Monofunctional epoxy compound, and production method and use therefor

Abstract

To provide a monofunctional epoxy compound that enables viscosity reduction when combined with a multifunctional epoxy compound, even if it is not a low-viscosity liquid (or exists as a solid) under normal temperature and pressure conditions, and a production method and a use therefor.SOLUTION: A monofunctional epoxy compound disclosed herein is represented by the formula (1) (where Ar represents a polycyclic arene ring, A1 represents an alkylene group, n1 represents an integer of 1-3, R1 represents a hydrogen atom or an alkyl group, R2 represents a substituent, and m2 is an integer of 0 or greater). A curable composition disclosed herein comprises a multifunctional epoxy compound, and the compound represented by formula (1).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a monofunctional epoxy compound having a polycyclic arene ring skeleton and an alkyleneoxy group, and a production method and uses thereof, such as a reactive diluent containing the monofunctional epoxy compound, a curable composition containing the reactive diluent, and a cured product thereof. [Background technology]

[0002] Epoxy resins (multifunctional epoxy compounds) have excellent properties and are widely used in various fields such as fiber-reinforced plastics (FRP), insulating materials, adhesives, and paints. However, epoxy resins are often difficult to handle due to their high viscosity. In particular, multifunctional epoxy compounds with a 9,9-bisarylfluorene skeleton are characterized by high heat resistance and chemical resistance due to their structure, but tend to have high viscosity and are difficult to handle due to their rigid structure. Generally, a method of reducing the viscosity of high-viscosity multifunctional epoxy compounds is known in which a liquid, low-viscosity monofunctional epoxy compound is blended as a reactive diluent.

[0003] However, reactive diluents generally reduce other properties such as heat resistance (such as the glass transition temperature Tg of the cured product), making it difficult to achieve both easy handling of the curable composition and heat resistance of the cured product after curing.

[0004] Toshikazu Misaki et al., "Effect of Glycidyl Diluents on Fracture Toughness of Epoxy Resin," December 1986, "Zairyo," Vol. 35, No. 299, pp. 1399-1404 (Non-Patent Document 1), discloses that the viscosity of Epicoat 828, a bisphenol A type epoxy resin, was reduced by blending 10 phr of a glycidyl diluent (reactive diluent) such as butyl glycidyl ether (BGE) or phenyl glycidyl ether (PGE), and that the degree of viscosity reduction was greater the smaller the molecular weight of the glycidyl diluent. It also describes that the heat distortion temperature and glass transition temperature (Tg) were reduced when any glycidyl diluent was blended, compared to when no glycidyl diluent was added.

[0005] Incidentally, Japanese Patent Publication No. 49-16779 (Patent Document 1) discloses a method for improving the properties of an aromatic polyester molding, which comprises adding a glycidyl ether produced from an alkylene oxide adduct (number of moles added per active hydrogen: 2-40) of an alcohol, phenol or amine having an aromatic nucleus and an acid catalyst to the aromatic polyester molding, followed by heat treatment. In the examples of this document, it is described that the alkylene oxide adduct, such as an ethylene oxide adduct of o-phenylphenol (number of moles added: 5.0) or an ethylene oxide adduct of β-naphthol (number of moles added: 4.7), is reacted with epichlorohydrin to prepare the corresponding monoglycidyl ether, which is then used to treat a woven fabric made of polyethylene terephthalate or the like. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 49-16779 [Non-patent literature]

[0007] [Non-Patent Document 1] Toshikazu Misaki et al., "Effect of Glycidyl Diluents on the Fracture Toughness of Epoxy Resins", December 1986, "Materials", Vol. 35, No. 299, pp. 1399-1404 Summary of the Invention [Problem to be solved by the invention]

[0008] In Patent Document 1, it is only assumed that the glycidyl ether of an alkylene oxide adduct of phenol is used together with an acid catalyst to improve the properties of polyester moldings, and there is no mention or suggestion of using the glycidyl ether as a reactive diluent for epoxy resins. Moreover, in the examples of Patent Document 1, the number of moles added in the glycidyl ether of an ethylene oxide adduct of β-naphthol is about 5, and there is no specific mention of glycidyl ethers with an addition mole number of about 1 to 3.

[0009] All of the reactive diluents described in Non-Patent Document 1 are liquid epoxy compounds with low viscosity at room temperature and normal pressure, and therefore are less stable to external stimuli (or environmental changes) than solid diluents, and if they accidentally leak or flow out during use, storage, transportation, etc., the high fluidity of these compounds makes the leakage area likely to spread. In addition, because they are liquid rather than solid, they are also less easy to handle (handle or work) when used for weighing, etc.

[0010] Therefore, an object of the present disclosure is to provide a monofunctional epoxy compound that can reduce viscosity when combined with a multifunctional epoxy compound even if it is not in a low-viscosity liquid state (or even if it is in a solid state) at room temperature and normal pressure, and to provide a production method and uses thereof. [Means for solving the problem]

[0011] As a result of intensive research to achieve the above object, the present inventors have found that a monofunctional epoxy compound having a specific chemical structure can have a low viscosity when combined with a multifunctional epoxy compound even if the monofunctional epoxy compound is not a low-viscosity liquid at room temperature and normal pressure, and have completed the present disclosure. That is, the present disclosure may include the following aspects.

[0012] Aspect [1]: A compound represented by the following formula (1).

[0013] [ka]

[0014] (wherein Ar represents a polycyclic arene ring; A 1 represents an alkylene group, n1 represents an integer of 1 to 3, R 1 represents a hydrogen atom or an alkyl group, R 2 represents a substituent, and m2 represents an integer of 0 or more).

[0015] Aspect [2]: In the formula (1), Ar is a polycyclic C 10-14 Represents an arene ring; A 1 is C 2-6 represents an alkylene group, n1 represents an integer of 1 to 2, R 1 is a hydrogen atom or C 1-6 represents an alkyl group, R 2 represents a hydrocarbon group or a halogen atom.

[0016] Mode [3]: In the formula (1), Ar represents a naphthalene ring or a biphenyl ring, A 1 is C 2-4 represents an alkylene group, n1 represents 1; R 1 is a hydrogen atom or C 1-4 represents an alkyl group, R 2represents a hydrocarbon group, and m2 represents an integer of 0 to 7.

[0017] Aspect [4]: ​​The compound according to any one of aspects [1] to [3], which is a solid at a temperature of 25° C. and a pressure of 1 atmosphere.

[0018] Aspect [5]: A method for producing a compound represented by formula (1) according to any one of aspects [1] to [4], comprising reacting a compound represented by the following formula (2) with an epihalohydrin component:

[0019] [ka]

[0020] (Wherein, Ar, A 1 , n1, R 2 and m2 are the same as in formula (1) above).

[0021] Aspect [6]: A reactive diluent comprising a compound represented by formula (1) according to any one of aspects [1] to [4].

[0022] Aspect [7]: A curable composition comprising a polyfunctional epoxy compound and a compound represented by formula (1) according to any one of aspects [1] to [4].

[0023] Aspect [8]: The curable composition according to aspect [7], wherein the polyfunctional epoxy compound comprises at least a compound represented by the following formula (3):

[0024] [ka]

[0025] (In the formula, R 3 represents a substituent, m3 represents an integer of 0 to 8, Z 1a and Z 1b each independently represents an arene ring, A 2a and A 2beach independently represents an alkylene group; n2a and n2b each independently represent an integer of 0 or more; R 4a and R 4b each independently represents a hydrogen atom or an alkyl group, R 5a and R 5b each independently represents a substituent, and m5a and m5b each independently represent an integer of 0 or more).

[0026] Aspect [9]: In the formula (3), R 3 is a halogen atom, a hydrocarbon group, or a group [-OR h ](wherein, R h represents a hydrocarbon group) or a cyano group, m3 represents an integer of 0 to 4, Z 1a and Z 1b is independently C 6-14 Represents an arene ring; A 2a and A 2b is independently C 2-6 An alkylene group is represented, and n2a and n2b each independently represent an integer of 0 to 10. R 4a and R 4b are independently hydrogen atoms or C 1-6 represents an alkyl group, R 5a and R 5b each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a mono- or di-substituted amino group; and m5a and m5b each independently represent an integer of 0 to 4.

[0027] Aspect

[10] : The curable composition according to aspect [8] or [9], wherein, in formula (3), m5a and m5b each represent 0.

[0028] Aspect

[11] : In the formula (3), R 5a and R 5b each independently represents an alkyl group; and m5a and m5b each independently represent an integer of 1 to 4.

[0029] Aspect

[12] : The curable composition according to any one of aspects [7] to

[11] , wherein the proportion of the compound represented by formula (1) is 0.1 to 50 parts by mass per 100 parts by mass of the total amount of the polyfunctional epoxy compound and the compound represented by formula (1).

[0030] Aspect

[13] : A cured product of the curable composition according to any one of aspects [7] to

[12] .

[0031] Aspect

[14] : A molded article comprising the cured product according to aspect

[13] .

[0032] Aspect

[15] : A method for reducing viscosity by mixing a polyfunctional epoxy compound with a compound represented by formula (1) according to any one of aspects [1] to [4].

[0033] In addition, the present disclosure may achieve the following secondary objectives (solve the problems).

[0034] That is, another object of the present disclosure is to provide a monofunctional epoxy compound that can reduce the viscosity of a curable composition when combined with a multifunctional epoxy compound and can suppress a decrease in heat resistance in a cured product, as well as a production method and uses thereof.

[0035] Still another object of the present disclosure is to provide a monofunctional epoxy compound capable of forming a curable composition having excellent storage stability, and a production method and use thereof.

[0036] In this specification and claims, the number of carbon atoms of a substituent is represented as C1, C6, C 10 For example, an alkyl group with one carbon atom is represented as a "C1 alkyl group," and an aryl group with 6 to 10 carbon atoms is represented as a "C 6-10 Aryl group”.

[0037] In the present specification and claims, the term "independently" means that two components are independent components, for example, Z 1a and Z 1bIn the case of Z 1a and Z 1b and do not necessarily have to be the same arene ring, but may be different arene rings.

[0038] In this specification and claims, a numerical range indicated as "X to Y" may include the numerical values ​​X and Y. Effect of the Invention

[0039] According to the present disclosure, it is possible to provide a monofunctional epoxy compound that can reduce viscosity when combined with a multifunctional epoxy compound even if it is not in a low-viscosity liquid state (or even if it is in a solid state) at room temperature and normal pressure, as well as a production method and uses thereof. [Brief description of the drawings]

[0040] [Figure 1] FIG. 1 is a 1H-NMR spectrum of NEOG obtained in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0041] [Monofunctional epoxy compound represented by formula (1)] The monofunctional epoxy compound represented by the following formula (1) of the present disclosure [also simply referred to as monofunctional epoxy compound (1)] is a glycidyl ether type compound having a polycyclic arene ring skeleton and an alkyleneoxy group in combination in the chemical structure. Perhaps due to such a specific chemical structure, the monofunctional epoxy compound (1) can prepare a curable composition having a lower viscosity than the viscosity (particularly, melt viscosity) of the polyfunctional epoxy compound when combined with a high-viscosity polyfunctional epoxy compound even if it is not a low-viscosity liquid (or a solid state that does not show fluidity) at room temperature and normal pressure, for example, 25°C and 1 atm. Therefore, the monofunctional epoxy compound (1) can be effectively used as a reactive diluent with excellent handleability at room temperature and normal pressure. Therefore, the present disclosure also includes a method of adding the monofunctional epoxy compound (1) to a polyfunctional epoxy compound to reduce the viscosity (particularly, melt viscosity) of the curable composition (a method of improving the handleability or handling ability) and a method of improving the storage stability.

[0042] In addition, probably because of its specific chemical structure, the monofunctional epoxy compound (1) can achieve a good balance between lowering the viscosity of the curable composition (improving handling properties) and suppressing the decrease in heat resistance of the cured product. Furthermore, it can form a curable composition with excellent storage stability.

[0043] [ka]

[0044] (wherein Ar represents a polycyclic arene ring; A 1 represents an alkylene group, n1 represents an integer of 1 to 3, R 1 represents a hydrogen atom or an alkyl group, R 2 represents a substituent, and m2 represents an integer of 0 or more).

[0045] In the above formula (1), examples of the polycyclic arene ring (polycyclic aromatic hydrocarbon ring) represented by Ar include a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring) and a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring).

[0046] The fused polycyclic arene ring includes, for example, fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes, for example, fused bicyclic C rings such as naphthalene ring and indene ring. 10-16 Examples of the fused tricyclic arene ring include fused tricyclic C arene rings such as anthracene ring and phenanthrene ring. 14-20 A preferred fused polycyclic arene ring is a fused polycyclic C ring such as a naphthalene ring. 10-14 It is an arene ring.

[0047] Examples of the ring assembly arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. Preferred ring assembly arene rings are C 12-18 This is a biarene ring.

[0048] In the present specification and claims, a "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly linked by single bonds or double bonds, and the number of bonds directly linking the rings is one less than the number of ring systems. For example, as described above, a phenylnaphthalene ring, a binaphthyl ring, and the like are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as a naphthalene ring (non-ring assembly arene ring).

[0049] Preferred rings Ar include polycyclic C 10-14 arene rings, and more preferably polycyclic C such as naphthalene ring and biphenyl ring. 10-12An arene ring, particularly a naphthalene ring, is preferred. The ring Ar is preferably a condensed polycyclic arene ring such as a naphthalene ring, and more preferably a condensed polycyclic C 10-18 Arene ring, fused polycyclic C 10-16 Arene ring, fused polycyclic C 10-14 It may be an arene ring, and a naphthalene ring is particularly preferred.

[0050] A 1 Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, and a tetramethylene group. 2-6 Alkylene groups and the like are preferably C 2-4 C alkylene group, more preferably ethylene group, propylene group, etc. 2-3 An alkylene group is preferred, and an ethylene group is particularly preferred.

[0051] Alkyleneoxy group (-A 1 The repeat number (number of added moles) n1 of O-) may be an integer of 1 to 3, preferably 1 or 2, and more preferably 1. In the present specification and claims, the "repeated number (number of added moles)" may be an average value (arithmetic mean value, additive mean value) or an average number of added moles. n1 as an average value or average number of added moles may be selected, for example, from a range of about 0.5 to 3.5, and is preferably 0.8 to 3, 0.9 to 2.5, 1 to 2, and 1 to 1.5 in the following stepwise manner. When the upper limit value of n1 is within the above range, the handleability and refractive index of the monofunctional epoxy compound (1) tend to be improved, and the decrease in heat resistance and refractive index of the cured product tend to be suppressed.

[0052] When n1 is 2 or more, it is 2 or more alkyleneoxy groups (-A 1 The types of O-) may be different from each other, but are preferably the same.

[0053] R 1When is an alkyl group (straight-chain or branched-chain alkyl group), for example, C such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc. 1-6 Preferred alkyl groups are as follows, in order of decreasing order: 1-4 Alkyl group, C 1-3 Alkyl group, C 1-2 Alkyl groups and methyl groups.

[0054] Preferred R 1 The aryl group is a hydrogen atom or C 1-4 is an alkyl group, more preferably a hydrogen atom or C 1-3 an alkyl group, more preferably a hydrogen atom or C 1-2 An alkyl group, particularly a hydrogen atom or a methyl group, is preferred, and a hydrogen atom is particularly preferred.

[0055] Ring Ar and alkyleneoxy group (-A 1 O-) between the oxygen atom [in formula (1), "-(A 1 O) n1 The bonding position (substitution position) of the oxygen atom bonded to the left of "-" to the ring Ar may be any position. For example, when the ring Ar is a naphthalene ring, it may be either the 1st or 2nd position, and the 2nd position is preferred.

[0056] R 2 The substituent represented by the formula (I) may be a non-reactive substituent that is inactive in the reaction, and examples thereof include a hydrocarbon group and a halogen atom.

[0057] Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0058] Examples of the alkyl group (linear or branched alkyl group) include C alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. 1-10 Alkyl groups are preferred, and C 1-6 Alkyl groups, more preferably C 1-4 It is an alkyl group.

[0059] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are included.

[0060] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl group (or tolyl group), dimethylphenyl group (or xylyl group), etc. 1-4 Examples include alkyl-phenyl groups.

[0061] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of such groups include alkyl groups.

[0062] Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0063] Preferred R 2 Examples of the alkyl group include a hydrocarbon group such as an alkyl group. More preferably, the alkyl group is 1-6 Alkyl group, C 1-4 Alkyl group, C 1-3 Alkyl group, C 1-2 Alkyl groups and methyl groups.

[0064] R 2 The number of substitutions m2 is an integer of 0 or more, and may be, for example, an integer of about 0 to 9 depending on the type of the ring Ar, and is preferably an integer of 0 to 7, an integer of 0 to 5, an integer of 0 to 3, an integer of 0 to 2, stepwise, more preferably 0 or 1, and particularly preferably 0.

[0065] Representative monofunctional epoxy compounds (1) include, for example, those in which Ar is a naphthalene ring or a biphenyl ring, A 1 C such as ethylene group 2-4 Alkylene group, R 1is a hydrogen atom or a methyl group, and specifically, glycidyloxy (mono- or tri-)C such as 2-(2-glycidyloxyethoxy)naphthalene, 2-[2-(2-glycidyloxyethoxy)ethoxy]naphthalene, 2-(2-glycidyloxypropoxy)naphthalene, and 1-(2-glycidyloxyethoxy)naphthalene. 2-4 alkoxy]naphthalene; corresponding to these compounds, the glycidyl group in the chemical structure is changed to a β-methylglycidyl group (i.e., R 1 (β-methylglycidyl)oxy(mono- or tri-)C 2-4 Alkoxy]naphthalene and the like.

[0066] The monofunctional epoxy compound (1) may be liquid at a temperature of 25°C and a pressure of 1 atm, but is preferably solid (solid or solid state). In a solid state, it is more stable against external stimuli (or environmental changes) than in a liquid state, and even if it leaks or flows out accidentally, the leakage area is less likely to spread, and it is also easy to handle (handle or work) when used for weighing, etc. In addition, even if the monofunctional epoxy compound (1) is in a solid state that does not show fluidity at room temperature and normal pressure, it can effectively reduce the viscosity of the polyfunctional epoxy compound and improve the handleability in the curable composition.

[0067] The monofunctional epoxy compound (1) may be crystalline or amorphous, and is preferably crystalline. The melting point of the monofunctional epoxy compound (1) is, for example, 50 to 150° C., preferably 60 to 100° C., and more preferably 70 to 90° C. In the present specification and claims, the melting point can be measured by the method described in the Examples below.

[0068] The epoxy equivalent of the monofunctional epoxy compound (1) is, for example, 200 to 500 g / eq, preferably 230 to 300 g / eq, and more preferably 240 to 280 g / eq. In this specification and claims, the epoxy equivalent can be measured according to JIS K 7236:2001 by the method described in the examples below.

[0069] Since the monofunctional epoxy compound (1) has a high refractive index, even when combined with a polyfunctional epoxy compound, the decrease in the refractive index of the curable composition can be suppressed (the refractive index can be maintained or improved). Therefore, the curable composition and its cured product can be used for optical applications such as optical members and optical adhesives. The refractive index of the monofunctional epoxy compound (1) is, for example, 1.54 to 1.59, preferably 1.55 to 1.58, and more preferably 1.56 to 1.57 at a temperature of 25°C and a wavelength of 589 nm. In the present specification and claims, the refractive index can be measured by the method described in the Examples below.

[0070] [Method for producing monofunctional epoxy compound represented by formula (1)] The method for producing the monofunctional epoxy compound (1) is not particularly limited. For example, a compound represented by the following formula (2) [also simply referred to as alcohol compound (2)] can be prepared by reacting with an epihalohydrin component [addition reaction and ring-closing (dehydrohalogenation) reaction].

[0071] [ka]

[0072] (Wherein, Ar, A 1 , n1, R 2 and m2 are the same as those in the above formula (1) including preferred embodiments.

[0073] Examples of the alcohol compound (2) include alcohol compounds (compounds in which the glycidyloxy group in the chemical structure is replaced with a hydroxyl group) corresponding to the compounds exemplified as the above-mentioned representative monofunctional epoxy compounds (1). Specific examples of the alcohol compound (2) include [hydroxy(mono- or tri)C] such as 2-(2-hydroxyethoxy)naphthalene, 2-[2-(2-hydroxyethoxy)ethoxy]naphthalene, 2-(2-hydroxypropoxy)naphthalene, and 1-(2-hydroxyethoxy)naphthalene. 2-4These may be commercially available products, or may be prepared by a conventional method, for example, by reacting a polycyclic phenol corresponding to Ar, specifically a naphthol such as β-naphthol, with A 1 and an alkylene oxide (alkylene carbonate or haloalkanol) corresponding to n1 may be reacted to use the above-mentioned compound.

[0074] As the epihalohydrin component (epihalohydrins), R of the monofunctional epoxy compound (1) 1 In accordance with the type of the epihalohydrin, for example, epihalohydrin, β-methylepihalohydrin, etc. can be mentioned. As the epihalohydrin, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, etc. can be mentioned. As the β-methylepihalohydrin, for example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepiiodohydrin, etc. can be mentioned. These epihalohydrin components can be used alone or in combination of two or more. Among these epihalohydrin components, epihalohydrins such as epichlorohydrin and β-methylepichlorohydrin are preferred, and epichlorohydrin is more preferred.

[0075] The proportion of the epihalohydrin component may be, for example, 1 mol or more per mol of the alcohol compound (2), but may be an excess amount relative to the alcohol compound (2) and is, for example, 1.5 to 100 mol, preferably 2 to 50 mol, more preferably 3 to 10 mol, and particularly preferably 4 to 8 mol.

[0076] The reaction may be carried out in the presence of a base. Examples of the base include inorganic bases such as metal hydroxides, metal carbonates or hydrogen carbonates; and organic bases such as amines. Examples of the metal hydroxides include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide. Examples of the metal carbonates or hydrogen carbonates include alkali metal or alkaline earth metal carbonates or hydrogen carbonates such as sodium carbonate and sodium hydrogen carbonate. Examples of the amines include trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic tertiary amines such as pyridine. The base may be used alone or in combination. Among these bases, strong bases (strong alkalis) are preferred, and metal hydroxides such as sodium hydroxide are more preferred.

[0077] The ratio of the base is, for example, 1 to 20 mol, preferably 1.05 to 10 mol, 1.1 to 5 mol, or 1.2 to 1.5 mol, stepwise, relative to 1 mol of the alcohol compound (2). The base may be added all at once during the reaction, or may be added stepwise in multiple portions.

[0078] The reaction may be carried out in the presence or absence of a catalyst, as necessary. Examples of the catalyst include quaternary ammonium salts, specifically, tetramethylammonium chloride, tetramethylammonium bromide, and other tetra-C 1-20 Alkyl ammonium halides, benzyl trimethyl ammonium chloride, etc. 1-4 Alkyl ammonium halides, etc.; Trimethylamine borane, etc. 1-4 Examples of the catalyst include alkylamine borane, crown ether, phosphonium salt, pyridinium salt, etc. The catalyst may be used alone or in combination of two or more kinds.

[0079] When a catalyst is used, the amount of the catalyst is, for example, 0.001 to 1 mol, preferably 0.01 to 0.2 mol, and more preferably 0.05 to 0.1 mol, relative to 1 mol of the alcohol compound (2).

[0080] The reaction may be carried out in an inert solvent or without a solvent. As the solvent, an aprotic solvent or the like can be used, for example, hydrocarbons, specifically, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, esters such as ethyl acetate, ethers, specifically, dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran, ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), amides such as dimethylformamide (DMF) and dimethylacetamide, and sulfoxides such as dimethyl sulfoxide (DMSO). The solvent may be used alone or in combination of two or more. Among these solvents, ketones, amides, and sulfoxides are preferred from the viewpoint of reactivity, and ketones such as MIBK and sulfoxides such as DMSO are more preferred.

[0081] The amount of the solvent is, for example, 10 to 1000 parts by mass, preferably 50 to 500 parts by mass, and more preferably 80 to 200 parts by mass, relative to 100 parts by mass of the alcohol compound (2).

[0082] When the solvent contains a sulfoxide such as DMSO, the generation of by-products can be suppressed in some cases. Therefore, when the solvent contains a sulfoxide such as DMSO, the amount of the sulfoxide such as DMSO may be, for example, about 0.1 to 1 mol, preferably 0.3 to 0.7 mol, and more preferably 0.4 to 0.6 mol, per mol of the epihalohydrin component.

[0083] The reaction may be carried out in air or in an inert atmosphere such as nitrogen gas or a rare gas, with stirring, or under normal pressure, elevated pressure, or reduced pressure.

[0084] The reaction temperature and reaction time may be appropriately selected depending on the type of raw material. The reaction temperature is, for example, 30 to 120°C, preferably 50 to 100°C, 60 to 90°C, and 65 to 80°C in the following stepwise manner. The reaction may be carried out under reflux (at the reflux temperature). The reaction time is, for example, 30 minutes to 48 hours, preferably 2 to 6 hours.

[0085] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, such as washing, extraction, filtration, dehydration, concentration, decantation, drying, crystallization, reprecipitation, column chromatography, adsorption, or a combination of these methods.

[0086] [Reactive diluent] The monofunctional epoxy compound (1) can be used as a reactive diluent even if it is not liquid at room temperature and normal pressure, particularly if it is a solid that does not exhibit fluidity, and can effectively reduce the viscosity (particularly the melt viscosity) of a highly viscous polyfunctional epoxy compound (epoxy resin). Therefore, the reactive diluent of the present disclosure only needs to contain at least the monofunctional epoxy compound (1).

[0087] The reactive diluent of the present disclosure may not contain other epoxy compounds (other reactive diluent components) different from the monofunctional epoxy compound (1), but may contain them as necessary. Examples of the other epoxy compounds (other reactive diluent components) include conventional reactive diluents for epoxy resins, and may be, for example, liquid monofunctional or polyfunctional epoxy compounds having a viscosity at 25°C of about 200 mPa·s or less, preferably 100 mPa·s or less, more preferably 50 mPa·s or less, and particularly preferably 30 mPa·s or less.

[0088] Examples of the liquid monofunctional epoxy compound (conventional reactive diluent) include glycidyl ethers such as alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether, alkenyl glycidyl ethers such as allyl glycidyl ether, phenyl glycidyl ether, pt-butylphenyl glycidyl ether, and other phenyl glycidyl ethers; and glycidyl ethers of alkylene oxide adducts corresponding to these compounds; and alkene oxides such as octylene oxide, styrene oxide, and 4-vinylcyclohexene monoxide.

[0089] Examples of the liquid polyfunctional epoxy compound (conventional reactive diluent) include diglycidyl ether, polyol polyglycidyl ether, diglycidyl aniline, and cycloalkene oxide. Examples of the polyol polyglycidyl ether include (poly)alkanediol diglycidyl ethers such as butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, trimethylolpropane diglycidyl ether, triglycidyl ether, and glycerin diglycidyl ether. Examples of the cycloalkene oxide include vinylcyclohexene dioxide and methylated vinylcyclohexene dioxide.

[0090] These other epoxy compounds may be used alone or in combination of two or more. The proportion of the monofunctional epoxy compound (1) in the reactive diluent is, for example, 10% by mass or more, preferably 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, and more preferably 100% by mass, based on the total amount of the monofunctional epoxy compound (1) and the other epoxy compounds (conventional reactive diluents).

[0091] [Curable composition] The monofunctional epoxy compound (1) [or the reactive diluent of the present disclosure] can effectively reduce the viscosity of the polyfunctional epoxy compound (epoxy resin component), and the curable composition can be easily prepared. In addition, the monofunctional epoxy compound (1) is unlikely to precipitate and has excellent storage stability even when combined with a polyfunctional epoxy compound (epoxy resin component) to form a curable composition. Therefore, the curable composition of the present disclosure only needs to contain at least the monofunctional epoxy compound (1) and the polyfunctional epoxy compound (epoxy resin component), and may be a thermosetting or photocurable composition.

[0092] (Polyfunctional epoxy compound (epoxy resin component)) Examples of polyfunctional epoxy compounds (epoxy resin components) include glycidyl ether type epoxy resins, specifically, bi- or bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol AD ​​type, bisphenol S type, and biphenol type, novolac type epoxy resins such as phenol novolac type and cresol novolac type, phenol aralkyl type epoxy resins, triphenol alkane type epoxy resins, tetrakisphenol type epoxy resins such as tetrakis(glycidyloxyphenyl)ethane, condensed ring aromatic hydrocarbon modified epoxy resins such as 1,6-bis(glycidyloxy)naphthalene, glycidyl ether type epoxy resins having a 9,9-bisarylfluorene skeleton, and the like; aromatic diphenyl ether type epoxy resins, Examples of epoxy resins include glycidyl ester type epoxy resins such as diglycidyl esters of carboxylic acids (or their hydrogenated products); glycidyl amine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, tetraglycidylbisaminomethylcyclohexane, and triglycidylaminophenol; cyclic aliphatic type epoxy resins such as bis(3,4-epoxycyclohexylmethyl)adipate and (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate; stilbene type epoxy resins; heterocyclic type epoxy resins such as isocyanurate type epoxy resins, hydantoin type epoxy resins, and epoxy resins containing xanthene units; and bromine-containing epoxy resins such as tetrabromobisphenol A type epoxy resin.

[0093] These polyfunctional epoxy compounds (epoxy resin components) may be monomers or polymers such as dimers and trimers.

[0094] The epoxy equivalent of the polyfunctional epoxy compound is not particularly limited and may be, for example, about 100 to 1000 g / eq, preferably about 200 to 500 g / eq, and more preferably about 230 to 300 g / eq.

[0095] These polyfunctional epoxy compounds (epoxy resin components) may be used alone or in combination of two or more.Preferred polyfunctional epoxy compounds (epoxy resin components) are aromatic polyfunctional epoxy compounds (aromatic epoxy resin components) that tend to be easily viscous, more preferably bi- or bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, and glycidyl ether-type epoxy resins such as glycidyl ether-type epoxy resins having a 9,9-bisarylfluorene skeleton, and particularly preferably glycidyl ether-type epoxy resins having a 9,9-bisarylfluorene skeleton, because they can effectively reduce viscosity and can prepare a curable composition with high heat resistance and high refractive index.

[0096] Examples of glycidyl ether type epoxy resins having a 9,9-bisarylfluorene skeleton include a compound represented by the following formula (3) (including its polymer) [also simply referred to as polyfunctional epoxy compound (3)].

[0097] [ka]

[0098] (In the formula, R 3 represents a substituent, m3 represents an integer of 0 to 8, Z 1a and Z 1b each independently represents an arene ring, A 2a and A 2beach independently represents an alkylene group; n2a and n2b each independently represent an integer of 0 or more; R 4a and R 4b each independently represents a hydrogen atom or an alkyl group, R 5a and R 5b each independently represents a substituent, and m5a and m5b each independently represent an integer of 0 or more).

[0099] In the formula (3), R 3 The substituent represented by the formula (I) may be a non-reactive group (or a non-polymerizable group) that is inert to the reaction, and examples of the substituent represented by the formula (I) include a halogen atom, a hydrocarbon group, a group [-OR h ](wherein, R h represents a hydrocarbon group), an acyl group, a nitro group, a cyano group or a substituted amino group (mono- or di-substituted amino group).

[0100] In this specification and claims, R h The hydrocarbon groups represented by the following formula (I) each represent an independent hydrocarbon group, and may be the same or different from each other.

[0101] Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0102] Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. 2 Examples of the hydrocarbon groups include the same groups as those exemplified as the alkyl groups (alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups).

[0103] The group [-OR h ], wherein the hydrocarbon group R h Examples of the R in the formula (1) include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. 2 Examples of the hydrocarbon groups (alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups) exemplified as the above-mentioned groups [-OR h] is, for example, the hydrocarbon group R h Examples of the alkoxy group include an alkoxy group, a cycloalkyloxy group, an aryloxy group, and an aralkyloxy group. Examples of the alkoxy group (linear or branched alkoxy group) include C alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. 1-10 Examples of the cycloalkyloxy group include a C alkoxy group such as a cyclohexyloxy group. 5-10 Examples of the aryloxy group include C aryloxy groups such as phenoxy groups. 6-10 Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 An example of such a group is an alkyloxy group.

[0104] The acyl group is C 1-12 acyl groups, for example, C such as acetyl group. 1-6 Examples include alkyl-carbonyl groups.

[0105] Examples of the mono- or di-substituted amino group include mono- or di-alkylamino groups, mono- or bis(alkylcarbonyl)amino groups, etc. Examples of the mono- or di-alkylamino group include mono- or di-C groups such as mono- or dimethylamino groups. 1-4 Examples of the mono- or bis(alkylcarbonyl)amino group include mono- or bis(C alkylamino groups such as mono- or diacetylamino groups. 1-4 alkyl-carbonyl)amino groups.

[0106] Among these groups, representative R 3 Examples of the alkyl group include halogen atoms, hydrocarbon groups, and the group [-OR h and cyano group, and preferably a halogen atom, a hydrocarbon group such as an alkyl group or an aryl group, an alkoxy group, an aryloxy group, or the like [-OR h ] are some examples.

[0107] R 3 The number of substitutions m3 may be, for example, an integer of about 0 to 6, and is preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, stepwise, more preferably 0 or 1, and particularly preferably 0. In addition, the number of substitutions m3 in the two benzene rings constituting the fluorene ring may be an integer of about 0 to 6, and is preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, stepwise, more preferably 0 or 1, and particularly preferably 0. 3 The numbers of substitutions (the numbers of substitutions at positions 1 to 4 and the numbers of substitutions at positions 5 to 8) may be different from each other, but are preferably the same.

[0108] In addition, the group R 3 When the number of substitutions m3 is more than one (2 or more), two or more groups R 3 The types of may be the same or different; and the groups R 3 The types of groups R may be different, but are preferably the same. 3 The bonding positions (substitution positions) of are not particularly limited as long as they are 1-8 positions of the fluorene ring. Examples include 2-positions, 7-positions, and 2,7-positions of the fluorene ring, with 2,7-positions being preferred.

[0109] Z 1a ,Z 1b Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (1) include monocyclic arene rings such as a benzene ring, polycyclic arene rings such as a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring), and ring-assembly arene rings (ring-assembly aromatic hydrocarbon rings). Examples of the fused polycyclic arene ring and ring-assembly arene ring include the same ring as the ring Ar in the formula (1).

[0110] Preferred Ring Z 1a ,Z 1b is C 6-14 arene rings, more preferably benzene rings, naphthalene rings, biphenyl rings, etc. 6-12 arene rings, and more preferably benzene rings, naphthalene rings, etc. 6-10Among the arene rings, a benzene ring is particularly preferred in that it is easier to prevent the heat resistance of the cured product from decreasing, and a naphthalene ring is particularly preferred in that it is more effective in reducing the viscosity. 1a ,Z 1b is a condensed polycyclic arene ring such as a naphthalene ring, for example, a condensed polycyclic C 10-14 It appears that the viscosity can be reduced more effectively with an arene ring. 1a and Z 1b The types of may be different from each other, but are preferably the same.

[0111] Z attached to the 9-position of the fluorene ring 1a and Z 1b The substitution position of is not particularly limited, and for example, Z 1a , Z 1b When is a benzene ring, it may be at any position, and Z 1a , Z 1b When is a naphthalene ring, it is either the 1-position (1-naphthyl) or the 2-position (2-naphthyl), preferably the 2-position; Z 1a , Z 1b When is a biphenyl ring, it is at the 2-, 3- or 4-position, preferably the 3-position.

[0112] A 2a ,A 2b As the alkylene group (linear or branched alkylene group) represented by the formula (1), 1 Examples of the alkylene groups include those exemplified as the alkylene groups. 2a ,A 2b As for C 2-6 Alkylene group, more preferably C 2-4 C alkylene group, more preferably ethylene group, propylene group, etc. 2-3 An alkylene group is preferable, and an ethylene group is particularly preferable. 2a ,A 2b The types may be the same or different from each other.

[0113] A 2a ,A 2bThe repeat numbers (number of moles added) n2a and n2b may each be, for example, an integer of about 0 to 15, and preferably, in the following stepwise order, an integer of 0 to 10, an integer of 0 to 8, an integer of 0 to 6, an integer of 0 to 4, or an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. n2a and n2b may each be an average value (arithmetic mean value, additive mean value) or an average number of moles added, and may be, for example, in the range of about 0 to 15, and preferably, in the following stepwise order, 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, 0 to 1, or 0 to 0.5. When the upper limit values ​​of n2a and n2b are within the above ranges, there is a tendency that a decrease in heat resistance and refractive index can be suppressed.

[0114] In addition, n2a and n2b may be the same or different. When n2a is 2 or more, two or more alkyleneoxy groups (-A 2a The types of alkyleneoxy groups (-A-O-) may be different from each other, but are preferably the same. When n2b is 2 or more, two or more alkyleneoxy groups (-A 2b The types of O-) may be different from each other, but are preferably the same.

[0115] R 4a ,R 4b When R is an alkyl group (straight-chain or branched-chain alkyl group), the alkyl group is, for example, R 1 Examples of the alkyl group include the same groups as those exemplified as the alkyl groups.

[0116] Preferred R 4a ,R 4b The aryl group is a hydrogen atom or C 1-6 is an alkyl group, preferably a hydrogen atom or C 1-4 Alkyl group, hydrogen atom or C 1-3 Alkyl group, hydrogen atom or C 1-2 R is an alkyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. 4a ,R 4b The types of may be different from each other, but are preferably the same.

[0117] The group [-O-(A2a O) n2a -],[-O-(A 2b O) n2b -] (i.e., 9,9-bisarylfluorene skeleton and R 4a ,R 4b Ring Z of an ether bond connecting a glycidyl group containing 1a , Z 1b The substitution position for Z is not particularly limited. 1a ,Z 1b The group [-O-(A 2a O) n2a -],[-O-(A 2b O) n2b -] Ring Z 1a ,Z 1b The substitution position for Z 1a ,Z 1b When Z is a benzene ring, it is preferred that the substituent is at any one of the 2-, 3-, or 4-position, particularly the 3- or 4-position, and particularly the 4-position, of the phenyl group bonded to the 9-position of the fluorene ring. 1a ,Z 1b When Z is a naphthalene ring, it is often substituted at any one of the 5-8 positions of the naphthyl group bonded to the 9-position of the fluorene ring. For example, the 1- or 2-position of the naphthalene ring is substituted with respect to the 9-position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and it is preferred that Z is substituted with respect to this substitution position in a 1,5-position or 2,6-position relationship, particularly in a 2,6-position relationship. 1a ,Z 1b When is a ring assembly arene ring, the group [-O-(A 2a O) n2a -],[-O-(A 2b O) n2b The substitution position of Z -] may be, for example, on the arene ring bonded to the 9-position of the fluorene or on the arene ring adjacent to this arene ring. For example, Z 1a ,Z 1b is a biphenyl ring (or Z 1a ,Z 1b is a benzene ring, m5a and m5b are 1 or more, R 5a , R 5bis a phenyl group), the 3- or 4-position of the biphenyl ring, preferably the 3-position, may be bonded to the 9-position of the fluorene. When the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, the group [-O-(A 2a O) n2a -],[-O-(A 2b O) n2b The substitution position of -] may be, for example, any of the 2-, 4-, 5-, 6-, 2'-, 3'-, or 4'-position of the biphenyl ring, preferably the 6- or 4'-position, and particularly preferably the 6-position.

[0118] R 5a ,R 5b The substituent represented by the formula (I) may be a non-reactive group (or a non-polymerizable group) that is inert to the reaction, and examples of the substituent represented by the formula (I) include a halogen atom, a hydrocarbon group, a group [-OR h ](wherein, R h represents a hydrocarbon group), the group [-SR h ](wherein, R h represents a hydrocarbon group), an acyl group, a nitro group, a cyano group, a substituted amino group (mono- or di-substituted amino group), and the like.

[0119] Of these, halogen atoms, hydrocarbon groups, and groups [-OR h ], an acyl group, and a substituted amino group (mono- or di-substituted amino group) are each represented by the above R 3 Examples of the groups include the same groups as those exemplified as the groups.

[0120] The group [-SR h ] is, for example, the hydrocarbon group R h Examples of the alkylthio group include a C alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, etc. Examples of the alkylthio group include a C alkylthio group, such as a methylthio group, an ethylthio group, a propylthio group, an n-butylthio group, and a t-butylthio group. 1-10 Examples of the cycloalkylthio group include a C alkylthio group such as a cyclohexylthio group. 5-10 Examples of the arylthio group include a C thiophenoxy group. 6-10Examples of the aralkylthio group include C arylthio groups such as benzylthio groups. 6-10 Aryl-C 1-4 Examples of such groups include alkylthio groups.

[0121] Representative R 5a ,R 5b Examples of R include a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group. 5a ,R 5b Examples of the alkyl group include a hydrocarbon group such as an alkyl group (straight-chain or branched-chain alkyl group), a cycloalkyl group, or an aryl group, and an alkoxy group (straight-chain or branched-chain alkoxy group) [-OR h More preferably, C such as a methyl group. 1-6 C such as alkyl group and cyclohexyl group 5-8 Cycloalkyl groups, phenyl groups, etc. 6-14 C such as aryl group and methoxy group 1-4 Alkoxy groups are particularly preferred. Among these, alkyl groups and aryl groups (C groups such as phenyl groups) are particularly preferred. 6-10 Preferred are hydrocarbon groups such as alkyl groups (e.g., aryl groups, etc.), and in particular, C alkyl groups such as methyl groups. 1-4 R is preferably an alkyl group. 5a ,R 5b The types of R may be the same or different from each other. 5a and / or R 5b When R is an alkyl group such as a methyl group, the polyfunctional epoxy compound (3) may be prone to precipitation. However, in the curable composition of the present disclosure, the precipitation from the curable composition can be effectively suppressed, probably because it is combined with the monofunctional epoxy compound (1), and the storage stability is likely to be improved. 5a ,R 5b is an aryl group, R 5a ,R 5b are rings Z 1a , Z 1b may form the ring assembly arene ring.

[0122] R 5a ,R 5bThe number of substitutions m5a and m5b of the ring Z 1a ,Z 1b can be appropriately selected depending on the type of m5a and m5b, and may be, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0 or 1. In order to more effectively reduce the viscosity, 0 is particularly preferred. In order to effectively improve the storage stability, m5a and m5b can be an integer of 1 or more, and are preferably, in the following stepwise order, an integer of 1 to 6, an integer of 1 to 4, an integer of 1 to 3, more preferably 1 or 2, and especially preferably 2; when m5a and m5b are each an integer of 1 or more, R 5a and / or R 5b may contain at least an alkyl group. m5a and m5b may be different from each other, but are preferably the same. When m5a is 2 or more, R 5a may be the same or different from each other, and when m5b is 2 or more, R 5b The types may be the same or different from each other.

[0123] Also, R 5a ,R 5b The substitution position of Z is not particularly limited. 1a ,Z 1b In the formula (I), the group [-O-(A 2a O) n2a -],[-O-(A 2b O) n2b -] and the position other than the bonding position with the 9-position of the fluorene ring. For example, Z 1a ,Z 1b The group [-O-(A 2a O) n2a -],[-O-(A 2b O) n2b --] may be substituted at the ortho position (the carbon atom adjacent to the bonding position of the ether bond).

[0124] Representative polyfunctional epoxy compounds (3) include: R 3 is a halogen atom, a hydrocarbon group, or a group [-OR h](wherein, R h represents a hydrocarbon group) or a cyano group, m3 represents an integer of 0 to 4, Z 1a and Z 1b is independently C 6-14 Represents an arene ring; A 2a and A 2b is independently C 2-6 An alkylene group is represented, and n2a and n2b each independently represent an integer of 0 to 10. R 4a and R 4b are independently hydrogen atoms or C 1-6 represents an alkyl group, R 5a and R 5b each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a mono- or di-substituted amino group, and m5a and m5b each independently represent an integer of 0 to 4;

[0125] Preferably, R 3 represents a hydrocarbon group (such as an alkyl group or an aryl group), m3 represents an integer from 0 to 3, Z 1a and Z 1b is independently C 6-12 Represents an arene ring; A 2a and A 2b is independently C 2-4 An alkylene group, n2a and n2b each independently represent an integer of 0 to 6, R 4a and R 4b are independently hydrogen atoms or C 1-4 represents an alkyl group, R 5a and R 5b each independently represents a hydrocarbon group (such as an alkyl group or an aryl group), and m5a and m5b each independently represent an integer of 0 to 4;

[0126] More preferably, R 3 represents an alkyl group, m3 represents an integer of 0 to 2, Z 1a and Z 1b is independently C 6-12 Represents an arene ring; A 2a and A 2b is independently C 2-3 An alkylene group is represented, and n2a and n2b each independently represent an integer of 0 to 3. R 4a and R 4b are independently hydrogen atoms or C 1-3 represents an alkyl group, R 5a and R 5b each independently represents an alkyl group, and m5a and m5b each independently represent an integer of 0 to 4.

[0127] Among them, in terms of being easy to reduce the viscosity more effectively, a compound in which m5a and m5b are both 0 in the formula (3) is preferred, for example, R 3 is C 1-6 an alkyl group such as an alkyl group; m3 represents an integer of 0 to 2 (e.g., 0 or 1, or 0 or 2); Z 1a and Z 1b are independently C such as benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 Represents an arene ring; A 2a and A 2b is independently C 2-3 represents an alkylene group, n2a and n2b each independently represent an integer of 0 to 3 (preferably 0 to 2), R 4a and R 4b are independently hydrogen atoms or C 1-2 represents an alkyl group, m5a and m5b are compounds each showing 0;

[0128] Particularly preferably, R 3 is C 1-4 m3 represents an integer of 0 to 2 (preferably 0 or 2, particularly 0); Z 1a and Z1b are independently C such as benzene ring, naphthalene ring, etc. 6-10 Represents an arene ring (particularly a benzene ring), A 2a and A 2b is independently C 2-3 an alkylene group (particularly, an ethylene group); n2a and n2b each independently represent 0 or 1 (particularly, 0); R 4a and R 4b each independently represents a hydrogen atom or a methyl group, Compounds in which m5a and m5b are 0 are exemplified.

[0129] In order to more effectively improve the storage stability, in the formula (3), m5a and m5b each independently represent an integer of 1 or more (preferably an integer of 1 to 4); 5a and R 5b contains at least an alkyl group (preferably R 5a and R 5b are independently an alkyl group), R 3 is C 1-6 an alkyl group such as an alkyl group; m3 represents an integer of 0 to 2 (e.g., 0 or 1, or 0 or 2); Z 1a and Z 1b are independently C such as benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 Represents an arene ring; A 2a and A 2b is independently C 2-3 represents an alkylene group, n2a and n2b each independently represent an integer of 0 to 3 (preferably 0 to 2), R 4a and R 4b are independently hydrogen atoms or C 1-2 represents an alkyl group, R 5a and R 5b is independently C 1-6 an alkyl group such as an alkyl group, and m5a and m5b each independently represent an integer of 1 to 4;

[0130] Particularly preferably, R 3 is C 1-4 m3 represents an integer of 0 to 2 (preferably 0 or 2, particularly 0); Z 1a and Z 1b are independently C such as benzene ring, naphthalene ring, etc. 6-10 Represents an arene ring (particularly a benzene ring), A 2a and A 2b is independently C 2-3 an alkylene group (particularly, an ethylene group); n2a and n2b each independently represent 0 or 1 (particularly, 0); R 4a and R 4b each independently represents a hydrogen atom or a methyl group, R 5a and R 5b are independently C such as methyl group 1-4 It is an alkyl group, and m5a and m5b each independently represent an integer of 1 to 3 (preferably 1 or 2, particularly 2).

[0131] Specific examples of the polyfunctional epoxy compound (3) include 9,9-bis(glycidyloxyaryl)fluorenes, 9,9-bis[glycidyloxy(poly)alkoxyaryl]fluorenes, and the like.

[0132] In this specification and claims, unless otherwise specified, the term "(poly)alkoxy" is used to include both an alkoxy group and a polyalkoxy group.

[0133] Examples of 9,9-bis(glycidyloxyaryl)fluorenes include 9,9-bis(glycidyloxyphenyl)fluorene, 9,9-bis(alkyl-glycidyloxyphenyl)fluorene, 9,9-bis(aryl-glycidyloxyphenyl)fluorene, 9,9-bis(glycidyloxynaphthyl)fluorene, and corresponding compounds in which the glycidyl group is replaced with a β-methylglycidyl group.

[0134] Examples of 9,9-bis(glycidyloxyphenyl)fluorene include 9,9-bis(4-glycidyloxyphenyl)fluorene.

[0135] Examples of the 9,9-bis(alkyl-glycidyloxyphenyl)fluorene include 9,9-bis[(mono or di)C]fluorene such as 9,9-bis(4-glycidyloxy-3-methylphenyl)fluorene and 9,9-bis(4-glycidyloxy-3,5-dimethylphenyl)fluorene. 1-4 alkyl-glycidyloxyphenyl]fluorene and the like.

[0136] Examples of the 9,9-bis(aryl-glycidyloxyphenyl)fluorene include 9,9-bis(C 6-10 aryl-glycidyloxyphenyl)fluorene and the like.

[0137] Examples of 9,9-bis(glycidyloxynaphthyl)fluorene include 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene and 9,9-bis(5-glycidyloxy-1-naphthyl)fluorene.

[0138] Examples of 9,9-bis[glycidyloxy(poly)alkoxyaryl]fluorenes include 9,9-bis[glycidyloxy(poly)alkoxyphenyl]fluorene, 9,9-bis[alkyl-glycidyloxy(poly)alkoxyphenyl]fluorene, 9,9-bis[aryl-glycidyloxy(poly)alkoxyphenyl]fluorene, 9,9-bis[glycidyloxy(poly)alkoxynaphthyl]fluorene, and corresponding compounds in which the glycidyl group is replaced with a β-methylglycidyl group.

[0139] Examples of the 9,9-bis[glycidyloxy(poly)alkoxyphenyl]fluorene include 9,9-bis[glycidyloxy(mono- to deca)C such as 9,9-bis[4-(2-glycidyloxyethoxy)phenyl]fluorene and 9,9-bis[4-(2-glycidyloxypropoxy)phenyl]fluorene. 2-4 alkoxy-phenyl]fluorene and the like.

[0140] Examples of the 9,9-bis[alkyl-glycidyloxy(poly)alkoxyphenyl]fluorene include 9,9-bis[(mono or di)C such as 9,9-bis[4-(2-glycidyloxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-glycidyloxyethoxy)-3,5-dimethylphenyl]fluorene, and 9,9-bis[4-(2-glycidyloxypropoxy)-3-methylphenyl]fluorene. 1-4 Alkyl-glycidyloxy (mono to deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0141] Examples of the 9,9-bis[aryl-glycidyloxy(poly)alkoxyphenyl]fluorene include 9,9-bis[C such as 9,9-bis(4-(2-glycidyloxyethoxy)-3-phenylphenyl)fluorene and 9,9-bis(4-(2-glycidyloxypropoxy)-3-phenylphenyl)fluorene. 6-10 Aryl-glycidyloxy (mono to deca)C 2-4 alkoxy-phenyl]fluorene and the like.

[0142] Examples of the 9,9-bis[glycidyloxy(poly)alkoxynaphthyl]fluorene include 9,9-bis[glycidyloxy(mono- to deca)C such as 9,9-bis[6-(2-glycidyloxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-glycidyloxyethoxy)-1-naphthyl]fluorene, and 9,9-bis[6-(2-glycidyloxypropoxy)-2-naphthyl]fluorene. 2-4alkoxy-naphthyl]fluorene and the like.

[0143] The polyfunctional epoxy compound (3) may contain at least the compound (monomer) represented by the formula (3) itself, and may be in the form of a mixture containing a multimer of the monomer, for example, a dimer to decamer such as a dimer, trimer, tetramer, etc. The multimer may be contained alone or in combination of two or more kinds.

[0144] In the present specification and claims, unless otherwise specified, the term "polymer" of a polyfunctional epoxy compound refers to a structure (skeleton) derived from a raw material [in the case of a compound represented by the above formula (3), R 4a ,R 4b The term "epoxy compound" refers to an epoxy compound having two or more structures derived from raw materials in the chemical structure, the structures being linked (connected) via a linking group derived from an epihalohydrin component, such as a 2-hydroxypropane-1,3-diyl group. Such a polymer may be mixed in the process of producing the compound (monomer) represented by the formula (3) as an unavoidable impurity or may be intentionally added to the monomer, if necessary, to a polymer prepared by a conventional method such as a one-stage method (taffy method or direct method) or a two-stage method (Advanced method, melting method or indirect method). If necessary, the curable composition may contain a polymer without containing a monomer of the polyfunctional epoxy compound (3) as a polyfunctional epoxy compound (epoxy resin component).

[0145] The epoxy equivalent of the polyfunctional epoxy compound (3) is, for example, 200 to 500 g / eq, preferably 220 to 450 g / eq, more preferably 230 to 400 g / eq, and particularly preferably 240 to 300 g / eq.

[0146] The ratio of the multimer to the total number of moles of the monomer and the multimer may be, for example, about 0 to 50 mol%, specifically about 0 to 20 mol%, preferably 0 to 10 mol%, and more preferably 0 to 5 mol%. The ratio may be, for example, 0.1 to 8 mol%, and preferably 0.2 to 3 mol%.

[0147] The polyfunctional epoxy compound (3) may be used alone or in combination of two or more kinds. The polyfunctional epoxy compound (3) may be a commercially available product or may be prepared by a conventional method.

[0148] The proportion of the polyfunctional epoxy compound (3) is, for example, 10 mass% or more, preferably 30 mass% or more, 50 mass% or more, 70 mass% or more, 90 mass% or more, and more preferably 100 mass% based on the entire glycidyl ether type epoxy resin having a 9,9-bisarylfluorene skeleton in the curable composition.

[0149] The proportion of the glycidyl ether type epoxy resin having a 9,9-bisarylfluorene skeleton, such as the polyfunctional epoxy compound (3), relative to the entire polyfunctional epoxy compound (epoxy resin component) in the curable composition is, for example, 10 mass% or more, preferably 30 mass% or more, 50 mass% or more, 70 mass% or more, 90 mass% or more, stepwise thereafter, and more preferably 100 mass%.

[0150] In the curable composition, the ratio of the monofunctional epoxy compound (1) may be, for example, about 0.1 to 50 parts by mass relative to 100 parts by mass of the total amount of the polyfunctional epoxy compound (epoxy resin component) and the monofunctional epoxy compound (1), and is preferably 1 to 40 parts by mass, 1.5 to 30 parts by mass, 2 to 25 parts by mass, 2.5 to 20 parts by mass, 3 to 15 parts by mass, 3.5 to 10 parts by mass, and 4 to 8 parts by mass in the following stepwise manner. When the lower limit of the ratio of the monofunctional epoxy compound (1) is within the above range, the viscosity of the curable composition can be more sufficiently reduced, and the storage stability of the curable composition can be easily improved, and the effects of the present disclosure tend to be more favorably exhibited. On the other hand, when the upper limit of the ratio of the monofunctional epoxy compound (1) is within the above range, it is easy to suppress a large decrease in Tg in the cured product, and it is easy to suppress a decrease in the storage stability of the curable composition.

[0151] Furthermore, the curable composition may or may not contain other components, such as a conventional reactive diluent other than the monofunctional epoxy compound (1) (the monofunctional or polyfunctional epoxy compounds exemplified in the above section [Reactive Diluent]), a curing agent, a curing accelerator, a photopolymerization initiator, a solvent, and an additive, as necessary.

[0152] (hardener, hardening accelerator, photopolymerization initiator) The curable composition may or may not contain at least one selected from a curing agent, a curing accelerator (curing assistant), and a photopolymerization initiator. Examples of the curing agent include an amine-based curing agent, a polyaminoamide-based curing agent, an acid anhydride-based curing agent, and a phenol resin-based curing agent.

[0153] The amine-based curing agent may be, in particular, a primary amine, and examples thereof include chain aliphatic amines, specifically, chain aliphatic polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine; cyclic aliphatic amines, specifically, monocyclic, bridged cyclic, or spirocyclic aliphatic polyamines such as menthene diamine, isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, norbornane diamine, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; aromatic aliphatic polyamines such as xylylene diamine; and aromatic amines such as metaphenylene diamine, diaminodiphenylmethane, and 4,4'-diaminodiphenylsulfone.

[0154] Examples of the polyaminoamide-based curing agent include condensates of polyethylene polyamines such as ethylene diamine, diethylene triamine, and triethylene hexamine, dimer acid, and, if necessary, fatty acid.

[0155] Examples of the acid anhydride curing agent include aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic anhydride; alicyclic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride and methylcyclohexene dicarboxylic anhydride; and aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and benzophenone tetracarboxylic anhydride.

[0156] Examples of the phenol resin-based hardener include novolak resins such as phenol novolak resins and cresol novolak resins, and resol-type phenol resins.

[0157] These curing agents may be used alone or in combination of two or more. Among these curing agents, phenolic resin-based curing agents are preferred, and novolak resins such as phenolic novolak resins are more preferred.

[0158] The ratio of the curing agent is, for example, 0.1 to 500 parts by mass, preferably 1 to 300 parts by mass, and more preferably 10 to 150 parts by mass, relative to 100 parts by mass of the total amount of the compound having an epoxy group in the curable composition. The ratio of active hydrogen in the curing agent is, for example, 0.1 to 4 moles, preferably 0.3 to 2 moles, 0.5 to 1.5 moles, and 0.8 to 1.2 moles in the following stepwise manner, relative to 1 mole of the epoxy group of the compound having an epoxy group in the curable composition.

[0159] Examples of curing accelerators (curing assistants) include amines such as tertiary amines, imidazoles and their derivatives; alkali metal or alkaline earth metal alkoxides; phosphines, specifically triarylphosphines such as triphenylphosphine; amide compounds such as dimer acid polyamide; Lewis acid complex compounds such as boron trifluoride-ethylamine complex; sulfur compounds such as polysulfides and mercaptan compounds (thiol compounds); boron compounds such as phenyldichloroborane; and condensable organometallic compounds such as organotitanium compounds and organoaluminum compounds. Regarding the amines, examples of tertiary amines include triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo[5.4.0]-7-undecene. Examples of the imidazoles include mono- or dialkylimidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and arylimidazoles such as 2-phenylimidazole. Examples of the derivatives include salts such as phenol salts, phenol novolac salts, carbonates, and formates. These curing accelerators may be used alone or in combination. Among these curing accelerators, phosphines are preferred, and triarylphosphines such as triphenylphosphine are more preferred.

[0160] The ratio of the curing accelerator (curing aid) is, for example, 0.01 to 30 parts by mass, preferably 0.05 to 20 parts by mass, 0.1 to 10 parts by mass, and 0.1 to 5 parts by mass in the following stepwise manner, relative to 100 parts by mass of the total amount of the compound having an epoxy group and the curing agent in the curable composition. The ratio of the curing accelerator is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass, relative to 100 parts by mass of the total amount of the compound having an epoxy group and the curing agent in the curable composition.

[0161] The curable composition may be, for example, a photocurable composition containing a photopolymerization initiator such as a cationic polymerization initiator, a photoacid generator, etc. Examples of the photopolymerization initiator include onium salts of Bronsted acids such as aromatic diazonium salts, aromatic sulfonium salts, and aromatic iodonium salts.

[0162] Examples of aromatic diazonium salts include benzenediazoniums such as benzenediazonium hexafluoroantimonate and benzenediazonium hexafluorophosphate.

[0163] Examples of aromatic sulfonium salts include triphenylsulfonium salts such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate, and 4,4'-bis(diphenylsulfonio)diphenylsulfide salts such as 4,4'-bis(diphenylsulfonio)diphenylsulfide bishexafluorophosphate.

[0164] Examples of aromatic iodonium salts include diphenyliodoniums such as diphenyliodonium tetrakis(pentafluorophenyl)borate and diphenyliodonium hexafluorophosphate, and di(4-nonylphenyl)iodoniums such as di(4-nonylphenyl)iodonium hexafluorophosphate.

[0165] These photopolymerization initiators can be used alone or in combination of two or more. The ratio of these photopolymerization initiators may be about 0.1 to 10 parts by mass, preferably about 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the epoxy resin components (compounds having an epoxy group) in the curing agent composition.

[0166] (solvent) The curable composition of the present disclosure may contain a solvent, although this is not necessarily required, since the viscosity can be reduced by the monofunctional epoxy compound (1). Examples of the solvent include hydrocarbons, specifically, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, alcohols such as methanol, ethanol, n-propanol, and benzyl alcohol, ethers, specifically, dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, aromatic ethers such as anisole, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether, ketones, specifically, acetone, methyl ethyl ether, and the like. Examples of suitable ketones include linear ketones such as methyl ketone (MEK) and methyl isobutyl ketone (MIBK), and cyclic ketones such as cyclohexanone; esters, acetate esters such as ethyl acetate, lactate esters such as methyl lactate, ethyl lactate, and butyl lactate, and lactones such as γ-butyrolactone; ether esters, specifically, alkylene glycol monoalkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA), and alkoxycarboxylic acid esters such as ethyl 3-ethoxypropionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and sulfoxides such as dimethyl sulfoxide.

[0167] These solvents may be used alone or in combination of two or more. The ratio of the solvent may be selected from the range of, for example, about 0 to 1000 parts by mass, specifically 10 to 500 parts by mass, relative to 100 parts by mass of the total amount of the compounds having an epoxy group in the curing agent composition, and may be added to an extent that the curable composition exhibits the desired fluidity (handling property).

[0168] (Additives) Examples of additives include conventional additives, such as colorants such as dyes and pigments, stabilizers, fillers, conductive agents, antistatic agents, flame retardants, flame retardant assistants, flexibilizers, plasticizers, surfactants, dispersants, compatibilizers, flow control agents, leveling agents, defoamers, surface modifiers, antibacterial agents, and preservatives. Examples of the stabilizers include heat stabilizers, antioxidants, and ultraviolet absorbers. Examples of the fillers include silica, talc, and mica. Examples of the flame retardants include phosphorus-based flame retardants, halogen-based flame retardants, and inorganic flame retardants. These additives may be used alone or in combination of two or more. The total proportion of these additives may be, for example, 10% by mass or less, preferably 0 to 3% by mass, based on the total solid content in the curable composition; for example, about 0.01 to 5% by mass, and preferably 0.1 to 1% by mass.

[0169] The curable composition may be prepared by mixing and dispersing the polyfunctional epoxy compound (epoxy resin component) and, if necessary, other components as described above, using a mixer or stirrer. Examples of the mixer or stirrer include a ball mill, a tumble mixer, a ribbon blender, a Henschel mixer, a mixing roll, a kneader, and a Banbury mixer. The temperature during mixing (kneading) or stirring may be, for example, about 50 to 250°C, and is preferably 100 to 200°C.

[0170] The curable composition of the present disclosure contains a monofunctional epoxy compound (1) which is a reactive diluent, and therefore can exhibit a lower viscosity than a polyfunctional epoxy compound (epoxy resin component). The viscosity of the curable composition can be reduced, for example, to 70 or less, preferably to 50 or less, 30 or less, 15 or less, 10 or less, or 5 or less, stepwise, when the viscosity of the curable composition not containing the monofunctional epoxy compound (1) [or the viscosity of the polyfunctional epoxy compound (epoxy resin component)] is taken as 100. The viscosity of a representative curable composition may be, depending on the type of polyfunctional epoxy compound (epoxy resin component), for example, 1 to 15,000 mPa·s, preferably 5 to 13,000 mPa·s, more preferably 20 to 10,000 mPa·s, even more preferably 50 to 5,000 mPa·s, and particularly 70 to 3,000 mPa·s, in terms of melt viscosity at a temperature of 150°C. 1a and Z 1b In the case where the polyfunctional epoxy compound (3) is a benzene ring, the viscosity may be preferably 10 to 145 mPa s, 50 to 140 mPa s, or 100 to 140 mPa s in the following stepwise manner: Z 1a and Z 1b In the case where the epoxy compound (3) contains a polyfunctional epoxy compound in which m is a condensed polycyclic arene ring such as a naphthalene ring, the viscosity is preferably 1000 to 12000 mPa s, 1500 to 5000 mPa s, and 2000 to 3000 mPa s in the following stepwise manner. In this specification and claims, the viscosity can be measured by a conventional method, and for example, the melt viscosity can be measured by the method described in the Examples below.

[0171] [Cured product and molded product] The cured product can be prepared by subjecting the curable composition to a curing reaction (curing treatment). The curing treatment can be carried out using a curing catalyst (the curing agent, curing accelerator, or photopolymerization initiator), heating, light irradiation (active energy ray irradiation), or the like, or a combination of these.

[0172] When the curing treatment is performed by heating, the heating temperature is, for example, 50 to 250°C, preferably 80 to 220°C, 100 to 200°C, 130 to 190°C, 150 to 185°C, and particularly 170 to 180°C in a stepwise manner. The curing treatment may be performed stepwise, for example, by heating at a relatively low temperature, specifically about 50 to 130°C, preferably 70 to 120°C, and then heating at a relatively high temperature, specifically about 140 to 350°C, preferably 150 to 300°C. Such a curing treatment may be performed during and / or after molding (or preforming) of the curable composition depending on the shape of the cured product. For example, if necessary, the curable composition is heated and melted, injected into a predetermined mold, and heated to cure, to obtain a molded product of a desired shape. The molding method and curing conditions are not particularly limited, and for example, when molding is performed using a predetermined mold, a molding method using heat and pressure or a low-temperature molding method called cold press may be used. The curable composition may be applied to the adhesion site and cured, or the curable composition may be coated on a substrate and cured, for example, by irradiation with light as described below.

[0173] When the curing treatment is carried out by light irradiation, the wavelength of the light may be appropriately selected depending on the type of photopolymerization initiator such as an acid generator, and may be ultraviolet light or visible light. The amount of light irradiation (exposure amount) can be selected depending on the thickness of the curable composition (coating film), and is, for example, 10 to 10,000 mJ / cm. 2 and preferably 100 to 5000 mJ / cm 2 , and more preferably 500 to 3000 mJ / cm 2 As the light source, for example, a high pressure mercury lamp, a deuterium lamp, a halogen lamp, a metal halide lamp, a xenon lamp, or a laser light such as an LED laser can be used. In order to promote the curing of the curable composition, not only the light irradiation but also the heat treatment may be performed.

[0174] The cured product of the present disclosure exhibits relatively high heat resistance even if it contains the monofunctional epoxy compound (1) which is a reactive diluent, since the decrease in heat resistance can be suppressed. The glass transition temperature Tg of the cured product can be maintained or improved within a range of, for example, -50°C to 10°C, preferably -20°C to 5°C, and more preferably -10°C to 0°C, based on the Tg of the curable composition not containing the monofunctional epoxy compound (1) [or the Tg of the cured product of the polyfunctional epoxy compound (epoxy resin component)]. The glass transition temperature Tg of a representative cured product may be, for example, 50 to 250°C, preferably 80 to 230°C, more preferably 100 to 200°C, and particularly 150 to 190°C, depending on the type of polyfunctional epoxy compound (epoxy resin component), and the like. 1a and Z 1b In the case where the polyfunctional epoxy compound (3) is a benzene ring, the reaction temperature may be preferably 80 to 190° C., 100 to 180° C., 130 to 175° C., 150 to 170° C., or 160 to 170° C. in the following stepwise order: Z 1a and Z 1b In the case where the epoxy compound (3) contains a polyfunctional epoxy compound (3) in which R is a condensed polycyclic arene ring such as a naphthalene ring, the temperature is preferably 150 to 210° C., 160 to 200° C., 165 to 195° C., and 170 to 190° C. in the following stepwise order. In the present specification and claims, the glass transition temperature Tg can be measured by the method described in the Examples below.

[0175] The molded article of the present disclosure is sufficient to contain at least the cured product, and may be formed from the cured product alone, or may be formed as a composite molded article in which the cured product is combined with another component.

[0176] The shape of the molded product (or cured product) is not particularly limited, and may be any one-dimensional shape (e.g., thread-like, rod-like, etc.), two-dimensional shape (e.g., sheet-like, film-like, plate-like, etc.), or three-dimensional shape [e.g., block-like, hollow (tubular or tubular), etc.]. Such molded products (cured products) exhibit high refractive index and high heat resistance, particularly when the curable composition contains a polyfunctional epoxy compound (3) or the like. EXAMPLES

[0177] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Details of the evaluation method are shown below.

[0178] [Evaluation method] ( 1 H-NMR) The sample was dissolved in a heavy solvent (CDCl3) containing tetramethylsilane as an internal standard, and the NMR spectrum was measured using a nuclear magnetic resonance spectrometer (BRUKER's "AVANCE III HD"). 1 H-NMR spectrum was measured.

[0179] (Melting Point) Using a differential scanning calorimeter (DSC) (TA Instruments, "Discovery DSC25"), measurements were performed under conditions of a nitrogen atmosphere, a measurement temperature of 30 to 250° C., and a temperature rise rate of 10° C. / min. The peak top temperature of the endothermic peak was read from the obtained DSC chart.

[0180] (epoxy equivalent) In accordance with JIS K 7236:2001, titration was carried out with a perchloric acid solution (acetic acid-based) using an automatic titrator (GT-100, manufactured by Mitsubishi Chemical Corporation).

[0181] (Refractive index nD) The refractive index was measured at a temperature of 25° C. and a wavelength of 589 nm (D-line) using a refractometer (RX-7000i, manufactured by Atago Co., Ltd.). The refractive index was calculated by dissolving the sample in N,N-dimethylformamide to prepare solutions with concentrations of 1.7 mass%, 6.1 mass%, and 9.8 mass%, and extrapolating the concentration to 100 mass% on a calibration curve (approximation line) prepared by measuring the refractive index of the obtained solutions and a concentration of 0 mass% (only N,N-dimethylformamide).

[0182] (Melt Viscosity) The melt viscosity was measured in accordance with JIS K 5600-2-3 using a melt viscometer ("CAP2000+" manufactured by BROOKFIELD Corp.) by selecting an optional rotor (cone 6) according to the viscosity to be measured, at a rotation speed of 900 rpm and a temperature of 150° C. In Comparative Example 3 and Examples 8 to 9 using BXFG, which will be described later, the temperature was changed to 200° C.

[0183] (Storage stability) The sample was stored at 25° C. and the condition was observed after 24 hours to confirm the storage stability according to the following evaluation criteria.

[0184] ○: No precipitation was observed △: Slight precipitation was observed ×: A large amount of precipitation was observed.

[0185] (glass transition temperature Tg) Using a differential scanning calorimeter (DSC) (TA Instruments, "Discovery DSC25"), measurements were performed under nitrogen gas flow at a measurement temperature of 30 to 250° C. and a temperature rise rate of 10° C. / min. The midpoint glass transition temperature (Tmg) was read from the resulting DSC chart and was taken as the glass transition temperature (Tg).

[0186] [Epoxy compound used in the curable composition] NEOG: 2-(2-glycidyloxyethoxy)naphthalene, synthesized according to Example 1 described below, solid at 25°C and 1 atm, epoxy equivalent 242 g / eq BPFG: 9,9-bis(4-glycidyloxyphenyl)fluorene, solid at 25°C and 1 atm, epoxy equivalent 242g / eq BNFG: 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene, solid at 25°C and 1 atm, epoxy equivalent 295g / eq BXFG: 9,9-bis(4-glycidyloxy-3,5-dimethylphenyl)fluorene, solid at 25°C and 1 atm, epoxy equivalent 265g / eq BOPPEFG: 9,9-bis[4-(2-(glycidyloxy)ethoxy)-3-phenylphenyl]fluorene, solid at 25°C and 1 atm, epoxy equivalent 392g / eq

[0187] [Example 1] Synthesis of NEOG

[0188] [ka]

[0189] 56.5g (0.30 mol) of β-naphthoxyethanol was charged with 138.8g (1.50 mol) of chloromethyloxirane and 58.6g (0.75 mol) of dimethyl sulfoxide (DMSO), and 13.2g (0.33 mol) of granular sodium hydroxide was added in portions, reacted at 75°C for 3 hours, and cooled to room temperature (about 25°C). The reaction solution was then concentrated under reduced pressure, and chloromethyloxirane was removed by distillation, and then dissolved in 100.0g of methyl isobutyl ketone (MIBK), and 8.0g of 30% by mass aqueous sodium hydroxide solution was added to carry out a ring-closing reaction at 70°C for 1 hour. After that, the operation of washing with 125.4g of distilled water was repeated four times, and after a portion of MIBK was removed by vacuum concentration again, reprecipitation was carried out using 282.3g of methanol, and 58.6g of white powder NEOG was obtained by filtration.

[0190] The melting point of the obtained NEOG was 80°C, the epoxy equivalent was 242g / eq, and the refractive index nD at 25°C was 1.565. 1 The H-NMR spectrum is shown in Figure 1 and below.

[0191] 1 H-NMR(300MHz CDCl3)δ7.80-7.71(m,3H),7.46-7.41(m,1H),7.37-7.31(m,1H),7.21-7.15(m,2H),4.27(t,J=4.7Hz, 2H),4.03-3.90(m,3H),3.56-3.50(m,1H),3.25-3.20(m,1H),2.83(t,J=4.1Hz,1H),2.67-2.65(m,1H).

[0192] [Comparative Example 1 and Examples 2 to 5] Preparation of curable composition and cured product BPFG and NEOG obtained in Example 1 were weighed and mixed in the mass ratio shown in Table 1, and then heated and stirred at 150°C for 10 minutes to make them homogenous, thereby preparing a curable composition. The melt viscosity and storage stability of the obtained curable composition were evaluated.

[0193] In addition, a phenol novolac resin (Gun-ei Chemical Industry Co., Ltd. "PSM-4261", hydroxyl equivalent 105 g / eq) as a curing agent and triphenylphosphine (TPP, Kanto Chemical Co., Ltd.) as a curing aid were added to the obtained curable composition. The amount of the phenol novolac resin added was adjusted so that the total amount of epoxy groups in the curable composition and the hydroxyl groups of the phenol novolac resin as a curing agent were in a molar ratio of 1:1, and the amount of TPP added was adjusted to 1 part by mass per 100 parts by mass of the total amount of BPFG, NEOG and the phenol novolac resin. The curable composition to which the curing agent and curing aid were added was cured in a thermostatic bath at 175°C for 5 hours to prepare a cured product, and the glass transition temperature (Tg) of the obtained cured product was measured.

[0194] The evaluation results of the curable compositions and cured products obtained in Examples 2 to 5 and Comparative Example 1 are shown in the following table.

[0195] [Table 1]

[0196] As is clear from Table 1, in the examples in which NEOG was added, the melt viscosity could be reduced to half or less of that in Comparative Example 1, and the handling properties were excellent. Although NEOG itself is a solid that does not exhibit fluidity, it was found that the handling properties of the curable composition can be effectively improved. Note that, although precipitation was observed in the curable composition in Example 5, and the storage stability was slightly decreased, all of the curable compositions in Examples 2 to 4 were transparent and had excellent storage stability.

[0197] Moreover, Examples 2 and 3 (particularly Example 2) exhibited an excellent balance between the handleability and storage stability of the curable composition and the heat resistance of the cured product.

[0198] [Comparative Example 2 and Examples 6-7] Preparation of curable composition and cured product Curable compositions and cured products were prepared in the same manner as in Comparative Example 1 and Examples 2 to 5, except that BNFG was used instead of BPFG and the mass ratio was as shown in Table 2. The melt viscosity and storage stability of the obtained curable compositions and the glass transition temperature (Tg) of the obtained cured products were measured.

[0199] The evaluation results of the curable compositions and cured products obtained in Examples 6 to 7 and Comparative Example 2 are shown in the following table.

[0200] [Table 2]

[0201] BNFG corresponds to a compound in which the benzene rings bonded to the 9,9-positions of the fluorene skeleton in BPFG are replaced with naphthalene rings. As is clear from Table 2, even for the solid BNFG (Comparative Example 2), in the Example in which NEOG was added, the melt viscosity was significantly reduced and the handling properties were excellent.

[0202] In addition, when comparing Examples 2 and 3 of BPFG with Examples 6 and 7 of BNFG, the melt viscosity of Example 3 (10 parts by mass of NEOG) was reduced to 60% of that of Example 2 (5 parts by mass of NEOG), whereas the melt viscosity of Example 7 (10 parts by mass of NEOG) was reduced to approximately 22.8% of that of Example 6 (5 parts by mass of NEOG). Therefore, it was found that when a curable composition is formed in combination with BNFG, the melt viscosity can be effectively reduced even if the proportion of NEOG is the same.

[0203] Moreover, all of the curable compositions of Examples 6 and 7 were transparent and had excellent storage stability.

[0204] Among Examples 6 and 7, Example 6 in particular exhibited an excellent balance between the handleability and storage stability of the curable composition, and the heat resistance of the cured product.

[0205] [Comparative Example 3 and Examples 8-9] Preparation of curable composition and cured product Curable compositions and cured products were prepared in the same manner as in Comparative Example 1 and Examples 2 to 5, except that BXFG was used instead of BPFG in the mass ratios shown in Table 3. The melt viscosity and storage stability of the obtained curable compositions, and the glass transition temperature (Tg) of the obtained cured products were measured.

[0206] The evaluation results of the curable compositions and cured products obtained in Examples 8 to 9 and Comparative Example 3 are shown in the following table.

[0207] [Table 3]

[0208] BXFG corresponds to a compound in which two methyl groups are bonded to each of the benzene rings bonded to the 9,9-positions of the fluorene skeleton in BPFG. As is clear from Table 3, in the example in which NEOG was added to BXFG (Comparative Example 3), the melt viscosity was significantly reduced and the handling properties were excellent.

[0209] In addition, when comparing Examples 8-9 (BXFG) with Examples 3-4 (BPFG) in which the blending ratio of NEOG is the same, by blending 10 parts by mass of NEOG, the melt viscosity of Example 8 (BXFG) was reduced to about 65.6% of Comparative Example 3 (BXFG alone), while the melt viscosity of Example 3 (BPFG) was reduced to about 29.5% of Comparative Example 1 (BPFG alone); by blending 20 parts by mass of NEOG, the melt viscosity of Example 9 (BXFG) was reduced to about 18.8% of Comparative Example 3 (BXFG alone), while the melt viscosity of Example 4 (BPFG) was reduced to about 10.5% of Comparative Example 1 (BPFG alone). Therefore, it was found that by combining BPFG rather than BXFG to form a curable composition, the melt viscosity can be effectively reduced even if the ratio of NEOG is the same.

[0210] In addition, in Comparative Example 3 (BXFG alone), precipitation was observed during storage of the sample, whereas in Examples 8 to 9, no precipitation was observed and the samples were transparent and had excellent storage stability. That is, in Examples 8 to 9, the addition of NEOG enabled more effective improvement of storage stability.

[0211] Among Examples 8 to 9, Example 8 in particular exhibited an excellent balance between the handleability and storage stability of the curable composition, and the heat resistance of the cured product.

[0212] [Comparative Example 4 and Examples 10-11] Preparation of curable composition and cured product Curable compositions and cured products were prepared in the same manner as in Comparative Example 1 and Examples 2 to 5, except that BOPPEFG was used instead of BPFG and the mass ratios were as shown in Table 4. The melt viscosity and storage stability of the obtained curable compositions, and the glass transition temperature (Tg) of the obtained cured products were measured.

[0213] The evaluation results of the curable compositions and cured products obtained in Examples 10 to 11 and Comparative Example 4 are shown in the following table.

[0214] [Table 4]

[0215] BOPPEFG corresponds to a compound in which the benzene rings bonded to the 9,9-positions of the fluorene skeleton in BPFG are changed to biphenyl rings, and this biphenyl ring and glycidyloxy group are linked by ethyleneoxy groups. As is clear from Table 4, in the example in which NEOG was added to BOPPEFG (Comparative Example 4), the melt viscosity was significantly reduced and the handling properties were excellent.

[0216] In addition, when comparing Examples 10-11 (BOPPEFG) with Examples 3-4 (BPFG) in which the blending ratio of NEOG is the same, by blending 10 parts by mass of NEOG, the melt viscosity of Example 10 (BOPPEFG) was reduced to about 28.4% of Comparative Example 4 (BOPPEFG alone), while the melt viscosity of Example 3 (BPFG) was reduced to about 29.5% of Comparative Example 1 (BPFG alone); by blending 20 parts by mass of NEOG, the melt viscosity of Example 11 (BOPPEFG) was reduced to about 8.3% of Comparative Example 4 (BOPPEFG alone), while the melt viscosity of Example 4 (BPFG) was reduced to about 10.5% of Comparative Example 1 (BPFG alone). Therefore, it was found that BOPPEFG and BPFG can obtain approximately the same viscosity reduction effect when combined with NEOG.

[0217] Moreover, all of the curable compositions of Examples 10 and 11 were transparent and had excellent storage stability.

[0218] Among Examples 10 and 11, Example 10 in particular exhibited an excellent balance between the handleability and storage stability of the curable composition, and the heat resistance of the cured product. [Industrial Applicability]

[0219] The monofunctional epoxy compound of the present disclosure can reduce the viscosity of a polyfunctional epoxy compound (or an epoxy resin), and can therefore be effectively used as a reactive diluent (viscosity reducer).

[0220] Furthermore, the curable composition or cured product thereof according to the present disclosure has excellent properties such as handleability and storage stability in the curable composition, and has excellent heat resistance in the cured product, and is therefore useful as a variety of materials, including, for example, insulating materials between layers of electronic components, solder resists for printed circuit boards, resist materials such as coverlays, color filters, inks such as printing inks, sealants such as sealants for electronic components or semiconductors, paints, coating agents, adhesives, pressure-sensitive agents, underfills, antistatic agents, fillers, conductive members or materials, laminating materials, heat-sensitive materials such as materials for heat-sensitive paper, carbon materials, insulating materials, foams, pressure-sensitive materials, and optical members or optical materials (transparent materials).

Claims

1. The following formula (1) 【Chemistry 1】 (wherein Ar represents a polycyclic arene ring; A １ represents an alkylene group; n1 represents an integer of 1 to 3; R １ represents a hydrogen atom or an alkyl group, R ２ represents a substituent, and m2 represents an integer of 0 or more. A compound represented by the formula:

2. In the formula (1), Ar is a polycyclic C １０－１４ Represents an arene ring; A １ is C ２－６ represents an alkylene group, n1 represents an integer of 1 to 2, R １ is a hydrogen atom or C １－６ represents an alkyl group, R ２ The compound according to claim 1, wherein represents a hydrocarbon group or a halogen atom.

3. In the formula (1), Ar represents a naphthalene ring or a biphenyl ring. A １ is C ２－４ represents an alkylene group, n1 represents 1, R １ is a hydrogen atom or C １－４ represents an alkyl group, R ２ 3. The compound according to claim 1 or 2, wherein m2 represents an integer of 0 to 7.

4. 3. The compound according to claim 1 or 2, which is a solid at a temperature of 25° C. and a pressure of 1 atmosphere.

5. The following formula (2) 【Chemistry 2】 (Wherein, Ar, A １ , n1, R ２ and m2 are the same as in formula (1).

3. A method for producing a compound represented by formula (1) according to claim 1 or 2, comprising reacting a compound represented by the following formula with an epihalohydrin component.

6. A reactive diluent comprising the compound represented by formula (1) according to claim 1 or 2.

7. A curable composition comprising a polyfunctional epoxy compound and a compound represented by formula (1) according to claim 1 or 2.

8. The polyfunctional epoxy compound is at least one represented by the following formula (3): 【Chemistry 3】 (In the formula, R ３ represents a substituent, m3 represents an integer of 0 to 8, Z １ａ and Z １ｂ each independently represents an arene ring, A ２ａ and A ２ｂ each independently represents an alkylene group; n2a and n2b each independently represent an integer of 0 or more; R ４ａ and R ４ｂ each independently represents a hydrogen atom or an alkyl group, R ５ａ and R ５ｂ each independently represents a substituent, and m5a and m5b each independently represent an integer of 0 or more. The curable composition according to claim 7, comprising a compound represented by the formula:

9. In the formula (3), R ３ is a halogen atom, a hydrocarbon group, a group [—OR ｈ ] (wherein, R ｈ represents a hydrocarbon group) or a cyano group; m3 represents an integer of 0 to 4; Z １ａ and Z １ｂ is independent and C ６－１４ Represents an arene ring; A ２ａ and A ２ｂ is independent and C ２－６ An alkylene group is represented, and n2a and n2b each independently represent an integer of 0 to 10. R ４ａ and R ４ｂ are independently a hydrogen atom or C １－６ represents an alkyl group, R ５ａ and R ５ｂ The curable composition according to claim 8, wherein m5a and m5b independently represent an integer of 0 to 4.

10. The curable composition according to claim 8, wherein, in the formula (3), m5a and m5b each represent 0.

11. In the formula (3), R ５ａ and R ５ｂ The curable composition according to claim 8, wherein m5a and m5b independently represent an alkyl group; and m5a and m5b independently represent an integer of 1 to 4.

12. The ratio of the compound represented by the formula (1) is 0.1 to 50 parts by mass per 100 parts by mass of the total amount of the polyfunctional epoxy compound and the compound represented by the formula (1). The curable composition according to claim 7.

13. A cured product of the curable composition according to claim 7.

14. A molded article comprising the cured product according to claim 13.

15. A method for reducing viscosity, comprising mixing a compound represented by formula (1) according to claim 1 or 2 with a polyfunctional epoxy compound.

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