JP2011195515A - Anthracene derivative, resin, curable composition, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anthracene derivative having specific characteristics of anthracene and a diversity of reactions, a resin having high functionality that is obtained from the anthracene derivative and can be applied to a variety of technical fields, and a composition and the like containing the anthracene derivative or the resin.SOLUTION: There are provided the anthracene derivative represented by formula (1), the resin obtained from the anthracene derivative, the composition containing the anthracene derivative or the resin, and a cured product of the composition, (wherein X and Y are each independently a hydroxyaryl group formed by substituting one or two or more hydrogen atoms on an aromatic ring with CHOZ, wherein a plurality of Z are each independently a hydrogen atom or a 1-4C alkyl group).

Description

  The present invention relates to a novel anthracene derivative, a resin and a curable composition using the same, and a cured product.

  Anthracene is a polycyclic aromatic compound in which three benzene rings are condensed. Conventionally, wood insecticides, storage stabilizers, paints, epoxy resin and carbon black production raw materials, anthraquinone dye synthesis raw materials, etc. It is used for various applications. In addition, since anthracene has the above-mentioned structure, in addition to features such as structural hardness, high carbon density, high melting point, and high refractive index, anthracene is useful in that π electrons act upon ultraviolet irradiation to emit fluorescence. It has characteristics. 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.

  As a technique relating to such an anthracene derivative, for example, a photo-curing polymer (acting as a sensitizer for photo radical polymerization by introducing a (meth) acrylate group at the 9th and 10th positions of anthracene to form a polymerizable monomer ( Japanese Laid-Open Patent Publication No. 2007-99637) and a technique for obtaining a polymer having ultraviolet absorbing ability and flame retardancy (see Japanese Laid-Open Patent Publication No. 2008-1637, etc.) have been proposed. Also in the field of photoresists, anthracene derivatives are radiation-sensitive resin compositions having advantages such as high sensitivity, high resolution, high etching resistance, and low sublimation (see JP 2005-346024 A). In addition, utilization as an antireflection film (see JP-A-7-82221 etc.) for preventing intermixing with a resist resin has been studied. Furthermore, application of anthracene to organic photoreceptors (OPCs), organic electroluminescent elements, organic solar cells, organic light emitting diodes, etc. as an electron transporting material or a light emitting material has been studied (Japanese Patent Laid-Open No. 2009-2009). No. 40765). 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 Use as a material has also been proposed (see JP-A-6-295151, etc.).

  On the other hand, focusing on the novolac type phenolic resin, this resin is generally a molded product, laminated product, shell mold, building material, adhesive material, friction material, grindstone, electronic material, thermal paper, pressure sensitive paper, epoxy resin curing agent. It is used for a wide range of applications. Under such circumstances, especially with the rapid development of IT field in recent years, high functionality and high added value such as high heat resistance, high refractive index, and improvement of fluorescence characteristics of novolak type phenol resin are eagerly desired. .

  Examples of highly functional novolak phenol resins include flame retardant resin raw materials that have improved heat resistance by introducing a rigid skeleton such as a fluorene skeleton (see JP 2003-226727 A), methylol, and the like. A photosensitive resin material excellent in heat resistance and etching resistance in which a fluorene skeleton is efficiently introduced using a bisphenol fluorene having a group (see JP 2008-273844 A), a biphenyl skeleton, a naphthalene skeleton, an anthracene skeleton, etc. A thermosetting resin molding material (see, for example, Japanese Patent Application Laid-Open No. 2009-286888) that has been improved by introducing heat resistance and mechanical strength has been proposed.

  In addition, phenol-glyoxal novolak resin having fluorescent properties is used as a raw material or additive for laminates used for high-density multilayer printed circuit boards and the like, and automatic optical inspection (AOI) that is a quality inspection of laminated products. It has also been proposed to use this information (see Japanese Patent Application Publication No. 2002-542389).

  As described above, various novolak-type phenolic resins having improved heat resistance and the like by introducing a rigid structure into the skeleton have been studied. Even in these novolak-type resins, there are various types including those in the IT field. There is still room for improvement in various functions such as high refractive index and fluorescence characteristics when applied to the above-mentioned applications. In addition, development of an anthracene derivative excellent in reactivity capable of synthesizing such a resin having a high added value is awaited.

JP 2007-99637 A JP 2008-1637 A JP 2005-346024 A JP-A-7-82221 JP 2009-40765 A JP-A-6-295151 JP 2003-226727 A JP 2008-273844 A JP 2009-286888 A Special Table 2002-542389

  The present invention has been made in view of such circumstances, and anthracene derivatives having high reactivity with characteristics unique to anthracene (such as high carbon density, high melting point, high refractive index, and fluorescence performance with respect to ultraviolet rays), and the anthracene It is an object of the present invention to provide a resin having a high functionality such as a high refractive index and excellent fluorescence characteristics using a derivative, and capable of being applied in various technical fields, and a composition containing these.

The invention made to solve the above problems is
It is an anthracene derivative represented by the following formula (1).

(In formula (1), X and Y are each independently a hydroxyaryl group in which one or more hydrogen atoms on the aromatic ring are substituted with * —CH ₂ OZ. * Is a hydroxyaryl group And a plurality of Z contained in X and Y are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

Since the anthracene derivative has an anthracene skeleton, it has various characteristics peculiar to anthracene, such as high carbon density, high refractive index, and fluorescence performance with respect to ultraviolet rays. In addition, since this anthracene derivative has two or more CH ₂ OZ (methylol group or alkoxymethyl group) at a predetermined position, it has reactivity such as thermosetting that is remarkably superior to conventional phenol compounds. . Therefore, the anthracene derivative can be suitably used as, for example, a highly functional resin material or curing agent.

X and Y are each independently preferably a hydroxyphenyl group in which one or two hydrogen atoms on the aromatic ring are substituted with * —CH ₂ OZ. The anthracene derivative is not complicated in structure and can be produced efficiently, and can exhibit excellent reactivity such as thermosetting.

  Said Z is good in it being a hydrogen atom. Thus, the said anthracene derivative can exhibit more excellent reactivity, such as thermosetting, by having two or more methylol groups.

  The resin of the present invention is a resin obtained using the above anthracene derivative. The resin has excellent reactivity such as thermosetting, and also has excellent functionality such as high refractive index, high glass transition point, and fluorescence characteristics.

  The composition of the present invention is a composition containing the above anthracene derivative or a resin obtained using this anthracene derivative, and is excellent in curability and the like. In addition, the cured product of the present invention is a cured product obtained by curing this composition, and has high functionality such as high heat resistance, high refractive index, high carbon density, and fluorescence performance, so it can be applied to various fields. It can be used as a possible resin.

  As described above, the anthracene derivative of the present invention has various characteristics peculiar to anthracene, such as high carbon density, high refractive index, and fluorescence performance with respect to ultraviolet rays. Furthermore, since the anthracene derivative has various properties peculiar to anthracene and exhibits high reactivity due to a methylol group or an alkoxymethyl group, it can be used as various resin raw materials and curing agents.

  Therefore, the anthracene derivative of the present invention, the resin obtained therefrom, the composition containing the same, and the cured product are extremely effective for enhancing the functionality of the material and imparting new characteristics. Curing agents, polycarbonate raw materials, building materials, shell molds, laminated materials, molding materials, paints, recording materials, photoresist materials, antireflection films, electronic materials such as semiconductor sealing materials, optical materials, magnetic materials such as molecular magnetic memory, etc. Applications can be developed in various technical fields.

1 is a diagram showing a ¹ H-NMR chart of an anthracene derivative of Example 1. FIG. 1 is a diagram showing a ¹³ C-NMR chart of an anthracene derivative of Example 1. FIG. 2 is a graph showing an absorption spectrum of an anthracene derivative of Example 1. FIG. 2 is a graph showing a fluorescence spectrum of an anthracene derivative of Example 1. FIG. It is a figure which shows the GPC chart of resin of Example 2. FIG. It is a figure which shows the absorption spectrum of resin of Example 2. FIG. It is a figure which shows the fluorescence spectrum of resin of Example 2. FIG. It is a figure which shows the GPC chart of resin of the comparative example 1. 4 is a graph showing an absorption spectrum of a compound of Comparative Example 2. FIG. 6 is a graph showing an absorption spectrum of a compound of Comparative Example 3. FIG. 4 is a graph showing a fluorescence spectrum of a compound of Comparative Example 3. FIG. It is a figure which shows the GPC chart of resin of the comparative example 4. It is a figure which shows the absorption spectrum of resin of the comparative example 4. It is a figure which shows the GPC chart of resin of the comparative example 5. It is a figure which shows the absorption spectrum of resin of the comparative example 5. It is a figure which shows the fluorescence spectrum of resin of the comparative example 5.

Hereinafter, an embodiment of the present invention will be described in detail in this order for an anthracene derivative, a resin obtained by using the anthracene derivative, a curable composition, and a cured product.
<Anthracene derivative>
The anthracene derivative of the present invention is represented by the above formula (1).

  The anthracene derivative of the present invention has an anthracene skeleton as described above, and thus has a high carbon density, a high refractive index, a fluorescence performance with respect to ultraviolet rays, and the like, which are characteristics unique to anthracene.

  The hydroxyaryl group constituting the anthracene derivative of the present invention is a substituent obtained by removing one hydrogen from an aromatic ring of an aromatic hydrocarbon which has at least one hydroxyl group and may have other substituents. is there. Specific examples of the hydroxyaryl group include a hydroxyphenyl group, a hydroxynaphthyl group, and the like, and a hydrogen atom on these aromatic rings is a substituent such as an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an amino group, or a mercapto group. Is substituted. In addition, although the substituent on the said aromatic ring may be plural, in order to maintain the reactivity of an aromatic ring, it is preferable that all the hydrogen atoms on an aromatic ring are not substituted.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of these alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl and isobutyl. , 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.

  Examples of the alkoxy group include linear, branched, monocyclic or condensed polycyclic alkoxy groups. Specific examples of these alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy , 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 and the like.

  Examples of the aryl group include groups in which one hydrogen is removed from an aromatic ring which may have a substituent, and specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 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 group, , 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, An o-mercaptophenyl group, a p-cyanophenyl group, an m-nitrophenyl group, an m-azidophenyl group, and the like can be given.

  Examples of the alkenyl group include straight chain, branched chain, monocyclic or condensed polycyclic alkenyl groups, and these 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.

  An anthracene derivative having a hydroxyaryl group having a substituent as described above as the hydroxyaryl group can be further added or adjusted while maintaining the characteristics of the anthracene derivative.

  For example, according to the anthracene derivative provided with a hydroxyaryl group having an alkyl group as a substituent, the refractive index, the melting point, and the like can be adjusted without reducing the various reactivity of the anthracene derivative. Such a substituted alkyl group preferably has a low carbon number from the viewpoint of the steric stability of the anthracene derivative, specifically an alkyl group having 5 or less carbon atoms, a methyl group or An ethyl group is particularly preferred.

  Further, according to the anthracene derivative having a hydroxyaryl group having two or more hydroxyl groups, since there are a plurality of hydroxyl groups on one aromatic ring, further application development such as improved cross-linking reactivity is achieved. Is possible.

Among these hydroxyaryl groups, from the viewpoint of high refraction, high carbon density, rigidity, etc., * -CH ₂ OZ (* is a bond that bonds to a carbon atom on the aromatic ring of the hydroxyaryl group as a substituent. In the following, the hydroxyphenyl group and hydroxynaphthyl group having only the bond are omitted, the hydroxyphenyl group having only CH ₂ OZ as the substituent is particularly preferable, and the bond with the anthracene skeleton side is preferred. Most preferred is a hydroxyphenyl group having a hydroxyl group at the para position and having only CH ₂ OZ as a substituent.

  X and Y may be different from each other, but are preferably the same from the viewpoints of high refraction, ease of manufacture, and the like.

The anthracene derivative has CH ₂ OZ (methylol group or alkoxymethyl group) in a hydroxyaryl group bonded directly or via a linking group from the 9th and 10th positions of the anthracene skeleton, thereby starting thermosetting. Has excellent reactivity.

In CH ₂ OZ of the anthracene derivative, the alkoxymethyl group in which Z is an alkyl group having 1 to 4 carbon atoms specifically includes a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, and an isopropoxymethyl group. N-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, and t-butoxymethyl group.

Further, as CH ₂ OZ, a methylol group (a group in which Z is a hydrogen atom) is preferable when importance is attached to the reactivity of the derivative, and a methylol group is an alkyl group when importance is placed on storage stability. A protected alkoxymethyl group (a group in which Z is an alkyl group having 1 to 4 carbon atoms) is preferred. Several Z in a molecule | numerator may mutually differ, However, It is preferable that it is the same from the point of the ease of manufacture.

The number of CH ₂ OZ groups in the anthracene derivative is preferably 2 or more and 4 or less, more preferably 1 or 2 in each hydroxyphenyl group, when the hydroxyaryl group is a hydroxyphenyl group. The anthracene derivative having such a number of CH ₂ OZ is not complicated in structure and can be efficiently produced, and can exhibit excellent reactivity such as thermosetting.

Further, in the anthracene derivative, when the hydroxyaryl group is a hydroxyphenyl group, the CH ₂ OZ is located in the ortho position or the para position with respect to the hydroxyl group from the point that it can be efficiently produced. preferable.

  In addition, the anthracene skeleton in the anthracene derivative may have a substituent at a position other than the 9th and 10th positions as long as the effects of the present invention are not hindered. Examples of the substituent substituted on the hydrogen atom of the anthracene skeleton include those similar to the above-described substituents of the hydroxyaryl group, but are unsubstituted from the viewpoint of efficient productivity and reaction controllability. Are preferred.

  Specific examples of the anthracene derivative include the following formulas (1-1) to (1-4).

Like these exemplified anthracene derivatives of the formulas (1-1) to (1-4), 1 or 2 hydrogen atoms on each aromatic ring are substituted with CH ₂ OZ in X and Y in the formula (1). Preferred anthracene derivatives are preferred. The anthracene derivative is more excellent in reactivity such as thermosetting and can be produced efficiently. In addition, anthracene derivatives in which Z in Formula (1) such as Formula (1-1) and Formula (1-2) is a hydrogen atom are also preferable in terms of excellent reactivity such as curability.

  In addition, since the anthracene derivative has a reactive hydroxyl group (hydroxyl group on the aromatic ring and hydroxyl group in the methylol group) and an aromatic ring, the anthracene derivative has various characteristics unique to anthracene and a variety of bisphenol compounds. Reactive. For example, the anthracene derivative can be allylated, glycidylated, acrylated. In order to obtain such a further derivative, it is easier to produce an anthracene derivative having an alkoxymethyl group that is relatively stable to heat than an anthracene derivative having a thermally unstable methylol group. Further derivatives as described above can be obtained.

  Thus, according to the anthracene derivative, high versatility such as being usable for various resin raw materials can be exhibited. In particular, the anthracene derivative is used as a resin raw material because the phenol skeleton is arranged from the 9th and 10th positions of the anthracene ring, and has high symmetry and can promote condensation only by heat. In addition to this, excellent application development such as modification of the base resin as a cross-linking agent becomes possible. In particular, the anthracene derivative has a phenol skeleton arranged at the 9th and 10th positions, which are the short axis of the anthracene skeleton, and therefore, when introduced into the polymer skeleton, the anthracene derivative has a unique characteristic such that the polymer has a very high carbon density. The function is expected to be demonstrated.

  Further, the anthracene derivative has an anthracene skeleton and has a high refractive index equal to or higher than that of a fluorene compound such as bisphenolfluorene having a methylol group or an alkoxymethyl group. Specifically, the refractive index of the anthracene derivative can be 1.6 or more and 2.0 or less. The physical properties such as refractive index and melting point of the anthracene derivative can be adjusted by selecting X, Y and Z.

  Since the anthracene derivative of the present invention has the above-mentioned structure, it is used for various purposes directly or as a reaction intermediate. For example, various synthesis of a novolak type phenol resin raw material, an epoxy resin raw material, a polycarbonate resin raw material, a curing agent, etc. It can be used as a 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 anthracene derivative>
The anthracene derivative of the present invention is obtained by reacting a phenol with an anthracene-9-carbaldehyde in the presence of a nonreactive oxygen-containing organic solvent and an acid catalyst to obtain a bisphenolanthracene compound, and The bisphenol anthracene compound is produced by a second step in which it is reacted with formaldehyde in the presence of a basic catalyst. In the third step, the anthracene derivative obtained in the second step is reacted with a saturated aliphatic alcohol having 1 to 4 carbon atoms in the presence of an acid catalyst to change the methylol group to an alkoxymethyl group. You can also.

<First step>
The phenols in the first step of this production method refer to compounds having a hydroxyl group on the aromatic ring, and examples thereof include phenolic compounds and naphtholic compounds. The said phenol type compound means the phenol by which the hydrogen on phenol and an aromatic ring was substituted by the other substituent. Examples of the substituent include an alkyl group and a hydroxyl group. The number of substituents is preferably 4 or less, more preferably 2 or less, and particularly preferably 0, from the reactivity with anthracene-9-carbaldehyde. Moreover, it is preferable that the substituent is not arrange | positioned in the para position of a hydroxyl group from the reactivity with anthracene-9-carbaldehyde.

  Examples of the phenol compound include phenol, o-cresol, m-cresol, p-cresol, 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, Zorushin, 2-methyl resorcinol, catechol, 4-methyl catechol, hydroquinone, pyrogallol.

  The naphthol compound refers to naphthol in which naphthol and hydrogen on the aromatic ring are substituted with other substituents. Examples of the substituent include an alkyl group and a hydroxyl group. The number of substituents is preferably 6 or less, more preferably 2 or less, and particularly preferably 0 from the viewpoint of reactivity with anthracene-9-carbaldehyde.

  Examples of the 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 can be mentioned.

  The phenols are not particularly limited to these, and are appropriately selected depending on the desired structure of the anthracene derivative of the present invention. For example, by selecting phenol as the phenol, an anthracene derivative in which X and Y in the above formula (1) are hydroxyphenyl groups can be produced. In addition, 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 the phenol is less than the above lower limit, an undesirable side reaction such as formation of a high-order condensate of the raw material may occur, and a large amount of energy is required for purification. Both are uneconomical because it requires a lot of energy to remove the phenols.

  In the first step of the production method, a non-reactive oxygen-containing organic solvent having one or more oxygen atoms in the molecule is used as a 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. Examples of the non-reactive oxygen-containing organic solvent include alcohols, polyhydric alcohol ethers, cyclic ethers, polyhydric alcohol esters, ketones, esters, sulfoxides, carboxylic acids, and the like.

  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 the like.

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

  As the acid catalyst in the first step of this production method, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and perchloric acid, organic acids such as oxalic acid, paratoluenesulfonic acid, methanesulfonic acid and phenolsulfonic acid, strongly acidic ions Exchange resin etc. can be mentioned. These catalysts may be used alone, or may be used in combination of two or more kinds, or a reaction promoter such as mercaptoacetic acid may be used in combination. The amount of the acid catalyst used may be appropriately set within a range where the reaction proceeds appropriately, but is generally 0.1 to 20 parts by mass with respect to 100 parts by mass of the phenols.

  The reaction step of the first step of the production method is performed by adding the above phenols, anthracene-9-carbaldehyde, a non-reactive oxygen-containing organic solvent and an acid catalyst to the 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 first 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 long. On the other hand, if the reaction temperature is too high, formation of reaction byproducts such as higher-order condensates and isomers is promoted, and the purity of the anthracene derivative is reduced. May be reduced.

  The pressure in the reaction vessel in the first reaction step of the production method is usually normal pressure, but may be increased or reduced pressure. Specifically, the internal pressure (gauge pressure) is -0.02. It is preferable to be in the range of ~ 0.2 MPa.

  The reaction time in the first reaction step of this production method depends on the phenols to be used, the type and amount of the non-reactive oxygen-containing organic solvent, the raw material molar ratio, the reaction temperature, the pressure, etc., and cannot be determined in general. Is generally in the range of 1 to 48 hours.

  After completion of the reaction in the first step of the production method, the product is extracted and 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 is no particular limitation such as a method of filtering off the Japanese salt or a method of passing the reaction solution through a column packed with an anionic filler.

  In the first step of the production method, after removing the catalyst, the bisphenolanthracene compound is taken out by purification. In general, a solvent (xylene, etc.) 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 and then filtered and dried. The bisphenol anthracene compound which is the target product of the first step can be purified by a method using a method such as column chromatography.

<Second step>
In the second step of the production method, the reaction is performed by reacting the bisphenolanthracene compound obtained in the first step with formaldehyde in the presence of a basic catalyst and a solvent such as water.

  Examples of the basic catalyst in the second step of the production method include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium phosphate and the like Alkali metal phosphates such as sodium methoxide, sodium ethoxide, sodium butoxide and the like; trimethylamine, triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5,4,0] undec-7-ene, Examples include tertiary amines such as 1,4-diazabicyclo [2,2,2] octane, and one or more of these can be used in combination. Among these, alkali metal hydroxides are preferable, and sodium hydroxide is preferably used among these. These basic catalysts are usually used after being diluted with water, but an organic solvent such as methanol may be used in combination as long as the water solubility of the bisphenolanthracene compound obtained in the first step is not impaired. As a usage-amount of a basic catalyst, 0.1-20 mass parts is preferable with respect to 1 mass part of bisphenol anthracene compounds, More preferably, it is 1-10 mass parts.

  As a reaction molar ratio of the bisphenol anthracene compound and the basic catalyst in the second step of this production method, 0.5 to 20 mol of the basic catalyst is preferable with respect to 1 mol of the bisphenol anthracene compound in the first step. Preferably, it is 1-10 mol.

  As the usage-amount of formaldehyde in the 2nd process of this manufacturing method, 2-20 mol is preferable with respect to 1 mol of bisphenol anthracene compounds. The formaldehyde in this second step may be paraformaldehyde.

  The reaction temperature in the 2nd process of this manufacturing method is -10-100 degreeC, Preferably, it is 0-50 degreeC. The reaction time depends on the catalyst amount, the reaction molar ratio, the reaction temperature, the pressure and the like, and thus cannot be determined unconditionally, but it is usually preferably within 48 hours.

  The reaction pressure in the second step of this production method is usually normal pressure, but the reaction may be performed under pressure or reduced pressure. Specifically, the internal pressure (gauge pressure) is -0.02 to 0. .2 MPa is preferred.

  After completion of the reaction in the second step of the production method, the product is extracted and the basic catalyst is removed. As a method for removing the catalyst, generally, after neutralization treatment, the product can be dissolved in a water-insoluble organic solvent such as methyl ethyl ketone or methyl isobutyl ketone, and neutralized salt can be removed by washing with water. . The neutralizing agent is not particularly limited, but dilute sulfuric acid is usually used.

  In the second step of this production method, the target product is taken out by purification after removing the basic catalyst. In general, a solvent (toluene, etc.) 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 added, precipitated, filtered and dried. The anthracene derivative (methylol form), which is the target product of the second step, can be purified and obtained by a method, a method by column gas chromatography, or the like.

<Third step>
The third step of the production method is not necessarily required, but is a step performed when it is desired to increase the stability of the anthracene derivative obtained in the second step, or when it is desired to increase the curing start temperature when used as a curing agent. is there. In the 3rd process of this manufacturing method, it manufactures by making the anthracene derivative obtained at the 2nd process, and a C1-C4 saturated aliphatic alcohol react under an acid catalyst.

  The saturated aliphatic alcohol having 1 to 4 carbon atoms in the third step of the production method is a reaction raw material that also serves as a reaction solvent, and may be appropriately selected so as to give a desired protective group to the methylol group. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol and the like. Among these, methanol and ethanol are preferable. The usage-amount of a C1-C4 lower alcohol is 50-5000 mass parts with respect to 100 mass parts of anthracene derivatives obtained at the 2nd process, Preferably it is 10-1000 mass parts.

  As the acid catalyst in the third step of this production method, concentrated sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, strong acidic ion exchange resin, etc. are used, among them. Concentrated sulfuric acid is preferred. Moreover, the usage-amount of this acid catalyst is 0.1-100 mass parts normally with respect to 100 mass parts of anthracene derivatives obtained at the 2nd process, Preferably, it is 0.5-20 mass parts.

  The reaction temperature in the third step of the production method is usually from 0 to 100 ° C, preferably from 40 to 70 ° C. Moreover, the pressure at the time of reaction is the same as that of the above-mentioned 2nd process, and reaction time is usually within 48 hours.

  After completion of the reaction in the third step of the production method, the acid catalyst is removed. As a method for removing this catalyst, in general, a saturated aliphatic alcohol having 1 to 4 carbon atoms, which is a reaction solvent and reaction raw material, is removed by distillation under reduced pressure, and then generated in a water-insoluble organic solvent such as methyl ethyl ketone or methyl isobutyl ketone. Dissolve the product and remove by washing with water. Before removing the saturated aliphatic alcohol having 1 to 4 carbon atoms under reduced pressure, it may be neutralized using a neutralizing agent such as sodium hydroxide.

  In the third step of the production method, the target product is removed by purification after removing the acid catalyst. In general, an organic solvent that acts as a poor solvent for the target product and that acts as a good solvent for other by-products and unreacted raw materials is added, precipitated, filtered, and dried. An anthracene derivative (alkoxymethyl derivative), which is the target product of the three steps, can be obtained.

<Resin>
The resin of the present invention is a resin obtained by using the anthracene derivative, for example, a novolak type phenol resin obtained by heating and condensing a mixture containing the anthracene derivative and phenols or bisphenols. Since the anthracene derivative has CH ₂ OZ (methylol group or alkoxymethyl group), it is more reactive than the case of condensing a general anthracene derivative and phenols or bisphenols using a condensing agent such as formaldehyde. Is expensive. Therefore, by using the anthracene derivative of the present invention as a monomer, an unreacted and low molecular weight anthracene skeleton hardly remains and a high molecular weight resin can be easily obtained.

  Specific examples of the phenols include phenol, cresol, xylenol, naphthol, resorcinol and the like. Examples of the bisphenols include bisphenol-A, bisphenol-F, bisphenol-S, and bisphenolfluorene.

As a ratio of the number of CH ₂ OZ (methylol group or alkoxymethyl group) of the anthracene derivative to one aromatic ring of phenols or bisphenols during polymerization, 1.0 to 2.0 is preferable. In addition, it is preferable to remove unreacted phenols or bisphenols by a method such as distillation under reduced pressure or recrystallization.

  Since the resin of the present invention is obtained from the anthracene derivative, it has a high refractive index, a glass transition point, a carbon density, and has fluorescence characteristics. For example, the refractive index of the resin is about 1.60 or more and 2.00 or less. Further, the glass transition temperature of the resin is about 135 ° C. or more and 150 ° C. or less. Moreover, the resin has a high carbon density, and the residual carbon ratio of the resin is about 35% to 50%.

<Curable composition>
The said curable composition contains the polymer obtained from the anthracene derivative of this invention or this anthracene derivative.

  As this curable composition, the composition containing a novolak-type phenol resin and a hardening | curing agent, and the other arbitrary component is mentioned, for example. However, in the above composition, the anthracene derivative is used as a curing agent, or a resin obtained from the anthracene derivative is used as a novolac-type phenol resin. The method for preparing this curable composition is not particularly limited, and for example, a novolac type phenol resin and a curing agent may be melt-mixed or pulverized or dissolved and mixed in the presence of an organic solvent. .

  Examples of the novolac type phenolic resin include resins obtained from the anthracene derivatives, phenol novolacs, cresol novolacs, xylenol novolacs, and the like. But it can also be used. A part of the phenolic hydroxyl group of the novolak type phenol resin may be glycidyl etherified.

  As said hardening | curing agent, a methylol compound, an alkoxymethyl compound, a hexamine etc. other than the said anthracene derivative can be mentioned. Examples of the methylol compound include monomeric dimethylol compounds such as 2,6-dimethylol-p-cresol, dimer dimethylol compounds such as bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, and 2,2- And tetramethylol compounds such as bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane. Examples of the alkoxymethyl compound include dialkoxymethyl compounds of monomers such as 2,6-dimethoxymethyl-p-cresol and dialkoxymethyl dimers such as bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) methane. Compounds, tetraalkoxymethyl compounds such as 2,2-bis (4-hydroxy-3,5-dimethoxymethylphenyl) propane, and the like.

  As another component in the said curable composition, the well-known thing used when manufacturing each resin is mentioned. Examples of other components include a solvent, an inorganic filler, a pigment, a thixotropic agent, a fluidity improver, and other monomers.

  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. Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, organic bentonite-based, and the like. Can be mentioned.

  In addition to being used for applications such as paints and adhesives, the curable composition can be used as a material for obtaining a cured product having high functionality, which will be described in detail below.

<Hardened product>
The cured product of the present invention is obtained by curing the curable composition by heating. The cured product can be used as various resins. In addition to imparting various properties useful for a wide range of applications such as high refractive index, high carbon density, and fluorescence performance derived from the anthracene skeleton, the cured product also imparts properties specific to electronic materials such as etching resistance. It can be used for various purposes as a highly versatile material.

  The cured product of the present invention is, for example, a magnetic material such as a building material, a friction material, a grindstone, a recording material, a photoresist material, an antireflection film, a semiconductor encapsulating material, an optical material, an organic EL material, a molecular magnetic memory, etc. Etc. can be used.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this Example. The obtained anthracene derivative, resin, and the like were measured by the following measuring equipment and measuring method.

<GPC purity>
The GPC purity was measured using a Tosoh HLC-8220 GPC, 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. Determined by area ratio.

<HPLC purity>
HPLC purity and reaction end point confirmation were performed using HPLC Promince series manufactured by Shimadzu Corporation, UV detector SPD-20A (246 nm), ODS-3 (4.6 mmφ × 250 mm) column manufactured by GL Science, and water / acetonitrile = developing solvent = 40/60 was fed at 1.0 ml / min, and the area ratio of the target product peak was determined.

<Molecular weight>
The molecular weight was measured by using Tosoh HLC-8220 GPC, detector (UV254 nm), TSK-Gel G4000H _XL + G2000H _XL (7.8 mmφ × 300 mm) column, and tetrahydrofuran as a developing solvent at 1.00 ml / min. The weight average molecular weight (Mw) in terms of standard polystyrene was measured.

<Melting point and glass transition temperature (Tg)>
The melting point was determined by a peak top method with a temperature rising rate of 5 ° C./min under a nitrogen atmosphere with a DSC8230 differential scanning calorimeter manufactured by Rigaku. Moreover, the glass transition temperature was measured on the same conditions, and the midpoint glass transition temperature was calculated | required.

<Remaining charcoal rate>
The residual charcoal rate was determined by a numerical value obtained by measuring up to 830 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere using a TG8230 differential thermal balance manufactured by Rigaku, and dividing the weight reduction rate from 100%.

^<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 is measured by dissolving in propylene glycol monomethyl ether acetate (PGMEA) at concentrations of 1, 5 and 10% by mass at 25 ° C. using a RA-520N refractometer manufactured by Kyoto Electronics Industry. And the converted refractive index at 100% by mass was determined.

<Absorption spectrum and fluorescence spectrum>
The absorption spectrum was measured by dissolving in DMSO at a concentration of 1 × 10 ⁻⁵ mol / L using a spectrophotometer V-570 manufactured by JASCO Corporation, and the fluorescence spectrum was measured by a fluorescence spectrophotometer F− manufactured by Hitachi High-Technologies Corporation. Using 4010, measurement was performed by dissolving in DMSO at a concentration of 1 × 10 ⁻⁵ mol / L and exciting at the 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.

[Synthesis Example 1]
Phenol (112.8 g, 1.20 mol), anthracene-9-carbaldehyde (49.4 g, 0.24 mol) and methanol (11.3 g) were placed in a 300 ml reaction vessel with a reflux tube and dissolved at 40 ° C. . Concentrated sulfuric acid (5.6 g) was added, and the reaction was performed at 40 ° C. for 24 hours. Next, the reaction solution was dissolved in methyl isobutyl ketone (169.2 g), and washed with distilled water (56.4 g) several times to remove the catalyst. After distilling off methyl isobutyl ketone and phenol under reduced pressure, xylene (169.2 g) and distilled water (11.3 g) were added and stirred at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 48.3 g (yield 53.3%) of pale yellow 9- (4-hydroxybenzyl) -10- (4-hydroxyphenyl) anthracene.

[Example 1]
Into a 300 ml reaction vessel equipped with a reflux tube, the crystals obtained in Synthesis Example 1 (26.3 g, 0.07 mol), pure water 263.2 g, 48% caustic soda (23.4 g, 0.28 mol) were placed, and at 40 ° C. Dissolved. A 37% aqueous formaldehyde solution (45.4 g, 0.56 mol) was added, and the reaction was performed at 40 ° C. for 24 hours. Next, the reaction solution was dissolved in methyl ethyl ketone (263.2 g), and then neutralized with 20% sulfuric acid. Stirring was stopped and the mixture was allowed to stand, and the aqueous layer was removed. Methyl ethyl ketone was distilled off under reduced pressure, methyl isobutyl ketone (263.5 g) and toluene (525.0 g) were added, and the mixture was stirred at 10 ° C. The precipitated crystals were separated by filtration to obtain 43.6 g of crude crystals. The obtained crude crystals were dissolved in methanol (43.6 g) and toluene (43.6 g) and then stirred at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain the anthracene derivative of Example 1. As a result, 25.4 g (yield 73.0%) of pale yellow crystals was obtained.

The obtained crystal (anthracene derivative of Example 1) had a GPC purity of 98.6%, an HPLC purity of 98.5%, a melting point of 161 ° C., a converted refractive index of 1.655 (25 ° C.), and ¹ H-NMR ( 400 MHz, DMSO-d6, δ, ppm / 4.4, 4.7, 8H, -C H ₂ OH / 5.0, 2H, -C H _2- / 5.0 to 6.0, 4H, -CH _{2 O H /7.0,7.2,4H,Phenyl- H /7.4,7.5,7.7,8.4,8H,Anthryl- H /7.8~9.2,2H} , Phenyl-O H) and ^{13 C-NMR (400MHz, DMSO} -d6, δ, ppm / 32.8, - C H 2 - / 52.5,52.5- C H 2 OH / 125.5,128. 4,128.5,128.7,129.2,131.7,150.1,151.3 , - Phenyl /125.2,125.4,125.9,127.7,129.9,130.2,132.7,137.0,- Anthryl) at 9- (4-hydroxy-3, 5-Dihydroxymethylbenzyl) -10- (4-hydroxy-3,5-dihydroxymethylphenyl) anthracene was confirmed. FIG. 1 shows a ¹ H-NMR chart, and FIG. 2 shows a ¹³ C-NMR chart. Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. FIG. 3 shows an absorption spectrum, and FIG. 4 shows a fluorescence spectrum (excitation wavelength: 381 nm).

[Example 2]
M-Cresol (27.0 g, 0.25 mol) and the crystals obtained in Example 1 (24.8 g, 0.05 mol) were placed in a 300 ml reaction vessel equipped with a reflux tube, and the temperature was raised while stirring. Succinic acid (0.08 g) was added at 80 ° C., and a reflux reaction was performed at an internal temperature of about 105 ° C. for 3 hours. Next, the reflux tube was removed and atmospheric pressure dehydration was performed up to 170 ° C., and then unreacted m-cresol was removed under reduced pressure to obtain the novolak resin (35.5 g) of Example 2.

  The resin of Example 2 had a molecular weight (Mw) of 4086, a glass transition temperature of 141.3 ° C., a residual carbon ratio of 43.6%, and a converted refractive index of 1.663 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. FIG. 5 shows a GPC chart, FIG. 6 shows an absorption spectrum, and FIG. 7 shows a fluorescence spectrum (excitation wavelength: 383 nm).

[Comparative Example 1]
In Example 2, instead of the crystal (24.8 g, 0.05 mol) obtained in Example 1, the crystal (18.8 g, 0.05 mol) obtained in Synthesis Example 1 and paraformaldehyde (6.9 g, The same operation as in Example 2 was performed except that 0.21 mol) was used, to obtain a novolak resin (44.0 g) of Comparative Example 1.

  The resin of Comparative Example 1 is a resin having a molecular weight (Mw) of 547 and no transparency. From the GPC chart, the raw material 9- (4-hydroxybenzyl) -10- (4-hydroxyphenyl) anthracene is contained in the resin structure. It was confirmed that it was not taken in and remained. FIG. 8 shows a GPC chart.

[Comparative Example 2]
Example 1 was the same as Example 1 except that bisphenol-A (16.0 g, 0.07 mol) was used instead of the crystals (26.3 g, 0.07 mol) obtained in Synthesis Example 1. Operation was performed to obtain 12.9 g (yield 53.0%) of 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane (compound of Comparative Example 2).

  The obtained crystal (compound of Comparative Example 2) had a GPC purity of 97.0%, an HPLC purity of 90.8%, a melting point of 126 ° C., a converted refractive index of 1.599 (25 ° C.), and UV lamp (365 nm) irradiation. However, light emission could not be confirmed visually. FIG. 9 shows an absorption spectrum.

[Comparative Example 3]
In Example 1, instead of the crystals (26.3 g, 0.07 mol) obtained in Synthesis Example 1, BPAF which is a commercial product of bisphenolfluorene [trade name: 9,9-bis (4-hydroxy, manufactured by JFE Chemical Co., Ltd.] Phenyl) fluorene] (24.5 g, 0.07 mol) was used in the same manner as in Example 1 except that 21.8 g (yield 66.3%) of 9,9-bis (4-hydroxy-) 3,5-Dihydroxymethylphenyl) fluorene (Compound of Comparative Example 3) was obtained.

  The obtained crystal (compound of Comparative Example 3) had a GPC purity of 96.2%, an HPLC purity of 92.8%, a melting point of 185 ° C., a converted refractive index of 1.645 (25 ° C.), and irradiation with a UV lamp (365 nm). However, light emission could not be confirmed visually, and the fluorescence intensity by the fluorescence spectrophotometer was very weak. FIG. 10 shows an absorption spectrum, and FIG. 11 shows a fluorescence spectrum (excitation wavelength: 313 nm).

[Comparative Example 4]
In Example 2, except that the crystal (17.4 g, 0.05 mol) obtained in Comparative Example 2 was used instead of the crystal (24.8 g, 0.05 mol) obtained in Example 1, The same operation as in Example 2 was performed to obtain a novolak resin (29.7 g) of Comparative Example 4.

  The resin of Comparative Example 4 had a molecular weight (Mw) of 4234, a glass transition temperature of 113.9 ° C., a residual carbon ratio of 25.0%, and a converted refractive index of 1.623 (25 ° C.). Moreover, although UV lamp (365 nm) irradiation was performed, light emission was not able to be confirmed visually. FIG. 12 shows a GPC chart, and FIG. 13 shows an absorption spectrum.

[Comparative Example 5]
In Example 2, except that the crystal (14.1 g, 0.05 mol) obtained in Comparative Example 3 was used instead of the crystal (24.8 g, 0.05 mol) obtained in Example 1, The same operation as in Example 2 was performed to obtain a novolak resin (20.7 g) of Comparative Example 5.

  The resin of Comparative Example 5 had a molecular weight (Mw) of 4729, a glass transition temperature of 128.3 ° C., a residual carbon ratio of 39.9%, and a converted refractive index of 1.638 (25 ° C.). Moreover, although UV lamp (365 nm) irradiation was performed, light emission was not able to be confirmed visually and the fluorescence intensity by a fluorescence spectrophotometer was also very weak. FIG. 14 shows a GPC chart, FIG. 15 shows an absorption spectrum, and FIG. 16 shows a fluorescence spectrum (excitation wavelength: 313 nm).

  As the above evaluation results, the evaluation results of the anthracene derivative of Example 1 and the compounds of Comparative Example 2 and Comparative Example 3 of this Comparative Example are shown in Table 1, the resin of Example 2 and Comparative Examples 1 and Comparative Example of this Comparative Example are shown in Table 1. 4 and the evaluation results of the resins of Comparative Example 5 are shown again in Table 2.

  As shown in this example, the anthracene derivative of Example 1 was shown to have a higher refractive index and fluorescence properties with respect to ultraviolet light than other thermosetting bisphenol derivatives (Comparative Examples 2 and 3). It was.

  In addition, the resin of Example 2 obtained using the anthracene derivative of Example 1 as a raw material is more efficient than the resin produced using anthracene derivative having no methylol group and formaldehyde as raw materials (resin of Comparative Example 1). Since the anthracene skeleton was incorporated into the structure, it was possible to increase the molecular weight and to show a high glass transition temperature and a residual carbon ratio.

  In addition, the resin shown in Example 2 is similar in refractive index to glass compared with resins produced from bisphenol-A derivatives and bisphenolfluorene derivatives having methylol groups (Comparative Examples 4 and 5). It was shown that it has excellent characteristics in all of transition temperature, residual carbon ratio, and fluorescence characteristics.

The anthracene derivative of the present invention can be used, for example, as a resin raw material or a crosslinking agent. Resins obtained from this anthracene derivative include, for example, molded products, laminated products, shell molds, building materials, adhesives, friction materials, paints, grindstones, electronic materials, thermal paper, pressure sensitive paper, epoxy resin curing agents, and photoresists. It can be used for materials, antireflection films, semiconductor encapsulants, recording materials and the like.

Claims (6)

An anthracene derivative represented by the following formula (1).
(In formula (1), X and Y are each independently a hydroxyaryl group in which one or more hydrogen atoms on the aromatic ring are substituted with * —CH ₂ OZ. * Is a hydroxyaryl group And a plurality of Z contained in X and Y are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) _2. The anthracene derivative according to claim 1, wherein X and Y are each independently a hydroxyphenyl group in which one or two hydrogen atoms on the aromatic ring are substituted with * —CH ₂ OZ.   The anthracene derivative according to claim 1 or 2, wherein Z is a hydrogen atom.   A resin obtained by using the anthracene derivative according to claim 1, claim 2 or claim 3.   A curable composition comprising at least one selected from the group consisting of the anthracene derivative according to claim 1, claim 2 or claim 3 and the resin according to claim 4.   A cured product obtained by curing the curable composition according to claim 5.