, dynamic mechanical analysis (DMA) was performed under the following conditions to measure the storage modulus (E') at Tg + 50°C. • Analytical instrument: HITACHI DMA7100 • Measurement mode: Tensile mode • Measurement temperature range: 30°C to 250°C • Heating rate: 5°C / min

[0163] [Raw materials, etc.] The raw materials and their synthesis methods used in the following examples and comparative examples are as follows.

[0164] [Examples of epoxy resin synthesis] <Example 1> In a 1L three-necked flask equipped with a thermometer, stirrer, and condenser, 100g of bisphenol M (compound (1-1)), 348g of purified epichlorohydrin (glycidol content: 0.01% by mass or less), 136g of 2-propanol, and 48g of pure water were charged. The mixture was heated to 40°C to dissolve the compounds, and then 55.4g of a 48.5% by mass sodium hydroxide aqueous solution was added dropwise over 1.5 hours. During this time, the temperature was gradually increased until the system reached 65°C at the end of the dropwise addition. The reaction was then carried out at 65°C for 30 minutes. After the reaction was complete, the unreacted epichlorohydrin and isopropyl alcohol were removed by distillation under reduced pressure while raising the temperature to 145°C. Next, 162 g of methyl isobutyl ketone was added to the system and dissolved. The temperature was then raised to 65°C, and 2.8 g of a 48.5% by mass sodium hydroxide solution was added and the mixture was reacted for 1 hour. After the reaction, the solution was washed four times with pure water, and the methyl isobutyl ketone was removed by distillation under reduced pressure at a temperature of 100-150°C to obtain 119 g of liquid bisphenol M-type epoxy resin (epoxy resin (A-1)) at room temperature. Using the method described above, the content (area %) of compound (1-1) and compound (2-1) in epoxy resin (A-1), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0165] <Example 2> Except for replacing the purified epichlorohydrin described in Example 1 with epichlorohydrin with added glycidol (glycidol content: 0.65% by mass), the procedure was carried out in the same manner as in Example 1 to obtain 120 g of liquid bisphenol M-type epoxy resin (epoxy resin (A-2)) at room temperature. Using the method described above, the content (area %) of compound (1-1) and compound (2-1) in epoxy resin (A-2), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0166] <Example 3> Except that a mixture of epichlorohydrin (glycidol content: 0.27% by mass), 2-propanol, and pure water, which was used in the epoxy resin production process in the same manner as in Example 1 and recovered, was used (composition: 150 g epichlorohydrin, 136 g 2-propanol, 64 g water), and the rest of the process was carried out in the same manner as in Example 1 to obtain 118 g of liquid bisphenol M type epoxy resin (epoxy resin (A-3)) at room temperature. Using the method described above, the content (area %) of compound (1-1) and compound (2-1) in epoxy resin (A-3), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0167] <Example 4> Except for changing the amount of pure water described in Example 1 to 0 g, the procedure was carried out in the same manner as in Example 1 to obtain 123 g of liquid bisphenol M-type epoxy resin (epoxy resin (A-4)) at room temperature. Using the method described above, the content (area %) of compounds (1-1) and (2-1) in (epoxy resin (A-4)) was calculated, the content (area %) of n=0 compound was calculated, and the epoxy equivalent (g / eq) and total chlorine content (ppm) were measured. The results are shown in Table 1.

[0168] <Example 5> Except for replacing the bisphenol M described in Example 1 with 20 g of BisOC-M, the procedure was carried out in the same molar ratio as in Example 1 to obtain 25 g of liquid BisOC-M type epoxy resin (epoxy resin (A-5)) at room temperature. Using the method described above, the content (area %) of compounds (1-2) and (2-2) in epoxy resin (A-5), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0169] <Example 6> Except for replacing the bisphenol M described in Example 2 with 20 g of BisOC-M, the procedure was carried out in the same molar ratio as in Example 2 to obtain 22 g of liquid BisOC-M type epoxy resin (epoxy resin (A-6)) at room temperature. Using the method described above, the content (area %) of compounds (1-2) and (2-2) in epoxy resin (A-6), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0170] <Example 7> Except for replacing the bisphenol M described in Example 3 with 20 g of BisOC-M, the procedure was carried out in the same molar ratio as in Example 3 to obtain 26 g of liquid BisOC-M type epoxy resin (epoxy resin (A-7)) at room temperature. Using the method described above, the content (area %) of compounds (1-2) and (2-2) in epoxy resin (A-7), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0171] <Example 8> Except for replacing the bisphenol M described in Example 4 with 20 g of BisOC-M, the procedure was carried out in the same molar ratio as in Example 4 to obtain 25 g of liquid BisOC-M type epoxy resin (epoxy resin (A-8)) at room temperature. Using the method described above, the content (area %) of compounds (1-2) and (2-2) in epoxy resin (A-8), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0172] <Example 9> Except for replacing the bisphenol M described in Example 3 with 66g of BIOC-F, the procedure was carried out in the same manner as in Example 3 to obtain 89g of liquid BIOC-F type epoxy resin (epoxy resin (A-9)) at room temperature. Using the method described above, the content (area %) of compounds (1-3) and (2-3) in epoxy resin (A-9), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0173] <Example 10> Except for replacing the bisphenol M described in Example 3 with 74 g of Bis-C, the procedure was carried out in the same manner as in Example 3 to obtain 96 g of liquid Bis-C type epoxy resin (epoxy resin (A-10)) at room temperature. Using the method described above, the content (area %) of compounds (1-4) and (2-4) in epoxy resin (A-10), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0174] <Example 11> Except for replacing the bisphenol M described in Example 1 with 97 g of Bis-AF, the procedure was carried out in the same manner as in Example 3 to obtain 120 g of liquid Bis-AF type epoxy resin (epoxy resin (A-11)) at room temperature. Using the method described above, the content (area %) of compounds (1-5) and (2-5) in epoxy resin (A-11), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0175] <Example 12> Except for replacing the bisphenol M described in Example 1 with 98 g of BIOC-TMC, the procedure was carried out in the same manner as in Example 3 to obtain 114 g of liquid BIOC-TMC type epoxy resin (epoxy resin (A-12)) at room temperature. Using the method described above, the content (area %) of compounds (1-6) and (2-6) in epoxy resin (A-12), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0176] <Comparative Example 1> Except for replacing the purified epichlorohydrin described in Example 1 with epichlorohydrin with added glycidol (glycidol content: 5.0% by mass), the procedure was carried out in the same manner as in Example 1 to obtain 123 g of liquid bisphenol M-type epoxy resin (epoxy resin (E-1)) at room temperature. Using the method described above, the content (area %) of compound (1-1) and compound (2-1) in epoxy resin (E-1), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0177] <Comparative Example 2> The epoxy resin synthesized in Example 1 was dissolved in hexane / ethyl acetate (3:1) to saturate it, and compound (2-1) was removed by silica gel column chromatography using hexane / ethyl acetate (3:1) as the developing solvent to obtain epoxy resin (E-2). Using the method described above, the content (area %) of compound (1-1) and compound (2-1) in epoxy resin (E-2), the content (area %) of n=0 compound, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured. The results are shown in Table 1.

[0178] <Comparative Example 3> jER828US (manufactured by Mitsubishi Chemical Corporation) was prepared as epoxy resin (E-3), and the content (area %) of compound (1'-1) and compound (2'-1), the content (area %) of n=0, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured using the method described above. The results are shown in Table 1.

[0179] <Comparative Example 4> jER1750 (manufactured by Mitsubishi Chemical Corporation) was prepared as epoxy resin (E-4), and the content (area %) of compound (1'-2) and compound (2'-2), the content (area %) of n=0, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured using the method described above. The results are shown in Table 1.

[0180] <Comparative Example 5> A commercially available orthocresol novolac type epoxy resin was prepared as epoxy resin (E-5), and the content (area %) of compound (1'-3) and compound (2-3), the content (area %) of n=0, the epoxy equivalent (g / eq), and the total chlorine content (ppm) were measured using the method described above. The results are shown in Table 1.

[0181] [Table 1]

[0182] In obtaining a curable composition containing epoxy resin, the following curing agent (B), other epoxy resin (C), and curing accelerator (D) were used.

[0183] [Hardening agent (B)] Hardener (B-1): Commercially available polyarylate resin (polyarylate with a bisphenol skeleton, activity equivalent: 220 g / equivalent)

[0184] [Other epoxy resins (C)] Epoxy resin (C-1): As another epoxy resin that acts as a film-forming agent, high-molecular-weight epoxy resin (Mitsubishi Chemical Co., Ltd., product name "YX7891T30", Mn: 10,000, Mw: 30,000, epoxy equivalent: 6,000 g / equivalent, resin content: 30% by mass)

[0185] [Curing accelerator (D)] Curing accelerator (D-1): 4,4'-dimethylaminopyridine (DMAP)

[0186] [Examples 13-24, Comparative Examples 6-10] The curing agent (B-1) was dissolved in cyclohexanone to a content of 40% by mass. The curing accelerator (D-1) was dissolved in toluene to a content of 5% by mass. Each solution was mixed as shown in Tables 2 and 3 to prepare a curable composition. The obtained curable composition was applied to a release PET film (silicone-treated polyethylene terephthalate film) using a 300 μm thick, 5 cm wide applicator, dried at 160°C for 1.5 hours, and then cured at 200°C for 1.5 hours to obtain an epoxy resin cured film. The dielectric properties (10 GHz) and storage modulus (MPa) of these films were evaluated according to the method described above. The results are shown in Tables 2 and 3.

[0187] [Table 2]

[0188] [Table 3]

Claims

1. An epoxy resin comprising the epoxy resin represented by the following formula (1) and a compound represented by the following formula (2), wherein the ratio of the peak area of ​​the compound represented by the following formula (2) in high-performance liquid chromatography measurement is 0.001 to 5.0 area%. 【Chemistry 1】 (In formula (1) above, each of the substituents R is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Each of the linking groups X is independently a divalent hydrocarbon group having 1 to 18 carbon atoms, -C(CF) ３ ) ２ - or a single bond. p is 0 or 1. n is a non-negative integer representing the number of repetitions. However, if p is 0, the linking group X is -C(CH ３ ) ２ - and -CH ２ (Excluding -) 【Chemistry 2】 (In the above formula (2), the plurality of substituents R are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The linking group X is a divalent hydrocarbon group having 1 to 18 carbon atoms, -C(CF ３ ), ２ -, or a single bond. p is 0 or 1. However, when p is 0, the linking group X excludes -C(CH ３ ), ２ - and -CH ２ -.)

2. The epoxy resin according to claim 1, wherein the epoxy equivalent is 150 to 500 g / equivalent.

3. The epoxy resin according to claim 1, wherein the ratio of peak areas of epoxy resins where n in formula (1) is 0 in the high-performance liquid chromatography measurement is 50 area % or more.

4. The epoxy resin according to claim 1, wherein the total chlorine content is 5,000 ppm or less.

5. A curable composition comprising the epoxy resin and curing agent according to any one of claims 1 to 4.

6. The curable composition according to claim 5, comprising 0.1 to 100 parts by mass of the curing agent in terms of solid content per 100 parts by mass of the solid content of the epoxy resin.

7. The curable composition according to claim 5, wherein the curing agent is at least one selected from the group consisting of phenolic curing agents, amide curing agents, imidazoles, and active ester curing agents.

8. A cured product obtained by curing the curable composition described in claim 5.

9. An electrical or electronic component comprising the curable composition described in claim 5.

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