JP5719631B2 - Compound, derivative, composition, cured product, and method for producing compound and derivative - Google Patents

Description

  The present invention relates to a novel compound, a derivative thereof, a composition containing these, a cured product, and a method for producing the above compound and derivative.

  Conventionally, anthracene has been used in various applications such as wood insecticides, storage stabilizers, paints, production raw materials for epoxy resins and carbon black, and synthetic raw materials for anthraquinone dyes. Since this anthracene is a condensed polycyclic aromatic compound in which three benzene rings are condensed, it has useful characteristics such as structural hardness, high carbon density, high melting point, and high refractive index. Various application developments of anthracene have been attempted in order to further utilize such characteristics as added value. Various anthracene derivatives have been developed as high value-added materials in various technical fields.

  For example, by introducing a (meth) acrylate group at the 9th and 10th positions of anthracene to form a polymerizable monomer, a photocuring polymer (see JP 2007-99637 A) that acts as a sensitizer for photo radical polymerization, In addition, a polymer having ultraviolet absorbing ability and flame retardancy (see JP 2008-1637 A) can be obtained.

  Also in the field of photoresists, an anthracene derivative is used, and a radiation-sensitive resin composition having advantages such as high sensitivity, high resolution, high etching resistance, and low sublimation (see JP-A-2005-346024), Further, an antireflection film (see JP-A-7-82221) for preventing intermixing with a resist resin can be obtained.

  Furthermore, taking advantage of the feature that anthracene has a high refractive index, in addition to its use as an optical material, a hologram recording that mixes high refractive index material, low refractive index material, sensitizing dye, etc. and records interference fringes by exposure It is also used as a material (see JP-A-6-295151).

  However, since anthracene and this derivative are condensed polycyclic aromatic compounds, they have fluorescent properties. Therefore, anthracene derivatives also have inconveniences such as limited application in the field of optical materials.

  On the other hand, when attention is focused on bisphenol compounds having two or more aromatic rings, for example, bisphenol fluorene uses a hydroxyl group bonded to an aromatic ring in the molecule and / or the reactivity of the aromatic ring itself to produce various new types. It is used for the production of polymers such as epoxy resins, polycarbonate resins, acrylate resins, aryl oligomers and the like (for example, see JP-A-9-328534). These resins derived from bisphenol compounds are applied to various uses such as optical materials and electronic materials. As described above, bisphenol compounds are attracting particular attention because they have various reactions and have versatility that enables a wide variety of applications.

  In view of the above circumstances, the development of a compound having a novel bisphenol structure that enables high-performance materials and imparting new properties is awaited.

JP 2007-99637 A JP 2008-1637 A JP 2005-346024 A JP-A-7-82221 JP-A-6-295151 JP-A-9-328534

  The present invention has been made based on the above-mentioned circumstances, and has a novel compound that does not have fluorescence characteristics and has high melting point, high photorefractive property, and reaction diversity due to bisphenol structure, and its production It aims to provide a method. Another object of the present invention is to provide a derivative of this compound, a composition containing these, and a cured product obtained from this composition.

（式（１）中、Ｘは、（ｎ_１＋１）価の芳香族基であり、この芳香族基が置換基を有していてもよい。Ｙは、（ｎ_２＋１）価の芳香族基であり、この芳香族基が置換基を有していてもよい。ｎ_１及びｎ_２は、それぞれ独立して、１〜３の整数である。） The invention made to solve the above problems is
It is a compound represented by the following formula (1).

(In the formula (1), X is an (n ₁ +1) -valent aromatic group, and this aromatic group may have a substituent. Y is an (n ₂ +1) -valent aromatic group. (This aromatic group may have a substituent. N ₁ and n ₂ are each independently an integer of 1 to 3).

  Since the compound has a hydroanthracene skeleton similar to the anthracene skeleton, the compound has performance equivalent to or higher than that of the anthracene compound in, for example, high melting point and high photorefractive property. On the other hand, unlike anthracene, the compound does not have fluorescence characteristics because the central benzene ring is hydrogenated. Since the compound further has a reactive hydroxyl group and an aromatic ring, the compound has various reactivity provided by the bisphenol compound. Therefore, the compound has high versatility such that it can be used for various resin raw materials.

  X and Y may have at least one alkyl group as a substituent. When X and Y each have at least one alkyl group as a substituent, the compound can be efficiently produced from the corresponding anthracene derivative and is excellent in productivity. Further, the melting point and the optical refractive index can be finely controlled by adjusting the type and number of alkyl groups.

  The derivative of the present invention is a derivative of the above compound. The derivative is imparted with more specific properties by introducing various functional groups, and can be used as a resin raw material for synthesizing various resins.

  The composition of the present invention is a composition containing the above compound or derivative. The composition can be used as a raw material composition for various resins having high versatility and added value.

  The cured product of the present invention is a cured product obtained by curing the above composition. The cured product can have a high melting point, a high photorefractive property, and the like, and can be used as a resin that can be applied to various fields.

（式（１）中、Ｘは、（ｎ_１＋１）価の芳香族基であり、この芳香族基が置換基を有していてもよい。Ｙは、（ｎ_２＋１）価の芳香族基であり、この芳香族基が置換基を有していてもよい。ｎ_１及びｎ_２は、それぞれ独立して、１〜３の整数である。） The method for producing the compound of the present invention comprises:
A method for producing a compound represented by the following formula (1), which comprises a step of reacting a phenol with an anthracene-9-carbaldehyde in the presence of a catalyst containing a non-reactive oxygen-containing organic solvent and an oxo acid.

(In the formula (1), X is an (n ₁ +1) -valent aromatic group, and this aromatic group may have a substituent. Y is an (n ₂ +1) -valent aromatic group. (This aromatic group may have a substituent. N ₁ and n ₂ are each independently an integer of 1 to 3).

  According to this production method, the occurrence of side reactions can be suppressed, and the desired compound can be produced efficiently by selecting the type of phenols.

  The phenols may be phenolic compounds having at least one alkyl group. According to the manufacturing method, generation of side reactions can be further suppressed, and productivity can be increased.

（式（１）中、Ｘは、（ｎ_１＋１）価の芳香族基であり、この芳香族基が置換基を有していてもよい。Ｙは、（ｎ_２＋１）価の芳香族基であり、この芳香族基が置換基を有していてもよい。ｎ_１及びｎ_２は、それぞれ独立して、１〜３の整数である。）

（式（２）中、Ｘは、（ｎ_１＋１）価の芳香族基であり、この芳香族基が置換基を有していてもよい。Ｙは、（ｎ_２＋１）価の芳香族基であり、この芳香族基が置換基を有していてもよい。ｎ_１及びｎ_２は、それぞれ独立して、１〜３の整数である。） The method for producing the derivative of the present invention comprises:
It is a manufacturing method of the derivative represented by following formula (2) which has the process of making the compound represented by following formula (1) react under an acidic catalyst.

(In the formula (1), X is an (n ₁ +1) -valent aromatic group, and this aromatic group may have a substituent. Y is an (n ₂ +1) -valent aromatic group. (This aromatic group may have a substituent. N ₁ and n ₂ are each independently an integer of 1 to 3).

(In the formula (2), X is an (n ₁ +1) -valent aromatic group, and this aromatic group may have a substituent. Y is an (n ₂ +1) -valent aromatic group. (This aromatic group may have a substituent. N ₁ and n ₂ are each independently an integer of 1 to 3).

  According to the method for producing the derivative, the hydroxyanthracene skeleton in the compound can be converted to an anthracene skeleton in the above-mentioned one step. Therefore, according to the production method, a highly useful derivative having further fluorescence characteristics and the like can be efficiently obtained from the compound of the present invention.

  As described above, the compound of the present invention does not have fluorescence characteristics, and has a high melting point, high photorefractive properties, and reaction diversity resulting from a bisphenol structure. In addition, various derivatives having various characteristics can be obtained from the compound of the present invention. The composition and cured product of the present invention containing these are extremely effective for enhancing the functionality of the material and imparting new characteristics, and are a resin material having high versatility and added value, such as a phenol resin and an epoxy resin material. Polycarbonate resin raw material, acrylic resin raw material, laminated material, coating material such as paint, optical material such as lens and optical sheet, recording material such as hologram recording material, organic photoreceptor, photoresist material, antireflection film, semiconductor encapsulation It can be applied in various technical fields as high-functional materials such as materials, magnetic materials such as molecular magnetic memory, organic solar cells, and organic EL elements. Furthermore, according to the production method of the present invention, the desired compound and derivatives thereof can be produced efficiently.

2 is an HPLC chart after completion of the reaction in Example 1. 1 is a ¹ H-NMR chart of a target product of Example 1. 3 is a ¹³ C-NMR chart of the target product of Example 1. FIG. 2 is an HPLC chart after completion of the reaction of Example 2. 2 is a ¹ H-NMR chart of a target product of Example 2. 3 is a ¹³ C-NMR chart of the target product of Example 2. FIG. 2 is an HPLC chart after completion of the reaction of Comparative Example 1. 2 is a ¹ H-NMR chart of a target product of Comparative Example 1. 6 is a ¹³ C-NMR chart of a target product of Comparative Example 1. 4 is an HPLC chart after completion of the reaction of Comparative Example 2.

  Hereinafter, embodiments of the present invention will be described in detail in the order of a compound and a production method thereof, a derivative obtained using the same, a production method thereof, a composition containing them, and a cured product thereof.

<Compound>
The compound of the present invention is represented by the above formula (1).
Since the compound has a hydroanthracene skeleton similar to the anthracene skeleton, the compound has performance equivalent to or higher than that of the anthracene compound in, for example, high melting point and high photorefractive property. As melting | fusing point of the said compound, it is 180 degreeC or more, for example, and can also be 200 degreeC or more. The refractive index of the compound is, for example, 1.650 or more, and may be 1.660 or more. This melting point and photorefractive index can be adjusted by a substituent or the like described in detail later. On the other hand, unlike anthracene, the compound does not have fluorescence characteristics because the central benzene ring is hydrogenated.

  Since the compound further has a reactive hydroxyl group and an aromatic ring, the compound has various reactivity provided by the bisphenol compound. For example, the compound can be allylated, glycidylated, (meth) acrylated, methylolated, benzoxazine and the like.

  Therefore, the compound has high versatility such that it can be used for various resin raw materials. In particular, the compound has high symmetry because the aromatic ring is arranged at the 9th and 10th positions of the hydroanthracene ring, and it is bridged by two or more hydroxyl groups in the polymer main chain. It is possible to introduce a hydroanthracene skeleton. Therefore, according to the compound, it is possible to obtain a polymer having excellent mechanical properties utilizing the rigidity derived from the hydroanthracene skeleton, and aromatic rings at the 9th and 10th positions which are the short axes of the hydroanthracene skeleton. Due to the arrangement, when introduced into the polymer skeleton, unique functions such as the polymer having an extremely high carbon density are exhibited.

In the above formula (1), the aromatic groups represented by X and Y are each an aromatic hydrocarbon such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, etc., each optionally having a substituent. And groups obtained by removing (n ₁ +1) or (n ₂ +1) hydrogen atoms on the aromatic ring. Among the aromatic hydrocarbons, benzene and naphthalene are preferable, and benzene is more preferable, from the viewpoints of the ease of production of the compound and the controllability of light absorption and fluorescence.

Examples of the substituent that the aromatic group represented by X and Y may have include an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an amino group, a mercapto group, and a hydroxyl group. One or more of these substituents may be present for each of X and Y. The valences of X and Y do not depend on the presence or absence of these substituents and the number of substituents, X is an (n ₁ +1) valence, and Y is an (n ₂ +1) valence. That is, n ₁ and n ₂ are the number of hydroxyl groups directly bonded to the aromatic rings (parts other than the substituent) in X and Y.

  The alkyl group may be a linear, branched, monocyclic or condensed polycyclic alkyl group, or a linear, branched, monocyclic or condensed polycyclic interrupted by one or more —O—. An alkyl group etc. are mentioned.

  Specific examples of linear, branched, monocyclic or condensed polycyclic alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl groups. , Dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group , Cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

Specific examples of the linear or branched alkyl group interrupted by one or more —O— include —CH ₂ —O—CH ₃ , —CH ₂ —CH ₂ —O—CH ₂ —. CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _m1 —CH ₃ (where m1 is an integer of 1 to 8), − (CH ₂ —CH ₂ —CH ₂ —O) _p1 —CH ₃ (where p1 is an integer of 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —CH ₃ , —CH ₂ -CH- _{(OCH 3) 2,} and the like. Examples of the monocyclic or condensed polycyclic alkyl group interrupted by one or more —O— include a tetrahydrofuranyl group, a tetrahydropyranyl group, and a 7-oxanorbornyl group.

  Examples of the alkoxy group include a linear, branched, monocyclic or condensed polycyclic alkoxy group, or a linear, branched, monocyclic or condensed polycyclic interrupted by one or more —O—. An alkoxy group etc. are mentioned.

  Specific examples of linear, branched, monocyclic or condensed polycyclic alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, Nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert-pentyloxy group, tert- Octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decylcyclohexyloxy group, etc. Door can be.

Specific examples of the linear or branched alkoxy group interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , —O—CH ₂ —CH ₂ —O. —CH ₂ —CH ₃ , —O—CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —O— (CH ₂ —CH ₂ —O) _{m 2} —CH ₃ (where m 2 is 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _{p 2} —CH ₃ (where p 2 is an integer of 1 to 5), —O—CH ₂ —CH (CH _{3 ) -O-CH 2 -CH 3,} -O-CH 2 -CH- (OCH 3) may be mentioned _2. Examples of the monocyclic or condensed polycyclic alkoxy group interrupted by one or more —O— include a tetrahydrofuranyloxy group, a tetrahydropyranyloxy group, and a 7-oxanorbornyloxy group.

  Examples of the aryl group include groups in which one hydrogen atom has been removed from an aromatic ring which may have a substituent. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, 1- Anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2- Fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group, p-dodecylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl 3,4,5-trimethoxyphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl Group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like.

  Examples of the alkenyl group include linear, branched, monocyclic or condensed polycyclic alkenyl groups, which may have a plurality of carbon-carbon double bonds in the structure. Specific examples As, vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group Groups and the like.

  Of these substituents of X and Y, an alkyl group is preferable. In X and Y, according to the compound having an aromatic group having an alkyl group as a substituent, the refractive index, the melting point, and the like can be adjusted without reducing the reactivity of the compound. The alkyl group as the substituent is preferably low molecular weight from the viewpoint of conformational stability. Specifically, an alkyl group having 5 or less carbon atoms is preferred, and a methyl group or an ethyl group is preferred. More preferred is a methyl group. The number of alkyl groups is preferably 1 or more, more preferably 1 to 3, and even more preferably 1 or 2 in each of X and Y. The number and type of the alkyl group may be the same or different in X and Y.

n ₁ and n ₂ are each independently an integer of 1 to 3. The n ₁ and n ₂ are the number of hydroxyl groups directly bonded to the X and Y aromatic rings. n ₁ and n ₂ are both preferably 1 from the viewpoints of easiness of synthesis, reaction controllability of hydroxyl groups, and the like.

Furthermore, n ₁ and n ₂ are 1, and the aromatic group represented by X and Y is each optionally substituted with two hydrogen atoms on the benzene ring from benzene which may have a substituent. In the case of the excluded group, the hydroxyl group is preferably located in the para position with respect to the bonding position on the hydroanthracene side. In addition, when the benzene has an alkyl group as a substituent, the alkyl group is preferably located in the ortho position with respect to the hydroxyl group. When the compound has such a structure, synthesis is easy and productivity is excellent. In such a case, the symmetry of the molecule is high, and it is possible to increase the melting point and increase the carbon density.

  Since the compound of the present invention has the structure described above, it can be used directly or as a reaction intermediate, and as various synthetic resin raw materials such as an epoxy resin raw material, a polycarbonate resin raw material, and an acrylic resin raw material. Moreover, besides a synthetic resin raw material, it can be used as, for example, an agrochemical intermediate or a pharmaceutical intermediate.

<Method for producing compound>
The compounds of the present invention are, for example,
It is produced by a method comprising a step of reacting phenols with anthracene-9-carbaldehyde in the presence of a catalyst containing a non-reactive oxygen-containing organic solvent and an oxo acid. Although the reaction mechanism of this reaction is not clear, non-reactive oxygen-containing organic solvent and oxo acid can localize electrons on specific carbon of anthracene-9-carbaldehyde and cause reaction with phenols. Etc. are considered. When an acid other than oxo acid (for example, hydrochloric acid) is used as a catalyst, the anthracene skeleton of anthracene-9-carbaldehyde is not hydrogenated.

  The above phenols refer to compounds having a hydroxy group on the aromatic ring, such as phenolic compounds and naphtholic compounds.

  The phenolic compound refers to phenol in which hydrogen on the aromatic ring is substituted with other substituents. Examples of the substituent include an alkyl group and a hydroxy group. Examples of the alkyl group include those exemplified in the description of the compound, an alkyl group having 5 or less carbon atoms is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.

  Examples of phenolic compounds include phenol, cresol (o-cresol, m-cresol, p-cresol), xylenol (2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol), 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 4-ethylphenol, 2-isopropylphenol, 4-isopropylphenol 2-tert-butylphenol, 4-tert-butylphenol, 2-cyclohexylphenol, 4-cyclohexylphenol, 2-phenylphenol, 4-phenylphenol, thymol, 2-tert-butyl-5-methylphenol, 2-cyclohexyl 5-methylphenol, resorcinol, 2-methyl resorcinol, catechol, 4-methyl catechol, hydroquinone, pyrogallol.

  A naphthol compound refers to naphthol in which naphthol and hydrogen on an aromatic ring are substituted with other substituents. Examples of the substituent include an alkyl group and a hydroxy group.

  Examples of naphthol compounds include 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2 , 7-dihydroxynaphthalene and the like.

  Among these phenols, phenols having at least one alkyl group are preferable, phenolic compounds having at least one alkyl group are more preferable, and cresol and xylenol are more preferable. By using these compounds as phenols, the occurrence of side reactions can be further suppressed, and productivity can be increased.

  These phenols are not particularly limited, and are appropriately selected according to the desired structure of the compound. Moreover, you may use these individually or in combination of 2 or more types.

  Moreover, as a minimum of the compounding quantity of this phenol, 2 mol is preferable with respect to 1 mol of anthracene-9-carbaldehyde, and 4 mol is more preferable. The upper limit of the amount of the phenols is preferably 100 mol, more preferably 50 mol, and particularly preferably 20 mol with respect to 1 mol of anthracene-9-carbaldehyde. If the blending amount of phenols is less than the above lower limit, a large amount of energy is required for purification because a higher-order condensate of the raw material is formed. Conversely, if the upper limit is exceeded, enormous energy is required to remove unreacted phenols. Both are uneconomical.

  In this production method, a non-reactive oxygen-containing organic solvent having one or more oxygen atoms in the molecule is used as the reaction solvent. The term “non-reactive” means that it does not react with phenols, anthracene-9-carbaldehyde and synthesized anthracene derivatives in this reaction system. As the non-reactive oxygen-containing organic solvent, for example, alcohols, polyhydric alcohol ethers, cyclic ethers, polyhydric alcohol esters, ketones, esters, sulfoxides, carboxylic acids and the like can be used.

  Examples of alcohols include monohydric alcohols such as methanol, ethanol, propanol, and butanol, butanediol, pentanediol, hexanediol, ethylene glycol, propylene glycol, trimethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, Examples thereof include dihydric alcohols such as propylene glycol and polyethylene glycol, and trihydric alcohols such as glycerin.

  Examples of the polyhydric alcohol ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol mono Examples include glycol ethers such as phenyl ether.

  Examples of cyclic ethers include 1,3-dioxane, 1,4-dioxane, tetrahydrofuran and the like. Examples of the polyhydric alcohol ester include glycol esters such as ethylene glycol acetate. Examples of ketones include acetone, methyl ethyl ketone, and methyl ethyl ketone. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate and the like. Examples of the sulfoxides include dimethyl sulfoxide and diethyl sulfoxide. Examples of carboxylic acids include acetic acid and acetic anhydride.

  Among these, alcohols and polyhydric alcohol ethers are preferable, methanol, ethylene glycol, and ethylene glycol monomethyl ether are more preferable, and methanol is particularly preferable.

  The non-reactive oxygen-containing organic solvent is not limited to the above examples, and each may be used alone or in admixture of two or more. The lower limit of the amount of the non-reactive oxygen-containing organic solvent is preferably 1 part by mass, more preferably 5 parts by mass, and particularly preferably 10 parts by mass with respect to 100 parts by mass of the phenols. Moreover, as an upper limit of the compounding quantity of a non-reactive oxygen-containing organic solvent, 1000 mass parts is preferable with respect to 100 mass parts of phenols, 500 mass parts is further more preferable, and 10 mass parts is especially preferable. When the blending amount of the non-reactive oxygen-containing organic solvent is less than the above lower limit, the production of reaction by-products becomes remarkable, and the productivity may be reduced. On the other hand, when the blending amount of the non-reactive oxygen-containing organic solvent exceeds the above upper limit, the reaction rate is lowered and the productivity may be lowered.

  The oxo acid as the catalyst refers to a compound in which a hydroxyl group and an oxo group (═O) are bonded to a certain atom, and the hydroxyl group gives an acidic proton. As this oxo acid, inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, nitric acid, perchloric acid, perbromic acid, carboxylic acid, phthalic acid, maleic acid, paratoluenesulfonic acid, methanesulfonic acid, phenol Examples thereof include organic acids such as sulfonic acid. Among these, inorganic acids are preferable, and sulfuric acid is more preferable.

  These oxo acids may be used singly or in combination of two or more, and a reaction promoter such as mercaptoacetic acid or other catalysts may be used in combination. The amount of oxo acid used may be set in such a range that the reaction is not extreme and dangerous and is not too small for promoting the reaction. 20% by mass.

  The compound is produced by adding a catalyst containing the above phenols, anthracene-9-carbaldehyde, a non-reactive oxygen-containing organic solvent and an oxo acid to a reaction vessel and stirring for a predetermined time. In addition, the order of the input of the input material into the reaction vessel is not limited.

  The reaction temperature in the reaction step of the production method is usually 0 to 100 ° C, preferably 25 to 60 ° C. If the reaction temperature is too low, the reaction time may be longer. On the other hand, if the reaction temperature is too high, formation of reaction by-products such as higher-order condensates and isomers is promoted, and the purity of the compound decreases. there's a possibility that.

  The pressure in the reaction vessel in the reaction step of the production method is usually normal pressure, but may be increased or reduced, and specifically, the internal pressure (gauge pressure) is -0.02 to 0.00. The range is preferably 2 MPa.

  The reaction time in the reaction process of the production method depends on the phenols used, the type and amount of the non-reactive oxygen-containing organic solvent, the molar ratio, the reaction temperature, the pressure, etc. 1 to 48 hours.

  After completion of the reaction of the production method, the acid catalyst is removed. As a method for removing the catalyst, generally, the product is dissolved in a water-insoluble organic solvent such as methyl ethyl ketone and methyl isobutyl ketone, and is removed by washing with water. There are no particular restrictions, such as a method of filtering out a salt, a method of directly removing a resin acid such as an ion exchange resin, or a method of passing a reaction solution through a column packed with an anionic packing material.

  In the production method, after removing the catalyst, the compound is removed by purification. In general, an organic solvent that acts as a poor solvent for the target product, and acts as a good solvent for other by-products and unreacted raw materials, is precipitated, filtered, and dried. The compound which is a product can be obtained.

<Derivatives of the compound>
The derivative of the present invention is a derivative of the above compound of the present invention. The derivative can be obtained by subjecting the above compound to glycidylation, (meth) acrylation, allylation, methylolation, benzoxazine formation and the like by a known method.

  The glycidylation can be performed, for example, by reacting the compound with epichlorohydrin. Moreover, the said (meth) acrylation can be performed by making the said compound and (meth) acryloyl halide (for example, acryloyl chloride etc.) react, for example.

  Each derivative thus obtained can be used as a resin raw material such as an epoxy resin raw material or an acrylic resin raw material. The derivative can also have excellent characteristics such as a high melting point and high photorefractive properties.

Examples of the derivatives include derivatives having an anthracene skeleton. An example of such a derivative is a derivative represented by the above formula (2). The definitions of X, Y, n ₁ and n _{2 in} the above formula (2) are the same as those in the above formula (1). Since the derivative represented by the formula (2) has an anthracene skeleton, it has various characteristics peculiar to anthracene, such as a high carbon density, a high refractive index, and fluorescence performance with respect to ultraviolet rays.

<Method for producing derivative represented by formula (2) (hereinafter also referred to as “specific derivative”)>
The said specific derivative can be manufactured by the method which has the process of making the compound represented by following formula (1) react under an acidic catalyst.

  Specifically, the compound is converted into the specific derivative by dissolving the compound in a solvent and adding an acidic catalyst. Although it does not specifically limit as said solvent, For example, the non-reactive oxygen-containing organic solvent described in the said paragraphs 0051-0054, phenols, etc. are mentioned, These can be used individually or in mixture of 2 or more types. Among these solvents, phenols are preferable, and cresol is more preferable.

  The acidic catalyst is not particularly limited, but from the viewpoint of the reactivity of the conversion reaction, acids other than the above-mentioned oxo acids, for example, halogen hydroacids (HF, HCl, HBr, HI) are preferable, and HCl (hydrochloric acid) is more preferable. . After the reaction, the specific derivative can be extracted by purification or the like by a known method.

<Composition>
The compound or a composition containing a derivative obtained using this compound as an intermediate can be used for resin raw materials such as epoxy resin raw materials, polycarbonate resin raw materials, acrylic resin raw materials, adhesives, paints, and the like. As another component in the said composition, the well-known thing used when manufacturing each resin is mentioned. Examples of the other components include a curing agent, a curing accelerator, a solvent, an inorganic filler, a pigment, a thixotropic agent, a fluidity improver, and other monomers.

  As said hardening | curing agent, the hardening | curing agent for general epoxy resins is used, For example, polyhydric phenols, acid anhydrides, amines, imidazoles etc. can be mentioned.

  Examples of the polyphenols include resorcin, catechol, hydroquinone, bisphenol-F, bisphenol-A, biphenol, phenol novolacs, cresol novolacs, xylenol novolacs, bisphenol-A novolacs, trisphenol methanes, tetrakisphenol ethane Aralkyl polyphenols, dicyclopentadiene polyphenols, cyclized polybutadiene polyphenols and the like.

  Examples of the acid anhydrides include methylhexahydroacetic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Examples include acid, methylendomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.

Examples of the amines include bis (4-aminocyclohexyl) methane, bis (aminomethyl) cyclohexane, m-xylylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [ 5.5] Aliphatic and alicyclic amines such as undecane, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol , Tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-azabicyclo [4.3.0] -nonene-7 and salts thereof, and the like. Mention may also be made of BF ₃ complex compounds.

Examples of the imidazoles include 2-methylimidazole and 2-ethyl-4-methylimidazole.
Examples of other curing agents include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and the like.

  Examples of the curing accelerator include 2-methylimidazole, 2-ethylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl). -2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, tin octylate and the like.

  The solvent varies depending on the composition of the composition. For example, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether pro Pionates, aromatic hydrocarbons, ketones, esters and the like can be mentioned.

  Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. Includes organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite. Examples of the fluidity improver include phenyl glycidyl ether, naphthyl glycidyl ether, and the like. be able to.

<Hardened product>
Moreover, the hardened | cured material obtained by hardening | curing this composition can be used as various resin. These hardened | cured material can be used for various uses as a highly versatile material which provides various characteristics, such as a high melting point derived from a hydroanthracene skeleton, and high optical refraction. In addition, the said hardened | cured material can be obtained by using the well-known method corresponding to each composition, such as light irradiation and a heating, said composition.

  These cured products are various synthetic resins such as phenol resin, epoxy resin, polycarbonate resin, acrylic resin, and further, taking advantage of functionality, optical materials such as lenses and optical sheets, recording materials such as hologram recording materials, and organic materials. It can be used as a highly functional material such as a photoreceptor, a photoresist material, an antireflection film, and a semiconductor encapsulant.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this Example. In addition, the measurement was performed with the following measuring equipment and measuring method.

<GPC purity>
GPC purity was measured by using HLC-8220 GPC manufactured by Tosoh Corporation, RI detector, TSK-Gel SuperHZ2000 + HZ1000 + HZ1000 (4.6 mmφ × 150 mm) column, and tetrahydrofuran was fed at 0.35 ml / min as a developing solvent. The area ratio was determined.

<HPLC purity>
The HPLC purity and the end point of the reaction were confirmed using HPLC Promince series manufactured by Shimadzu Corporation, UV detector SPD-20A (246 nm), and ODS-3 (4.6 mmφ × 250 mm) column manufactured by GL Science. As developing solvents, Examples 1, 3, 4 and Comparative Example 1 were water / acetonitrile = 25/75, Example 2 and Comparative Example 2 were water / acetonitrile = 20/80, and Example 6 was water / acetonitrile. = 40/60 was used, the solution was fed at 1.0 ml / min, and the ratio of the peak of the target product was obtained.

<Melting point and glass transition temperature (Tg)>
Melting | fusing point was calculated | required by the peak top method by the temperature increase rate of 5 degree-C / min in nitrogen atmosphere with the DSC8230 type | mold differential scanning calorimeter by Rigaku. Moreover, the glass transition temperature was measured on the same conditions, and the midpoint glass transition temperature was calculated | required.

^<1 H-NMR and ¹³ C-NMR>
¹ H-NMR and ¹³ C-NMR were measured with DMSO-d6 solvent using TUN as a reference substance, using UNITY-INOVA 400 MHz manufactured by Varian.

<Refractive index>
The refractive index was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at concentrations of 1 mass%, 5 mass parts, and 10 mass% at 25 ° C. using an RA-520N refractometer manufactured by Kyoto Electronics Industry Co., Ltd. Measurement was made to create a calibration curve, and the converted refractive index at 100% by mass was determined.

<Absorption spectrum and fluorescence spectrum>
The absorption spectrum was dissolved in DMSO at a concentration of 1 × 10 ⁻⁵ mol / L using a spectrophotometer V-570 manufactured by JASCO Corporation and measured in the wavelength range of 250 nm to 600 nm. The fluorescence spectrum was measured using a fluorescence spectrophotometer F-4010 manufactured by Hitachi High-Technologies Corporation, dissolved in DMSO at a concentration of 1 × 10 ⁻⁵ mol / L and excited at a maximum wavelength. Moreover, the presence or absence of light emission was observed by irradiating 365 nm ultraviolet rays using a handy UV lamp SLUV-4 manufactured by ASONE.

<Linear expansion coefficient>
The coefficient of linear expansion is a measurement for confirming dimensional stability. A cured product is cut into a 2.5 mm × 3.0 mm × 15.0 mm test piece, and the air atmosphere is measured with a RMA TMA8141BS type thermomechanical measuring device. The length of the test piece up to 300 ° C. was measured at a rate of temperature increase of 5 ° C./min, and the average coefficient of thermal expansion (ppm / ° C.) in the range of 30 ° C. to 280 ° C. was determined.

<Water absorption rate>
The water absorption was determined by measuring the mass increase (mass%) after cutting the cured product into 10 mm × 10 mm × 2.5 mm test pieces and boiling it in hot water for 8 hours.

<Remaining charcoal rate>
There is a proportional relationship between the residual carbon ratio and the oxygen index, and it is generally said that a resin with high flame retardancy has a high residual carbon ratio (see Document 1 below). With reference to this document, the residual carbon ratio was measured as an index of flame retardancy. The measurement method was a TG8230 type differential thermobalance made by Rigaku, measured up to 830 ° C. at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and obtained by subtracting the mass reduction rate (%) from 100%. .

  (Reference 1) “It was confirmed that there was a linear relationship between the Krevelen oxygen index and the degree of carbonization of the polymer (Char Residue). D. W. van Krevelen, polymer, 16, p615 (1975) D. W. van Krevelen, Chimia, 28, p504 (1974)

[Example 1] Synthesis of biscresol hydroanthracene In a 300 mL reaction vessel with a reflux tube, o-cresol (108.0 g, 1.0 mol), anthracene-9-carbaldehyde (41.2 g, 0.2 mol) and methanol ( 108.0 g) was added and dissolved at 40 ° C. 98% concentrated sulfuric acid (5.4 g) was added, and the reaction was carried out at 40 ° C. for 24 hours. It was confirmed by HPLC that the anthracene-9-carbaldehyde peak had disappeared and that the target product was mainly produced. The HPLC chart of the reaction end point is shown in FIG. Next, the reaction solution was dissolved in methyl isobutyl ketone (216.0 g), and washed with distilled water (108.0 g) several times to remove the catalyst. After distilling off methyl isobutyl ketone and o-cresol under reduced pressure, toluene (324.0 g) and cyclohexane (21.8 g) were added and stirred at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 54.2 g (yield 67.0%) of reddish brown crystals.

The obtained crystal had GPC purity of 99.3%, HPLC purity of 99.0%, melting point of 188 ° C., converted refractive index of 1.666 (25 ° C.), ¹ H-NMR (400 MHz, DMSO-d6, δ, ppm / 2.0, 2.1, 6H, -C H ₃ /6.9, 1H , -C H ₁ = / 6.6, 6.7, 6.9, 7.0, 6H, Phenyl- H /5.2,7.1,7.2,7.3,7.4,9H,Hydroxyanthryl- H /9.2,9.5,2H,-O H /) and ¹³ C-NMR (400MHz, _{DMSO-d6, δ, ppm /} 16.3,16.4, - C H 3 /129.6,- C H 1 = / 114.7,114.8,123.7,124.0,125.4 , 125.6, 126.7, 127.5, 127.8, 133.2, 153.9, 155. , - Phenyl /50.9,123.8,126.8,127.0,127.6,128.0,128.4,128.6,131.6,134.5,135.5,138. 5, 139.3, 141.3, -Hydroanthryl ) 9- (3-methyl-4-hydroxybenzylidene) -10- (3-methyl-4-hydroxyphenyl) -10-hydroanthracene (shown by the following formula) Compound). FIG. 2 shows a ¹ H-NMR chart, and FIG. 3 shows a ¹³ C-NMR chart. Further, it was visually confirmed that there was no light emission upon irradiation with a UV lamp (365 nm).

[Example 2] Synthesis of bisxylenol hydroanthracene The same operation as in Example 1 was performed except that orthocresol was changed to 2,6-xylenol (12.2 g) in Example 1, and 49.0 g of white crystals ( Yield 56.6%). The HPLC chart of the reaction end point is shown in FIG.

The obtained crystal had a GPC purity of 99.6%, an HPLC purity of 99.4%, a melting point of 226 ° C., a converted refractive index of 1.669 (25 ° C.), and ¹ H-NMR (400 MHz, DMSO-d6, δ, _{ppm / 2.0,2.1,12H, -C H 3 /6.9,1H,-C} H 1 = / 6.8,7.0,4H, Phenyl- H /5.2,7.0 7.1-7.2, 7.2-7.3, 7.3-7.4, 7.4-7.7, 9H, Hydroanthryl- H / 7.8-8.2, 8.2. ˜8.7, 2H, —OH /) and ¹³ C-NMR (400 MHz, DMSO-d6, δ, ppm / 16.94, 16.98- C H ₃ /129.1, -C H ₁ = / 123 .6,124.3,125.3,126.6,127.2,133.3,151.7,152.9, - P enyl /50.8,124.2,126.7,126.9,127.7,127.9,128.1,128.4,128.6,134.7,135.7,138.3, 13-9.5,141.1, -Hydroanthryl ) 9- (3,5-dimethyl-4-hydroxybenzylidene) -10- (3,5-dimethyl-4-hydroxyphenyl) -10-hydroanthracene It was confirmed that it was a compound represented by FIG. 5 shows a ¹ H-NMR chart, and FIG. 6 shows a ¹³ C-NMR chart. It was visually confirmed that there was no light emission when irradiated with a UV lamp (365 nm).

[Comparative Example 1] Synthesis of biscresol anthracene The same operation as in Example 1 was carried out except that 98% sulfuric acid was changed to 35% hydrochloric acid (10.8 g). Rate 55.7%). An HPLC chart of the reaction end point is shown in FIG.

The obtained crystals had a GPC purity of 99.4%, an HPLC purity of 99.6%, a melting point of 168 ° C., a converted refractive index of 1.682 (25 ° C.), and visually observed blue light emission when irradiated with a UV lamp (365 nm). Confirmed. ^{1 H-NMR (400MHz, DMSO} -d6, δ, ppm / 2.0,2.1-C H 3 /4.9,2H,-C H 2 - / 6.6,6.7,6.9 , 7.0,6H, Phenyl- H /7.3,7.4,7.6,8.3,8H,Anthryl- H /9.1,9.6,2H,-O H) and ¹³ C -NMR (400MHz, DMSO-d6, δ, ppm / 16.3, - C H 3 /32.1,- C H 2 - / 114.7,114.8,123.8,124.2,126. 2,129.4,129.7,130.2,132.6,133.3,153.7,155.1, - Phenyl /125.1,125.2,125.7,127.6,128 .6,130.3,131.3,136.7, - Anthryl) at 9- (3-methyl - - it was confirmed that hydroxybenzyl) is -10- (3-methyl-4-hydroxyphenyl) anthracene (compound represented by the following formula). FIG. 8 shows a ¹ H-NMR chart, and FIG. 9 shows a ¹³ C-NMR chart.

[Comparative Example 2] Synthesis of bisxylenol hydroanthracene Except that 98% sulfuric acid was changed to 35% hydrochloric acid (12.2 g) in Example 2, the same procedure as in Example 1 was performed to obtain 49.1 g of pale yellow crystals ( Yield 56.8%). The HPLC chart of the reaction end point is shown in FIG. This compound is presumed to be 9- (3,5-dimethyl-4-hydroxybenzyl) -10- (3,5-dimethyl-4-hydroxyphenyl) anthracene (compound represented by the following formula).

  The obtained crystals had a GPC purity of 99.0%, an HPLC purity of 98.6%, a melting point of 190 ° C., a converted refractive index of 1.485 (25 ° C.), and visually observed blue light emission when irradiated with a UV lamp (365 nm). Confirmed.

[Example 3] Synthesis of derivative 1 (acrylic form of biscresol hydroanthracene)
Biscresol hydroanthracene (10.1 g, 0.025 mol), methyl isobutyl ketone (90.4 g) and triethylamine (6.3 g) obtained in Example 1 were placed in a 300 mL reaction vessel with a reflux tube, and dissolved by stirring. . Acryloyl chloride (5.2 g) was added dropwise to this solution at 25 ° C. After reacting at 40 ° C. for 5 hours, methanol (10.1 g) was added to terminate the reaction. The reaction solution was washed with 10% NaCl water (100 g), and then washed several times with distilled water (100 g). Methyl isobutyl ketone was distilled off under reduced pressure, methanol (60.1 g) was added, and crystallization was performed at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 7.9 g (yield 61.7%) of light tan crystals, which are acrylic bodies of biscresol hydroanthracene. The obtained crystals had a GPC purity of 97.0%, an HPLC purity of 99.1%, and a converted refractive index of 1.619 (25 ° C.).

Example 4 Synthesis of Derivative 2 (Biscresol Hydroanthracene Epoxy Compound)
Into a 300 mL reaction vessel with a reflux tube, the biscresol hydroanthracene (30.3 g, 0.074 mol), methanol (30.3 g) and epichlorohydrin (109.8 g) obtained in Example 1 were placed and dissolved by stirring. did. Caustic soda (5.9 g) was added to this solution at 40 ° C., and the temperature was raised to 60 ° C. After reacting at 60 ° C. for 3 hours, methyl ethyl ketone (93.2 g) was added and dissolved by stirring, followed by washing with distilled water (60 g) several times. The organic layer was concentrated under reduced pressure to obtain a resinous target product. The resin-like material which had been allowed to cool was crushed in a mortar and stirred with methanol (321.3 g) to precipitate crystals, which were filtered and dried to obtain 24.2 g of pale yellow crystals. The obtained crystals had a GPC purity of 97.1%, an HPLC purity of 95.3%, and a converted refractive index of 1.629 (25 ° C.).

[Example 5] Epoxy cured product of biscresol hydroanthracene 20.0 g of the crystals obtained in Example 4 and methylhexahydroacetic anhydride (14.4 g) as a curing agent are weighed and melt mixed on a 180 hot plate. did. Furthermore, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole (0.1 g) was added as a curing accelerator, and the mixture was sufficiently stirred and degassed to obtain an epoxy composition. The obtained liquid was poured into a mold, degassed under reduced pressure at 100 ° C. for 45 minutes, and then subjected to a pressure of 0.01 kgf / cm ² at normal pressure, over 100 ° C. (3 hours) and 150 ° C. (5 hours). After curing, aftercuring was performed at 220 ° C. for 3 hours to obtain a cured epoxy product.

  The obtained cured product was cut into the sizes of the various measurement methods described above, and the characteristics were evaluated. The glass transition temperature was 174 ° C., the linear expansion coefficient was 111 ppm / ° C., the water absorption was 0.55 mass%, and the residual carbon ratio was 9.29%.

[Example 6] Conversion reaction of biscresol hydroanthracene to biscresol anthracene In a 300 mL reactor equipped with a reflux tube, biscresol hydroanthracene obtained in Example 1 (8.13 g, 0.02 mol) and o-cresol (21.6 g) was added and dissolved at 50 ° C. After cooling to 30 ° C. or lower, 35% concentrated hydrochloric acid (2.08 g) was added, and the temperature was raised to 60 ° C. It was confirmed by HPLC that the hydroanthracene peak disappeared and that the desired product was mainly produced. Next, 48% NaOH was added to the reaction solution to adjust the pH to 6 to 7, and then washed with distilled water (100.0 g) several times to remove neutralized salts. The remaining pure water was distilled off under reduced pressure, followed by cooling and adding methanol (124.0 g) and distilled water (24.0 g) to crystallize at 10 ° C. The crystallized crystals were separated by filtration and dried under reduced pressure to obtain 5.6 g (yield 68.9%) of yellow crystals.

The obtained crystals had a GPC purity of 98.9%, an HPLC purity of 99.2%, a melting point of 168.2 ° C, and a converted refractive index of 1.692 (25 ° C). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. 9- (3-Methyl-4-hydroxybenzyl) -10- (3-methyl-4-hydroxyphenyl) anthracene (same as the compound obtained in Comparative Example 1) by ¹ H-NMR and ¹³ C-NMR I confirmed that there was.

[Comparative Example 3] General epoxy body Adeka Resin EP-4100 [trade name: manufactured by ADEKA Corporation / epoxy equivalent 190], which is a commercially available product of bisphenol-A type epoxy resin, was measured and its converted refractive index was measured. 572 (25 ° C.).

[Comparative Example 4] General epoxy cured product In Example 5, the crystal (20.0 g) obtained in Example 4 was used as EP-4100 (20.0 g) measured in Comparative Example 3, and anhydrous methylhexahydro Except that acetic acid (12.2 g) was changed to (15.9 g), the same operation as in Example 5 was performed to obtain a cured epoxy product.

  The obtained cured product was cut into the sizes of the various measurement methods described above, and the characteristics were evaluated. The glass transition temperature was 150 ° C., the linear expansion coefficient was 118 ppm / ° C., the water absorption was 0.68 mass%, and the residual carbon ratio was 2.57%.

  Each measured value is summarized in the following table. In order to facilitate comparison, the examples and comparative examples are rearranged.

  As shown in Table 1, the compound of the present invention has a higher melting point and refractive index than the corresponding comparative anthracene compounds (Example 1, Comparative Example 1, Example 2, and Comparative Example 2). In addition, derivatives obtained from these compounds also have an excellent refractive index. Furthermore, it turns out that the hardened | cured material of this invention has various performances compared with the epoxy hardened | cured material of the comparative example.

  The compound of the present invention and a derivative obtained using this as an intermediate can provide a highly versatile material that imparts various properties such as a high melting point and a high photorefractive property, such as an epoxy resin raw material, a polycarbonate resin raw material, and an acrylic resin. It can be used for resin raw materials such as resin raw materials. Resins using these compounds as raw materials include, for example, laminate materials, coating materials such as paints, optical materials such as lenses and optical sheets, recording materials such as hologram recording materials, organic photoreceptors, photoresist materials, and antireflections. It can be used for highly functional materials such as films and semiconductor encapsulants, magnetic materials such as molecular magnetic memory, etc., and these can be used as materials for organic solar cells, organic EL elements, liquid crystal display elements, etc. . The compound of the present invention can be used not only as a resin raw material but also as, for example, a pharmaceutical intermediate or a dye intermediate.

Claims (8)

A compound represented by the following formula (1).

(In the formula (1), X is an (n ₁ +1) -valent aromatic group, and this aromatic group may have a substituent. Y is an (n ₂ +1) -valent aromatic group. (This aromatic group may have a substituent. N ₁ and n ₂ are each independently an integer of 1 to 3).   The compound according to claim 1, wherein X and Y each have at least one alkyl group as a substituent. A derivative obtained by glycidylation, (meth) acrylation, allylation, methylolation or benzoxazine conversion of the compound according to claim 1 or claim 2.   A composition comprising the compound according to claim 1 or claim 2 or the derivative according to claim 3.   Hardened | cured material obtained by hardening | curing the composition of Claim 4. The manufacturing method of the compound represented by following formula (1) which has the process of making phenols and anthracene-9-carbaldehyde react in presence of the catalyst containing a non-reactive oxygen-containing organic solvent and oxo acid.

(In the formula (1), X is an (n ₁ +1) -valent aromatic group, and this aromatic group may have a substituent. Y is an (n ₂ +1) -valent aromatic group. (This aromatic group may have a substituent. N ₁ and n ₂ are each independently an integer of 1 to 3).   The method for producing a compound according to claim 6, wherein the phenol is a phenolic compound having at least one alkyl group. The manufacturing method of the derivative represented by following formula (2) which has the process of making the compound represented by following formula (1) react under an acidic catalyst.

(In the formula (1), X is an (n ₁ +1) -valent aromatic group, and this aromatic group may have a substituent. Y is an (n ₂ +1) -valent aromatic group. (This aromatic group may have a substituent. N ₁ and n ₂ are each independently an integer of 1 to 3).

(In the formula (2), X is an (n ₁ +1) -valent aromatic group, and this aromatic group may have a substituent. Y is an (n ₂ +1) -valent aromatic group. (This aromatic group may have a substituent. N ₁ and n ₂ are each independently an integer of 1 to 3).

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