Bisphenol C type diglycidyl ether, curable composition, cured product, and electrical / electronic components

Abstract

To provide an epoxy resin which has a low molecular weight and is excellent in handleability and is excellent in heat resistance and low dielectric characteristics, an epoxy resin composition containing the epoxy resin and a curing agent, and a cured product of the same, and an electric / electronic component formed of the epoxy resin composition.SOLUTION: Bisphenol C type diglycidyl ether is represented by formula (1), wherein a content of the bisphenol C type diglycidyl ether in which n is 0 in formula (1) is 50-99 mass%, and a content of the bisphenol C type diglycidyl ether in which n is 1 is 1-50 mass%. In formula (1), n represents a repeating number, and an integer of 0 or larger.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a diglycidyl ether, a curable composition, a cured product, and an electric and electronic component. More specifically, it relates to a bisphenol C type diglycidyl ether having excellent heat resistance and low dielectric properties, a curable composition containing the same, a cured product thereof, and an electric and electronic component.

Background Art

[0002] Epoxy resins represented by diglycidyl ethers are used in various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electric and electronic components because of their excellent adhesiveness, water resistance, mechanical strength, and electrical properties. In particular, in the electric and electronic fields, they are widely used in insulation casting, laminated materials, encapsulation materials, etc. In recent years, multilayer circuit boards used in electric and electronic devices have been advancing in miniaturization, weight reduction, and high functionality of the devices, and further requirements for multilayerization, high density, thinning, weight reduction, and improvement of reliability and molding processability have been made.

[0003] As an important performance required for epoxy resins used as materials for electric and electronic components such as laminated boards for electric and electronic circuits, low dielectric properties are mentioned. In recent years, for the improvement of the amount of information transmission and speed, the frequency of communication frequencies has been increasing, and among them, the increase in transmission loss (α) has become a major problem. The lower the value of this α, the less the attenuation of information signals, which means that high reliability of communication can be ensured. Since α is proportional to the frequency (f), α increases in communication in the high-frequency region, leading to a decrease in reliability. As a method for suppressing α, a method of reducing the dielectric tangent (tanδ) that is proportional to f, like f, can be mentioned. For high-speed transmission of communication signals, materials with a low tanδ, that is, materials having low dielectric properties, are required.

[0004] In addition, high reliability is required for electric and electronic components such as laminated boards for electric and electronic circuits, and for epoxy resins used as materials, a balance of various properties such as heat resistance and flame retardancy in addition to low dielectric properties is required. In particular, heat resistance is an essential property to ensure reliability in a wide temperature range.

[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. In recent years, diglycidyl ethers with various skeletons have been investigated, and Patent Document 1 discloses bisphenol type diglycidyl ethers with various structures as hydrophobic epoxy resin compositions. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 10344106 [Overview of the project] [Problems that the invention aims to solve]

[0007] In recent years, laminates for electrical and electronic circuits have become more complex and smaller. To improve dimensional stability in line with the thinning of these laminates, and to suppress energy loss in communication signals due to the increasing amount of information and communication speed in information and communication, the resin composition of these laminates tends to become more complex. As a result, 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.

[0008] Furthermore, the increased heat generation due to the increased processing speed of semiconductor devices, and the miniaturization of semiconductor integrated circuits ( To cope with the increased heat generation due to the increased density of the material, and to withstand continuous use under high-temperature conditions, higher heat resistance is required for the epoxy resins and their cured products used. Among low molecular weight bisphenol-type glycidyl ethers, bisphenol A-type diglycidyl ethers have generally not been sufficient in terms of heat resistance and dielectric properties.

[0009] The object of the present invention is to provide an epoxy resin with low molecular weight, excellent handling properties, and excellent heat resistance and low dielectric properties; a curable composition containing the epoxy resin and a curing agent; a cured product thereof; and electrical and electronic components made from the curable composition. [Means for solving the problem]

[0010] As a result of diligent research, the inventors have found that by using bisphenol C type diglycidyl ether among bisphenol type diglycidyl ethers, and by controlling various reaction conditions during the production of bisphenol C type diglycidyl ether, the content of bisphenol C type diglycidyl ether with 0 and 1 repeating constituent units can be controlled, and that this ratio correlates with dielectric properties and heat resistance. Furthermore, the inventors have found that the above problems can be solved by using bisphenol C type diglycidyl ether with these ratios within a specific range.

[0011] In other words, the gist of the present invention lies in the following [1] to [9]. [1] A bisphenol C type diglycidyl ether represented by the following formula (1), wherein the content of the bisphenol C type diglycidyl ether n=0 in the following formula (1) is 50 to 99% by mass, and the content of the bisphenol C type diglycidyl ether n=1 is 1 to 50% by mass. [ka] (In equation (1) above, n represents the number of repetitions and is a non-negative integer.) [2] The bisphenol C type diglycidyl ether described in [1], wherein the epoxy equivalent is 184 to 250 g / equivalent. [3] The bisphenol C type diglycidyl ether according to [1] or [2], which is liquid at room temperature and has a melt viscosity of 0.4P or less at 150°C. [4] A bisphenol C type diglycidyl ether as described in any one of items [1] to [3], wherein the total chlorine content is 5,000 ppm or less. A curable composition comprising bisphenol C type diglycidyl ether and a curing agent as described in any one of 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 bisphenol C type diglycidyl ether. [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 any one of the curable compositions described in [8] [5] to [7]. Electrical and electronic parts using the curable composition described in any one of items [9] [5] to [7] Product. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide epoxy resins, curable compositions, and cured products with excellent heat resistance and low dielectric properties. For this reason, the epoxy resins and curable compositions 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 materials, laminating materials, and sealing materials in the electrical and electronic field. The epoxy resins and curable compositions containing the present invention can be suitably used in multilayer printed circuit boards, laminates 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-LSIs, insulating sheets, prepregs, heat dissipation substrates, and the like. [Modes for carrying out the invention]

[0013] The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is just one example of how the present invention can be carried out, and the present invention is not limited to the following description as long as it does not exceed the gist of the invention. In this specification, when the expression "~" is used, it is used to mean an expression that includes the numerical value or physical property value before and after it.

[0014] 〔Bisphenol C type diglycidyl ether〕 The bisphenol C type diglycidyl ether which is one form of the present invention is a bisphenol C type diglycidyl ether (bisphenol C type epoxy resin) represented by the following formula (1). In the following formula (1), the proportion of the bisphenol C type diglycidyl ether with n = 0 (hereinafter sometimes abbreviated as "n = 0 form") is 50% by mass or more and 99% by mass or less, and the proportion of the bisphenol C type diglycidyl ether with n = 1 (hereinafter sometimes abbreviated as "n = 1 form") is 50% by mass or less and 1% by mass or more. The bisphenol C type diglycidyl ether of this form has a bisphenol C type structure, and by controlling the proportions of its n = 0 form and n = 1 form within the above ranges respectively, a balance between dielectric properties and heat resistance can be achieved.

[0015]

Chemical formula

[0016] The bisphenol C type diglycidyl ether of this form can maintain good dielectric properties and heat resistance by having a bisphenol C type structure. The bisphenol C type structure has a rotational barrier due to the methyl group of the substituent of the benzene ring in the structure. In addition to the effect of the increase in steric volume, it is less affected by the steric and electrostatic repulsion of the substituent, and the benzene rings in the structure interact with each other intermolecularly, so that the dielectric properties and heat resistance can be specifically maintained well.

[0017] In the bisphenol C type diglycidyl ether of this form, from the viewpoint of improving reactivity and maintaining good dielectric properties, the content of the n = 0 form is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. On the other hand, as the content of the n = 0 form increases, the load of purification processes such as distillation when producing bisphenol C type diglycidyl ether on an industrial scale may increase. Therefore, from the viewpoint of improving productivity, the content of the n = 0 form is preferably 98% by mass or less, more preferably 97% by mass or less, still more preferably 96% by mass or less, and particularly preferably 95% by mass or less.

[0018] In the bisphenol C type diglycidyl ether of this form, from the viewpoint of improving reactivity and being able to maintain good dielectric properties and heat resistance, the content of the n = 1 form is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 16% by mass or less, and particularly preferably 12% by mass or less. On the other hand, from the viewpoint of being able to improve productivity, the content of the n = 1 form is preferably 2% by mass or more, more preferably 4% by mass or more, still more preferably 6% by mass or more.

[0019] The bisphenol C type diglycidyl ether of this form can satisfy the above characteristics by the method for producing bisphenol C type diglycidyl ether described below.

[0020] The bisphenol C type diglycidyl ether of this form contains the n = 0 form and the n = 1 form as described above, but may also contain bisphenol C type diglycidyl ethers with n = 2 or more. When containing bisphenol C type diglycidyl ethers with n = 2 or more, the content is preferably 12% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less.

[0021] The content of n=0, n=1, and n=2 or more components in bisphenol C-type diglycidyl ether can be determined by gel permeation chromatography (GPC) analysis, as shown in the Examples section below.

[0022] [Epoxy equivalent] The epoxy equivalent of the bisphenol C type diglycidyl ether in this embodiment is preferably in the range of 184 to 250 g / equivalent. From the viewpoint of maintaining good heat resistance and dielectric properties, the epoxy equivalent is preferably 240 g / equivalent or less, more preferably 230 g / equivalent or less, and even more preferably 210 g / equivalent or less. Furthermore, from the viewpoint of improving productivity, it is preferably 185 g / equivalent or more, more preferably 186 g / equivalent or more, and particularly preferably 187 g / equivalent or more. The epoxy equivalent can be controlled by the method for producing bisphenol C type diglycidyl ether described later.

[0023] [Resin properties, melt viscosity] In this embodiment, the bisphenol C type diglycidyl ether is preferably liquid at room temperature, from the viewpoint of maintaining good handling properties, compatibility with various inorganic and organic fillers and polymer components, and facilitating dissolution in solvents. Furthermore, the melt viscosity of the bisphenol C type diglycidyl ether in this embodiment at 150°C is preferably 0.4P or less. From the viewpoint of maintaining good handling properties, increasing industrial productivity during use, maintaining good compatibility with curing agents, and improving dielectric properties and heat resistance, 0.4P or less is preferred, 0.35P or less is more preferred, 0.3P or less is even more preferred, and 0.25P or less is particularly preferred. The melt viscosity at 150°C can be measured using a rotational viscometer (ICI viscometer) or the like.

[0024] [Shear viscosity] In this embodiment of bisphenol C-type diglycidyl ether, from the viewpoint of maintaining good handling, increasing industrial productivity during use, maintaining good compatibility with curing agents, improving dielectric properties and heat resistance, and improving adhesion between substrates, the shear viscosity at 60°C is preferably 47,500 mPa·s or less, more preferably 47,000 mPa·s or less, even more preferably 46,500 mPa·s or less, and particularly preferably 46,000 mPa·s or less. On the other hand, there is no particular lower limit, but it is preferably 100 mPa·s or more, and more preferably 600 mPa·s or more. Furthermore, the shear viscosity at 80°C is preferably 10,000 nPa·s or less, and more preferably 7,000 mPa·s or less. On the other hand, there is no particular lower limit, but it is preferably 120 mPa·s or more, and more preferably 150 mPa·s or more. Furthermore, the shear viscosity at 100°C is preferably 1000 mPa·s or less, and more preferably 200 mPa·s or less. Furthermore, the shear viscosity at 125°C is preferably 70 mPa·s or less, while the lower limit is preferably 20 mPa·s or more. The shear viscosity at each of the above temperatures can be measured using a viscoelasticity measuring device or the like.

[0025] [Total chlorine content] The total chlorine content of the bisphenol C-type diglycidyl ether 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, and more preferably 2,000 ppm or less. A concentration of 1,500 ppm or less is particularly preferred. The total chlorine content can be measured in accordance with JIS K 7243-3.

[0026] [Method for producing bisphenol C type diglycidyl ether] Methods for producing this form of bisphenol C type diglycidyl ether include, for example, reacting bisphenol C with an epihalohydrin in the presence of an alkali, or epoxidizing bisphenol C by allylation followed by oxidation of the olefin portion.

[0027] In the present invention, a bisphenol compound represented by the following formula (2) is used as the bisphenol C used as a raw material. In this invention, the structure represented by the following formula (2) is defined as "bisphenol C".

[0028] [ka]

[0029] The reaction step of reacting the bisphenol compound represented by formula (2) with the epihalohydrin in the presence of an alkali is not particularly limited, but a reaction step in which the bisphenol compound represented by formula (2) and the epihalohydrin are reacted in a single step is preferred. The following describes the reaction process using this one-step method in detail.

[0030] [One-stage reaction process] A specific example of a one-step manufacturing method is to use 1 mole of hydroxyl groups of the bisphenol compound represented by formula (2) with 1 mole of epihalohydrin, usually 1.00 to 20.0 moles, preferably 1. One method of production involves reacting the epihalohydrin in a proportion of 0.50 to 15.0 moles, more preferably 2.0 to 12.0 moles, and even more preferably 4.0 to 10.0 moles. If the amount of epihalohydrin used is too small, it leads to the formation of high molecular weight compounds, resulting in increased viscosity, as well as deterioration of dielectric properties and heat resistance. If the amount of epihalohydrin is too large, the economic efficiency deteriorates.

[0031] More specifically, a bisphenol compound represented by formula (2) is mixed with an epihalohydrin such as epichlorohydrin and reacted in the presence of an alkali. Preferably, an alkali metal hydroxide is used as the alkali, either in solid or aqueous form. This reaction can be carried out under normal pressure or reduced pressure. The reaction temperature is typically 20-150°C under normal pressure and 30-80°C under reduced pressure. The reaction is carried out while maintaining a predetermined temperature as needed, azeotropically forming the reaction solution, cooling the volatile vapors to obtain a condensate, separating the oil / water, and returning the oil (without water) to the reaction system. To suppress a rapid reaction, the alkali metal hydroxide is preferably added to the reaction system in small amounts intermittently or continuously over 0.1-10 hours. The total reaction time is typically 1-15 hours.

[0032] After the reaction is complete, the insoluble by-product salt is removed from the reaction solution containing the target product, bisphenol C-type diglycidyl ether, by filtration or washing with water. Then, the unreacted epihalohydrin is removed by distillation under reduced pressure to obtain the target bisphenol C-type diglycidyl ether.

[0033] 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.

[0034] 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 be used in this reaction.

[0035] 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.

[0036] Furthermore, the amount of saponifiable halogens in the bisphenol C type diglycidyl ether obtained as described above can be reduced by reprocessing to obtain purified bisphenol C type diglycidyl ether with a sufficiently reduced amount of saponifiable halogens. In this case, the crude bisphenol C type diglycidyl ether obtained by the reaction is redissolved in an inert organic solvent such as isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, or dimethyl sulfoxide, and an alkali metal hydroxide is added in solid or aqueous solution. A re-cyclization reaction is carried out at a temperature of approximately 20 to 120°C for 0.5 to 8 hours. After removing excess alkali metal hydroxide and by-product salts by methods such as washing with water, the organic solvent is further removed by distillation under reduced pressure, thereby obtaining purified bisphenol C type diglycidyl ether in a single step.

[0037] Furthermore, the bisphenol C type diglycidyl ether represented by formula (1) above by a one-step method is shown. When manufacturing the product, at least a bisphenol compound represented by formula (2) is used as a raw material, but other polyhydric hydroxy compounds (sometimes referred to as "other polyhydric hydroxy compounds" in this specification) may also be used in combination, and the product may be manufactured as a mixture of the bisphenol C-type diglycidyl ether of formula (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 (2) 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.

[0038] Other polyhydric hydroxy compounds include 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, as well as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and guanine. Examples include polyhydric phenolic resins obtained by condensation reactions with various aldehydes such as lyo-xal, 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 resins 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.

[0039] Methods for controlling the amounts of n=0 and n=1 in equation (1) include, for example, adjusting the molar ratio of the bisphenol compound represented by equation (2) and the epihalohydrin used as raw materials in the reaction step described above, adjusting the amount of alkali used, controlling the amount through purification or distillation, and combining these methods.

[0040] 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 (2) 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.

[0041] 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 (2) of the starting material 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.

[0042] [Curable composition] One embodiment of the present invention is a curable composition comprising at least the bisphenol C type diglycidyl ether and curing agent described above. Furthermore, the curable composition of this embodiment may optionally contain other epoxy resins, inorganic fillers, coupling agents, antioxidants, and other additives besides the bisphenol C type diglycidyl ether of this embodiment. The curable composition of this embodiment offers improved handling properties through the inclusion of the bisphenol C type diglycidyl ether of this embodiment, thereby improving compatibility with other components, increasing the amount of filler that can be added, and improving impregnation into glass cloth. Moreover, its excellent high heat resistance and low dielectric properties make it advantageous for the miniaturization, multilayering, high density, and high frequency applications of electronic components.

[0043] [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 commonly 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.

[0044] The content of the curing agent in the curable composition of this embodiment is preferably 0.1 to 100 parts by mass, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less, based on 100 parts by mass of solids of bisphenol C type diglycidyl ether, which is one embodiment of the present invention.

[0045] When the curable composition of this embodiment contains other epoxy resins as described later, the mass ratio of solids between bisphenol C type diglycidyl ether and 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 90 parts by mass or less, and even more preferably 80 parts by mass or less, based on 100 parts by mass of the total solid content of the polycrystalline bisphenol C type diglycidyl ether and the other epoxy resin.

[0046] 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 bisphenol C type diglycidyl ether, which is one embodiment of the present invention, and other epoxy resins described later.

[0047] There are no particular restrictions on the curing agent used in this embodiment of the curable composition; all commonly known epoxy resin curing agents can be used. From the viewpoint of improving heat resistance, phenolic curing agents, amide curing agents, imidazoles, and activated ester curing agents are preferred. Examples of phenolic curing agents, amide curing agents, imidazoles, activated ester curing agents, and other usable curing agents are listed below.

[0048] <Phenol-based curing agent> For the curable composition of this embodiment, a phenolic curing agent is used. This is preferable from the viewpoint of improving the handling properties of the resulting curable composition and the heat resistance after curing.

[0049] Specific examples of phenolic curing agents include 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, 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 polyallylized dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, and the like.

[0050] The phenolic curing agents listed above may be used individually, or two or more may be mixed in any combination and ratio.

[0051] When using a phenolic curing agent, it is preferable to use one such agent so that the equivalent ratio of functional groups in the curing agent to epoxy groups in the total epoxy resin components of the curable composition is in the range of 0.8 to 1.5. This range is preferable because it reduces the likelihood of unreacted epoxy groups or functional groups of the curing agent remaining in the mixture.

[0052] <Amid-based hardener> In this embodiment of curable composition, it is preferable to use an amide-based curing agent as the curing agent, from the viewpoint of improving the heat resistance of the resulting curable composition.

[0053] 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.

[0054] <Imidazoles> In this embodiment of curable composition, it is preferable to use imidazoles (imidazole-based curing agents) as the curing agent, from the viewpoint of ensuring sufficient curing reaction and improving heat resistance.

[0055] 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, and 1-cyanoethyl-2-phenylimidazolium. Examples include limellitate, 2,4-diamino-6-[2'-methylimidazolyl-(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 generally have catalytic activity and can be classified as curing accelerators as described later, in this invention they are classified as curing agents.

[0056] The imidazoles listed above may be used individually, or two or more may be mixed in any combination and ratio. It is preferable to use imidazoles in an amount 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.

[0057] <Activated ester-based curing agent> In this embodiment of curable composition, it is preferable to use an active ester-based curing agent as the curing agent, from the viewpoint of exhibiting low water absorption and low dielectric properties in the resulting cured product.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] More specifically, as an active ester resin containing a dicyclopentadiene-phenol addition structure Examples include compounds represented by the following general formulas (I) and (II).

[0063] [ka] [In equation (I), B' represents the following structural formulas (B'-1) to (B'-6) independently.] [ka] (In formulas (B'-1) to (B'-6), R 1 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 2 Each of the following is independently an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, or a phenyl group; X is a linear alkylene group with 2 to 6 carbon atoms, an ether linkage, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group; and n and p are integers from 1 to 4. It is one of the structural sites selected from the group consisting of R 3 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; Z is 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 nucleus; l is 0 or 1; and k' is the average of the repeating units, ranging from 0.05 to 3.5.

[0064] [ka] [In formula (II), R 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.] In formula (II), from the viewpoint of reducing the dielectric loss tangent of the cured resin composition and improving heat resistance, R 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 activated ester resins represented by general formulas (I) and (II).

[0065] 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 with a bisphenol backbone).

[0066] The active ester curing agents listed above may be used individually, or two or more may be mixed in any combination and ratio. Preferably, the active ester curing agent is used such that the equivalent ratio of active ester groups in the curing agent to epoxy groups in the total epoxy resin in the curable composition is in the range of 0.2 to 2.0.

[0067] <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. The other curing agents listed above may be used individually or mixed in any combination and ratio of two or more types.

[0068] [Other epoxy resins] The curable composition in 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.

[0069] 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.

[0070] In the curable composition of this embodiment, when using bisphenol C type diglycidyl ether, which is one embodiment of the present invention, and other epoxy resins, the amount of other epoxy resins blended in 100% by mass of the total epoxy resin components 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, while 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 bisphenol C type diglycidyl ether is fully exhibited, which is preferable from the viewpoint of obtaining physical property improvement effects such as high heat resistance and low dielectric properties.

[0071] 〔solvent〕 In this embodiment of the curable composition, a solvent may be added and diluted to appropriately adjust the viscosity of the curable composition during handling when forming the coating film. In the curable composition of the present invention, 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 the aforementioned "solvent" are used to distinguish them according to their form of use, but they may be the same or different.

[0072] 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. The solvents listed above may be used individually or mixed in any combination and ratio of two or more.

[0073] [Other ingredients] The curable composition in this embodiment may contain components other than those listed above (which may be referred to as "other components" in this invention) for the purpose of further improving its functionality. Examples of such 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.

[0074] [Cured product] One embodiment of the present invention is a cured product, which is obtained by curing a curable composition, which is one embodiment of the present invention. The cured product of this embodiment, obtained by curing bisphenol C type diglycidyl ether, which is one embodiment of the present invention, with a curing agent, provides a curable composition with excellent handling properties, which allows for an increase in the amount of filler that can be added and an improvement in 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 is usually 5 to 95%.

[0075] The curing method for a curable composition, which is one embodiment of the present invention, varies depending on the components and their proportions in the curable composition, but typically involves heating at 80-280°C for 60-360 minutes. This heating is performed at 80-160°C for 10- It is preferable to perform a two-stage process consisting of a primary heating for 90 minutes and a secondary heating at 120-200°C for 60-150 minutes. Furthermore, in formulations where the glass transition temperature (Tg) exceeds the secondary heating temperature, it is preferable to perform a tertiary heating at 150-280°C for 60-120 minutes. Performing secondary and tertiary heating in this manner is preferable from the viewpoint of reducing curing defects and solvent residue.

[0076] 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.

[0077] [Application] One embodiment of the present invention, bisphenol C-type diglycidyl ether, offers excellent productivity and handling properties, as well as superior heat resistance and low dielectric properties. Furthermore, it improves the handling of its curable composition, allowing for increased filler addition, improved compatibility with other resin components, and enhanced impregnation into glass cloth. For these reasons, it is applicable to various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic components, and is particularly useful as an insulating casting material, laminating material, and sealing material in the electrical and electronic fields.

[0078] Examples of applications for bisphenol C type diglycidyl ether and curable compositions containing the same 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.

[0079] 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.

[0080] 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.

[0081] [Conductive metal] 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.

[0082] [Manufacturing method for laminated boards for electrical and electronic circuits] Examples of methods for manufacturing laminates for electrical and electronic circuits in this embodiment 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, and then using conductive metal foil and / or plating to form a conductive metal After creating the layers, circuits are formed using photoresist or the like, and 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]

[0083] 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.

[0084] [Methods for evaluating physical properties and characteristics] In the following examples and comparative examples, the physical properties and characteristics were evaluated using the methods described in (1) to (6) below.

[0085] (1) Analysis of the composition ratio in bisphenol C type diglycidyl ether Using the "HLC-8320GPC device" manufactured by Tosoh Corporation, separation was performed using "TSKGEL SuperHM-H+H5000+H4000+H3000+H2000" manufactured by Tosoh Corporation, and the content ratios of n=0, n=1, and n=2 (those with n=2) in the above formula (1) were determined from the analysis chart. Eluent: Tetrahydrofuran Flow rate: 0.5ml / min Detection: UV Temperature: 40℃ Sample concentration: 0.1-0.2% by mass Injection volume: 10 μl

[0086] (2) Epoxy equivalent Measurements were taken in accordance with JIS K 7236 and expressed as solid content equivalent values.

[0087] (3) Melt viscosity Using a cone plate viscometer (ICI viscometer) manufactured by Tokai Hachigami Co., Ltd., the sample was melted on the viscometer's hot plate, which was adjusted to 150°C, and the viscosity was measured at a rotation speed of 750 rpm.

[0088] (4) Total chlorine content The values ​​shown were measured in accordance with JIS K 7243-3.

[0089] (5) Handling and compatibility The resin compositions, formulated as shown in Table 2, were placed in 50 ml glass sample bottles and evaluated as follows. Appears clear to the naked eye, flows when the glass bottle is tilted, and is transparent: ○ Items that appear slightly cloudy to the naked eye: △ Items that appear cloudy to the naked eye and do not transmit light: ×

[0090] (6) Dielectric properties The epoxy resin cured film was cut into test pieces measuring 2 mm in width and 80 mm in length, and the test was performed. For each sample, the dielectric properties (dielectric constant: Dk, dielectric loss tangent: Df) were measured at measurement frequencies (1 GHz and 10 GHz) using the cavity resonance perturbation method with a network analyzer. Details of the equipment used and the measurement environment are shown below. Note that dedicated measurement software provided by the cavity resonator manufacturer was used to calculate the dielectric properties. Equipment used: Network analyzer manufactured by Agilent Technologies. E8361A Cavity resonators CP215 (1GHz), CP184 (10GHz) manufactured by Kanto Electronics Applied Development Co., Ltd. Measurement environment: Temperature 23°C, relative humidity 50%RH

[0091] (7) Glass transition temperature (Tg) The glass transition temperature of epoxy resin, after the solvent had been dried and removed, was measured using SII Nanotechnology Co., Ltd.'s "DSC7020" by increasing the temperature from 30 to 250°C at a rate of 10°C / min. The glass transition temperature referred to here was measured based on the "intermediate glass transition temperature: Tmg" described in JIS K7121 "Method for Measuring Transition Temperatures of Plastics".

[0092] (8) Shear viscosity Using a viscoelasticity analyzer, HAAKE MARS 40 TM-EL-H, manufactured by Thermo Fisher Scientific K.K., after dropping the sample onto the plate, a parallel plate was used. The viscosity was measured at 25°C, 40°C, 60°C, 80°C, 100°C, and 125°C when the temperature was increased from 25°C to 125°C at a rotational speed of 750 rpm.

[0093] [Raw materials, etc.] The raw materials and their synthesis methods used in the following examples and comparative examples are as follows.

[0094] [Example 1: Synthesis of bisphenol C type diglycidyl ether] 250 g of bisphenol C (4,4'-(1-methylethylidene)bis(2-methylphenol)), 1174 g of epichlorohydrin, 458 g of isopropyl alcohol, and 163 g of pure water were charged into a 2 L flask and stirred at 40°C to form a homogeneous solution. Then, 187 g of a 48.5% by mass sodium hydroxide solution was added dropwise over 1.5 hours at a temperature of 40-65°C, and the mixture was held at 65°C for 30 minutes to complete the epoxidation reaction. 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.

[0095] Next, 439 g of methyl isobutyl ketone was added to the system and dissolved. The temperature was then raised to 65°C, and 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 at 100-150°C under reduced pressure to obtain 346 g of bisphenol C type diglycidyl ether in liquid state at room temperature. The composition ratio (by mass) of the obtained bisphenol C type epoxy resin composition was 91.2% by mass for the n=0 isomer, 8% by mass for the n=1 isomer, and 0.8% by mass for the n=2 isomer, as determined by GPC analysis. The chemical structures of n=0 to n=2 bisphenol C-type diglycidyl ethers are shown in equations (3) to (5) below.

[0096] [ka]

[0097] [Example 2: Synthesis of bisphenol C type diglycidyl ether] Except for changing the amount of pure water to 490 g, 346 g of bisphenol C type diglycidyl ether in liquid state at room temperature was obtained in the same manner as in Example 1. The composition ratio (mass%) of the obtained bisphenol C type epoxy resin composition was 91.0 mass% for n=0 bisphenol C type diglycidyl ether, 8.4 mass% for n=1 bisphenol C type diglycidyl ether, and 0.6 mass% for n=2 bisphenol C type diglycidyl ether, as determined by GPC analysis.

[0098] [Example 3: Synthesis of bisphenol C type diglycidyl ether] 350 g of bisphenol C type diglycidyl ether in liquid state at room temperature was obtained in the same manner as in Example 1, except that 1807 g of epichlorohydrin, 704 g of isopropyl alcohol, and 251 g of pure water were used. The composition ratio (mass%) of the obtained bisphenol C type epoxy resin composition was 95.0 mass% for n=0, 4.5 mass% for n=1, and 0.5 mass% for n=2, as determined by GPC analysis.

[0099] [Example 4: Synthesis of bisphenol C type diglycidyl ether] 342 g of bisphenol C type diglycidyl ether in liquid state at room temperature was obtained in the same manner as in Example 1, except that 723 g of epichlorohydrin, 282 g of isopropyl alcohol, and 100 g of pure water were used. The composition ratio (mass%) of the obtained bisphenol C type epoxy resin composition was 87.7 mass% for n=0, 11.2 mass% for n=1, and 1.1 mass% for n=2, as determined by GPC analysis.

[0100] [Example 5: Synthesis of bisphenol C type diglycidyl ether] 340 g of bisphenol C type diglycidyl ether in liquid state at room temperature was obtained in the same manner as in Example 1, except that 271 g of epichlorohydrin, 106 g of isopropyl alcohol, and 38 g of pure water were used. The composition ratio (mass%) of the obtained bisphenol C type epoxy resin composition was 61.7 mass% for n=0, 27.0 mass% for n=1, and 11.3 mass% for n=2, as determined by GPC analysis.

[0101] <Comparative Example 1: Bisphenol A type diglycidyl ether (product name: jER828US (three Made by Hishi Chemical Co., Ltd. A bisphenol A type diglycidyl ether was obtained containing 84.0% by mass of formula (6) (n=0 isomer), 14.0% by mass of formula (7) (n=1 isomer), and 2.0% by mass of formula (8) (n=2 isomer), which have the chemical structures shown in formulas (6) to (8) below.

[0102] [ka]

[0103] <Comparative Example 2: Bisphenol C-type diglycidyl ether> 308 g of bisphenol C type diglycidyl ether in liquid state at room temperature was obtained in the same manner as in Example 1, except that 225.8 g of epichlorohydrin, 88 g of isopropyl alcohol, and 31 g of pure water were used. The composition ratio (mass%) of the obtained bisphenol C type epoxy resin composition was 41.0 mass% for n=0, 28.7 mass% for n=1, and 15.4 mass% for n=2, as determined by GPC analysis.

[0104] Table 1 shows the various analytical values ​​for Examples 1 to 5, Comparative Example 1, and Comparative Example 2.

[0105] [Table 1]

[0106] In obtaining an epoxy resin composition from bisphenol-type glycidyl ether, the following Using a hardening agent (B), other epoxy resins (D), and a curing accelerator (E).

[0107] [Hardening agent (B)] (B-1): Commercially available polyarylate resin (polyarylate with a bisphenol skeleton, activity equivalent: 220 g / equivalent)

[0108] [Other epoxy resins (D)] (D-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)

[0109] [Curing accelerator (E)] (E-1): DMAP: 4,4'-dimethylaminopyridine

[0110] [Examples 6-10, Comparative Examples 3-4] A commercially available polyarylate resin (B-1) was dissolved in cyclohexanone to a resin content of 40% by mass. 4,4'-dimethylaminopyridine (E-1) was dissolved in toluene to a resin content of 5% by mass. Each resin solution was prepared and mixed to the solid content shown in Table 2 to obtain epoxy resin compositions. The handling properties and compatibility of the obtained epoxy resin compositions were evaluated. The solutions of the obtained epoxy resin compositions were applied to a release PET film (silicone-treated polyethylene terephthalate film) using a 300 μm thick, 5 cm wide applicator, and dried at 160°C for 1.5 hours, then at 200°C for 1.5 hours, to obtain epoxy resin cured films. The heat resistance and dielectric properties of these films were evaluated according to the method described above. The results are also shown in Table 2.

[0111] [Table 2]

[0112] Tables 1 and 2 show that the bisphenol C-type diglycidyl ether of the present invention has excellent handling properties, dielectric properties, and heat resistance. [Industrial applicability]

[0113] According to the present invention, a bisphenol C-type diglycidyl ether, a curable composition, and a cured product thereof can be obtained that are easy to handle and have excellent heat resistance and low dielectric properties. The bisphenol C type diglycidyl ether, curable composition, and cured product of the same are applicable to various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic components. In particular, they are useful as insulating casting materials, laminating materials, and sealing materials in the electrical and electronic fields. Examples of applications for the bisphenol C type diglycidyl ether, curable composition, and cured product of the present invention include, but are not limited to, multilayer printed circuit boards, laminates for electrical and electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor encapsulating materials, underfill materials, interchip fills for 3D-LSIs, insulating sheets, prepregs, and heat dissipation substrates.

Claims

1. A bisphenol C type diglycidyl ether represented by the following formula (1), wherein the content of bisphenol C type diglycidyl ether with n=0 in the following formula (1) is 50 to 99% by mass, the content of bisphenol C type diglycidyl ether with n=1 is 1 to 50% by mass, and the epoxy equivalent is 184 to 199 g / equivalent. 【Chemistry 1】 (In equation (1) above, n represents the number of repetitions and is a non-negative integer.)

2. The bisphenol C type diglycidyl ether according to claim 1, wherein the total chlorine content is 5,000 ppm or less.

3. A curable composition comprising the bisphenol C type diglycidyl ether and curing agent described in claim 1 or 2.

4. The curable composition according to claim 3, 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 bisphenol C type diglycidyl ether.

5. The curing agent is a phenolic curing agent, an amide curing agent, imidazoles, and an active ester. The curable composition according to claim 3, which is at least one selected from the group consisting of system curing agents.

6. A cured product obtained by curing the curable composition described in claim 3.

7. An electrical or electronic component comprising the curable composition described in claim 3.

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