JP5778462B2 - Anthracene derivative and method for producing the same, curable composition, and cured product - Google Patents

Description

  The present invention relates to a novel anthracene derivative, a production method thereof, a curable composition, 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 photorefractive properties, it is useful 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.

  Examples of the anthracene derivative include a radiation-sensitive resin composition (see JP 2005-346024 A) having advantages such as high sensitivity, high resolution, high etching resistance, and low sublimation in the photoresist field. Use as an antireflection film (see JP-A-7-82221) 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).

  Furthermore, as an anthracene derivative, a photo-curing polymer that acts 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 Patent Application Laid-Open No. 2007-99637). And a technology for obtaining a polymer having ultraviolet absorbing ability and flame retardancy (see JP 2008-1637 A). However, such polymerizable anthracene derivatives are also expected to have higher functions in various performances such as high photorefractive properties.

JP 2005-346024 A JP-A-7-82221 JP 2009-40765 A JP-A-6-295151 JP 2007-99637 A JP 2008-1637 A

  The present invention has been made based on the above-described circumstances, and an anthracene derivative having both high photorefractive properties and anthracene-specific properties such as fluorescence performance with respect to ultraviolet rays, and high polymerizability, and a method for producing the anthracene derivative The purpose is to provide. Another object of the present invention is to provide a curable composition and a cured product that have high functionality such as high photorefractive properties and excellent fluorescence characteristics using this anthracene derivative and can be applied in various technical fields. To do.

（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。Ｒ^１及びＲ^２は、それぞれ独立して、水素原子又はメチル基である。Ｚ^１及びＺ^２は、それぞれ独立して、−Ｏ−（Ｒ−Ｏ）_ｍ−で表される基である。Ｒは、２価の炭化水素基であり、この炭化水素基がヒドロキシル基を有していてもよい。ｍは、０以上の整数である。ｍが２以上の場合、複数のＲは同一でも異なっていてもよい。） The invention made to solve the above problems is
It is an anthracene derivative 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. The aromatic group may have a substituent, n ₁ and n ₂ are each independently an integer of ^{1 to 3.} R ¹ and R ² are each independently Z ¹ and Z ² are each independently a group represented by —O— (R—O) _m —, where R is a divalent hydrocarbon group. The hydrocarbon group may have a hydroxyl group.m is an integer of 0 or more. When m is 2 or more, a plurality of R may be the same or different.)

  Since the anthracene derivative has an anthracene skeleton, it has various characteristics unique to anthracene such as fluorescence characteristics and photosensitization. In particular, since the anthracene derivative has aromatic rings connected from the 9th and 10th positions of the anthracene skeleton, it can exhibit excellent performance such as high carbon density, high melting point, and high photorefractive property. Furthermore, since the anthracene derivative has two or more (meth) acrylic groups, it is excellent in polymerizability (including crosslinkability).

（式（３）中、ｍ_１及びｌ_１は、それぞれ独立して、１〜４の整数である。
式（４）中、Ｒ^３及びＲ^４は、どちらか一方がメチル基であり、他方が水素原子である。ｌ_２は、１〜４の整数である。
式（６）中、ｍ_２及びｌ_３は、それぞれ独立して、１〜４の整数である。
式（７）中、Ｒ^５及びＲ^６は、どちらか一方がメチル基であり、他方が水素原子である。ｌ_４は、１〜４の整数である。
＊は、Ｘ又はＹとの結合箇所を表す。） It is preferable that Z ¹ and Z ² represented by the above formula (1) are each independently a group represented by any one of the following formulas (2) to (7).

(In formula (3), m ₁ and l ₁ are each independently an integer of 1 to 4.
In formula (4), one of R ³ and R ⁴ is a methyl group and the other is a hydrogen atom. l ₂ is an integer of 1 to 4.
In formula (6), m ₂ and l ₃ are each independently an integer of 1 to 4.
In formula (7), one of R ⁵ and R ⁶ is a methyl group and the other is a hydrogen atom. l ₄ is an integer of 1 to 4.
* Represents a bonding site with X or Y. )

According to the anthracene derivative, by introducing a group having the above structure as Z ¹ and Z ² , a (meth) acryl group can be easily introduced and the productivity is excellent.

X and Y represented by the above formula (1) may be a phenylene group, and n ₁ and n ₂ may be 1. The anthracene derivative is not complicated in structure and can be efficiently produced, and can further increase the optical refractive index and the like.

  The curable composition of the present invention includes the anthracene derivative and / or a polymer obtained from the anthracene derivative. The curable composition is excellent in curability due to polymerizability and photosensitization of the anthracene derivative and the like, and a cured product having properties specific to anthracene such as fluorescence characteristics and high photorefractive properties can be obtained.

  The cured product of the present invention is obtained by curing the curable composition. Since the cured product has high functionality such as high photorefractive property and fluorescence performance, it can be used as a resin that can be applied to various fields.

（式（８）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（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。Ｒ^１及びＲ^２は、それぞれ独立して、水素原子又はメチル基である。Ｚ^１及びＺ^２は、それぞれ独立して、下記式（２）又は（５）で表される基である。）

The method for producing the anthracene derivative of the present invention includes:
In the presence of a basic compound, the anthracene derivative represented by the following formula (8) is reacted with at least one selected from the group consisting of acrylic acid, methacrylic acid, halogenated acrylic, halogenated methacrylic, glycidyl acrylate and glycidyl methacrylate. It is a manufacturing method of the anthracene derivative represented by following formula (1 ') which has a process to make.

(In Formula (8), 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 (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. And n ₁ and n ₂ are each independently an integer of ^{1 to 3.} R ¹ and R ² are each independently a group. Z ¹ and Z ² are each independently a group represented by the following formula (2) or (5).

  According to the production method, a compound in which a plurality of (meth) acryl groups are introduced from the anthracene derivative represented by the above formula (8) can be efficiently obtained.

（式（８）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（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。Ｒ^１及びＲ^２は、それぞれ独立して、水素原子又はメチル基である。Ｚ^１及びＺ^２は、それぞれ独立して、下記式（３）、（４）、（６）又は（７）で表される基である。）

（式（３）中、ｍ_１及びｌ_１は、それぞれ独立して、１〜４の整数である。
式（４）中、Ｒ^３及びＲ^４は、どちらか一方がメチル基であり、他方が水素原子である。ｌ_２は、１〜４の整数である。
式（６）中、ｍ_２及びｌ_３は、それぞれ独立して、１〜４の整数である。
式（７）中、Ｒ^５及びＲ^６は、どちらか一方がメチル基であり、他方が水素原子である。ｌ_４は、１〜４の整数である。
＊は、Ｘ又はＹとの結合箇所を表す。） The production method different from the above for the anthracene derivative of the present invention is as follows.
In the presence of a basic compound, the anthracene derivative represented by the following formula (8) is reacted with at least one selected from the group consisting of halogenated alcohols, alkylene carbonates and alkylene oxides, and then acrylic acid, methacrylic acid, It is a method for producing an anthracene derivative represented by the following formula (1 ″) having a step of reacting at least one selected from the group consisting of halogenated acrylic, halogenated methacrylic, glycidyl acrylate and glycidyl methacrylate.

(In Formula (8), 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 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. And n ₁ and n ₂ are each independently an integer of ^{1 to 3.} R ¹ and R ² are each independently a group. Z ¹ and Z ² are each independently a group represented by the following formula (3), (4), (6) or (7).

(In formula (3), m ₁ and l ₁ are each independently an integer of 1 to 4.
In formula (4), one of R ³ and R ⁴ is a methyl group and the other is a hydrogen atom. l ₂ is an integer of 1 to 4.
In formula (6), m ₂ and l ₃ are each independently an integer of 1 to 4.
In formula (7), one of R ⁵ and R ⁶ is a methyl group and the other is a hydrogen atom. l ₄ is an integer of 1 to 4.
* Represents a bonding site with X or Y. )

  Also according to the production method, a compound into which a plurality of (meth) acryl groups are introduced can be efficiently obtained from the anthracene derivative represented by the above formula (8).

  As described above, the anthracene derivative of the present invention has high polymerizability along with anthracene-specific properties (high photorefractive properties, fluorescence performance with respect to ultraviolet rays, etc.), and is useful as various resin materials and photosensitizers. . Further, the curable composition containing the anthracene derivative and the cured product include, for example, an adhesive, a paint, a laminate, a molding material, a casting material, a semiconductor sealing material, a printed board insulating material, a coating material, an optical material, and a structure. Applications in various technical fields such as materials and photoresist raw materials can be developed.

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. FIG. 3 is a diagram showing a ¹ H-NMR chart of the compound of Example 3. 3 is a diagram showing a ¹³ C-NMR chart of the compound of Example 3. FIG. 4 is a graph showing an absorption spectrum of the compound of Example 3. FIG. 4 is a graph showing a fluorescence spectrum of the compound of Example 3. FIG. 4 is a diagram showing a ¹ H-NMR chart of an anthracene derivative of Example 4. FIG. 4 is a diagram showing a ¹³ C-NMR chart of an anthracene derivative of Example 4. FIG. 6 is a graph showing an absorption spectrum of an anthracene derivative of Example 4. FIG. 6 is a graph showing a fluorescence spectrum of an anthracene derivative of Example 4. FIG. 6 is a diagram showing a ¹ H-NMR chart of an anthracene derivative of Example 5. FIG. 6 is a diagram showing a ¹³ C-NMR chart of an anthracene derivative of Example 5. FIG. 6 is a graph showing an absorption spectrum of an anthracene derivative of Example 5. FIG. 6 is a graph showing a fluorescence spectrum of an anthracene derivative of Example 5. FIG.

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

In the above formula (1), the aromatic group represented by X and Y includes (n ₁ +1) hydrogen atoms from aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene and triphenylene. Or the group etc. which excluded (n < ₂ > +1) piece etc. are mentioned.

Both of the aromatic groups represented by X and Y may have a substituent. Examples of these substituents include an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an amino group, and 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, and are (n ₁ +1) valence or (n ₂ +1) valence.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups.

  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.

  Examples of the alkoxy group include linear, branched, monocyclic or condensed polycyclic alkoxy groups.

  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- List octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decylcyclohexyloxy group, etc. It can be.

  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 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.

  As the X or Y, the anthracene derivative having an aromatic group having a substituent can further add or adjust the function while maintaining the characteristics of the anthracene derivative. For example, in X or Y, according to the anthracene derivative 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 anthracene derivative. The substituted alkyl group preferably has a low molecular weight from the viewpoint of the steric stability of the anthracene derivative. Specifically, an alkyl group having 5 or less carbon atoms is preferable, and a methyl group or an ethyl group is preferable. Particularly preferred.

Among the aromatic groups represented by X or Y, (n ₁ +1) hydrogen atoms from an aromatic hydrocarbon having no substituent, in terms of high photorefractive properties, high carbon density, high melting point, and the like, Or a group obtained by removing (n ₂ +1) is preferable, and a group obtained by removing (n ₁ +1) or (n ₂ +1) hydrogen atoms from benzene and naphthalene having no substituent is more preferred. A group obtained by removing (n ₁ +1) or (n ₂ +1) hydrogen atoms from benzene having no group is more preferable. X and Y may be different, but are preferably the same from the viewpoint of high photorefractive properties, ease of production, and the like.

In the above formula (1), n ₁ and n ₂ are integers of 1 to 3, but n ₁ and n ₂ from the viewpoint of ease of synthesis, controllability of curing, toughness of the resulting cured product, and the like. Both are preferably 1 or 2, and more preferably 1.

In the anthracene derivative, both n ₁ and n ₂ are 1, and X and Y are groups obtained by removing two hydrogen atoms from benzene having no substituent (phenylene group). It is preferable in terms of melting point, high photorefractive property, toughness of the resulting cured product, ease of synthesis and manufacturability of the cured product from this compound. In this case, from the viewpoints of high melting point, ease of production, etc., it is preferable that the group having a (meth) acryl group in the phenylene group is located in the para position with respect to the anthracene skeleton.

R ¹ and R ² are each independently a hydrogen atom or a methyl group.

Z ¹ and Z ² are each independently a group represented by —O— (R—O) _m —. R is a divalent hydrocarbon group, and this hydrocarbon group may have a hydroxyl group. m is an integer of 0 or more. When m is 2 or more, a plurality of R may be the same or different.

  As the divalent hydrocarbon group, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group are linked. The group can be mentioned. Examples of the divalent aliphatic hydrocarbon group include a methanediyl group, an ethanediyl group, a propanediyl group, and a butanediyl group. Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group.

  Among the divalent hydrocarbon groups, a divalent aliphatic hydrocarbon group is preferable, and a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable. In addition, these hydrocarbon groups may have a hydroxy group.

  M is an integer of 0 or more, preferably 0 or more and 10 or less, more preferably 0 or more and 5 or less, and still more preferably 0 and 1.

Z ¹ and Z ² are preferably each independently a group represented by any one of the above formulas (2) to (7).

In Formula (3), m ₁ is an integer of 1 to 4, but 2 is preferable. l ₁ is an integer of 1 to 4, but 1 is preferable.

In formula (4), one of R ³ and R ⁴ is a methyl group and the other is a hydrogen atom. l ₂ is an integer of 1 to 4.

Wherein (6), _{m 2} is an integer of 1 to 4. l ₃ is an integer of 1 to 4.

In formula (7), one of R ⁵ and R ⁶ is a methyl group and the other is a hydrogen atom. l ₄ is an integer of 1 to 4.

In formulas (6) to (7), * represents a bonding site with X or Y. When l ₁ , l ₂ , l ₃ or l ₄ is 2 or more, the plurality of m ₁ , m ₂ and R ^{3 to} R ⁶ may be the same or different.

  Of the groups represented by formulas (2) to (7), groups represented by formulas (2), (3) and (5) are preferred from the viewpoint of ease of synthesis and the like.

  Since the anthracene derivative has the anthracene skeleton in this way, it has various characteristics peculiar to anthracene such as high carbon density, high photorefractive property, high melting point, and fluorescence performance with respect to ultraviolet rays.

  Among the above properties, for example, in terms of the photorefractive index, the anthracene derivative has an anthracene skeleton even when compared with a compound having a plurality of (meth) acrylic groups, and thus has a high refractive index equal to or higher than that. Have. Specifically, the refractive index of the anthracene derivative can be 1.6 or more. In addition, the refractive index of the said anthracene derivative, other carbon density, melting | fusing point, etc. can be adjusted by selecting the substituent shown by X and Y, etc.

  Since the anthracene derivative has a plurality of (meth) acrylic groups, the anthracene derivative has various characteristics peculiar to anthracene and has polymerizability (including crosslinkability). Therefore, according to the said anthracene derivative, by making it contain in a curable composition, it functions as a main component, a photosensitizer, etc., and can give high performance to the hardened | cured material obtained. In particular, the anthracene derivative has high symmetry because the aromatic rings are arranged at the 9th and 10th positions of the anthracene ring, and the main chain of the polymer is obtained by crosslinking two or more (meth) acryl groups. It is possible to introduce an anthracene skeleton into the chain. Therefore, according to the anthracene derivative, it is possible to obtain a polymer having excellent mechanical properties utilizing the rigidity derived from the anthracene skeleton, and the aromatic rings are arranged at the 9th and 10th positions, which are the short axes of the anthracene skeleton. Therefore, when introduced into the polymer skeleton, a specific function is exhibited such that the polymer has a very high carbon density.

<Method for producing anthracene derivative>
The anthracene derivative of the present invention is obtained, for example, by reacting a phenol with an anthracene-9-carbaldehyde in the presence of a non-reactive oxygen-containing organic solvent and an acid catalyst, and the like (represented by the above formula (8)). The anthracene derivative) can be produced by the first step, and the second step of (meth) acrylating the obtained bisphenolanthracene compound and the like.

In the formula (8), X, Y, of the defined and exemplified _{n 1} and _{n 2} are the same as in the above formula (1).

<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 phenolic compound means the phenol by which the hydrogen on a 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 an 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, an anthracene derivative in which X and Y in the above formula (8) are phenylene groups can be produced by selecting phenol as the phenol. 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, a non-reactive oxygen-containing organic solvent having one or more oxygen atoms in the molecule may be 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. Examples of the non-reactive oxygen-containing organic solvent include alcohols, polyhydric alcohol ethers, cyclic ethers, polyhydric alcohol esters, ketones, alkyl 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 isobutyl ketone. Examples of the alkyl 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.

  As a non-reactive oxygen-containing organic solvent, it is not limited to said illustration, Moreover, you may use each individually or in mixture of 2 or more types. As a minimum of the compounding quantity of a non-reactive oxygen-containing organic solvent, 1 mass part is preferred to 100 mass parts of phenols, 2 mass parts is still more preferred, and 5 mass parts is especially preferred. Moreover, as an upper limit of the compounding quantity of a non-reactive oxygen-containing organic solvent, 1,000 mass parts is preferable with respect to 100 mass parts of phenols, 500 mass parts is further more preferable, and 100 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 may be lowered, the productivity may be lowered, and the purification energy may be increased.

  Acid catalysts in the first step include 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, strong acid ion exchange resins, etc. I can list them. 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 in the first step 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 in the first step is usually 0-100 ° C, preferably 25-60 ° 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 reaction of the first step is usually normal pressure, but may be performed under pressure or reduced pressure. Specifically, the internal pressure (gauge pressure) is -0.02 to 0.2 MPa. It is preferable that it is the range of these.

  The reaction time in the reaction of the first step 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. Is preferably in the range of 1 to 48 hours.

  After completion of the reaction in the first step, the acid catalyst is removed and the product is separated. As a method for removing the catalyst, generally, the product is dissolved in a poorly water-soluble 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, after removing the catalyst, the anthracene derivative represented by the above formula (8) (bisphenol anthracene compound or the like) 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 anthracene derivative (bisphenol anthracene compound, etc.) represented by the above formula (8), which is the target product of the first step, can be purified by a method such as column chromatography or the like.

<Second step>
In the second step, the obtained anthracene derivative represented by the above formula (8) is (meth) acrylated. Specific examples of the second step include the following second step A and second step B.

(Second step A)
The second step A is selected from the group consisting of acrylic acid, methacrylic acid, halogenated acrylic, halogenated methacrylic, glycidyl acrylate and glycidyl methacrylate as an anthracene derivative represented by the above formula (8) in the presence of a basic compound. This is a step of reacting at least one selected from the above.

By passing through the second step A, an anthracene derivative represented by the above formula (1 ′) can be produced. By using acrylic acid, methacrylic acid, halogenated acrylic or halogenated methacrylic, a group represented by the formula (2) as Z ¹ and Z ^2, by using glycidyl acrylate or glycidyl methacrylate, Z ¹ and Z ² As described above, a group represented by the formula (5) can be introduced. In the above formula (1 ′), the definition and illustration of X, Y, n ₁ , n ₂ , R ¹ and R ² are the same as those in the above formula (1), and Z ¹ and Z ² are each independently It is group represented by the said Formula (2) or (5).

  Examples of the basic compound in the second step A include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, methylamine and triethylamine. An amine compound etc. are mentioned, etc., and 1 type, or 2 or more types of these can be used. The amount of the basic compound used is, for example, 0.1 to 10 mol, preferably 1 to 6 mol, relative to 1 mol of the anthracene derivative (bisphenol anthracene compound etc.) represented by the above formula (8). is there.

  Examples of the halogenated acrylic include acryloyl chloride and acryloyl bromide. Examples of the halogenated methacryl include methacryloyl chloride and methacryloyl bromide.

  The blending amount of acrylic acid, methacrylic acid, halogenated acrylic, halogenated methacrylic, glycidyl acrylate and glycidyl methacrylate in the second step A is based on 1 mol of the anthracene derivative (bisphenol anthracene compound etc.) represented by the above formula (8). For example, it is 2-30 mol, Preferably, it is 2-10 mol.

  The reaction in the second step A is usually performed in a solvent. The solvent is not particularly limited as long as no side reaction occurs, but alcohols, polyhydric alcohol ethers such as ethyl cellosolve (ethylene glycol monoethyl ether), cyclic ethers, polyhydric alcohol esters, methyl isobutyl Examples thereof include ketones such as ketones, alkyl esters, and the like. As the usage-amount of this solvent, 100-1,000 mass parts is preferable with respect to 100 mass parts of anthracene derivatives (bisphenol anthracene compound etc.) represented by the said Formula (8).

In addition, when using glycidyl acrylate or glycidyl methacrylate, it is preferable to react by adding a polymerization inhibitor such as p-methoxyphenol into the solvent.
The reaction time in the second step A depends on the reaction molar ratio, reaction temperature, pressure and the like and cannot be determined unconditionally. However, it is usually preferably 0.5 hours or more and 48 hours or less.

  As reaction temperature in the 2nd process A, it can be set as 30 to 100 degreeC, for example.

  After completion of the reaction in the second step A, the product is separated by a known method. Separation of the product can be efficiently performed by washing the reaction solution and then adding an alcohol such as methanol to precipitate it as crystals. The crystals thus precipitated can be filtered, washed and dried by a known method to purify the anthracene derivative represented by the above formula (1 ').

(Second step B)
In the second step B, an anthracene derivative represented by the following formula (8) is reacted with at least one selected from the group consisting of halogenated alcohols, alkylene carbonates and alkylene oxides in the presence of a basic compound, In this step, at least one selected from the group consisting of acrylic acid, methacrylic acid, halogenated acrylic, halogenated methacrylic, glycidyl acrylate and glycidyl methacrylate is reacted.

By passing through the second step B, an anthracene derivative represented by the above formula (1 ″) can be produced. Depending on the selection of the kind of halogenated alcohol, alkylene carbonate and alkylene oxide, the number of repetitions is ₁ to The structure of the portion of l ₄ is formed, and then represented by formula (3) or (4) as Z ¹ and Z ² by using acrylic acid, methacrylic acid, halogenated acrylic or halogenated methacrylic. By using glycidyl acrylate or glycidyl methacrylate as the group, the group represented by the formula (6) or (7) can be introduced as Z ¹ and Z ^{2. In the} above formula (1 ″), X, Y , the defined and exemplified _{n ^1, n 2,} ^R 1 and ^{R 2} are the same as in the above formula (1), ^{Z 1} and ^{Z 2} are each independently the above formula (3) (4) a group represented by (6) or (7). Examples of the groups represented by the above formulas (3), (4), (6) and (7) are as described above.

  In the presence of a basic compound, the anthracene derivative represented by the following formula (8) is reacted with at least one selected from the group consisting of halogenated alcohols, alkylene carbonates, and alkylene oxides, to obtain the following formula (9). The compounds represented are synthesized.

In the above formula (9), the definitions and examples of X, Y, n ₁ , n ₂ , Z ¹ and Z ² are the same as those in the above formula (1 ″). The compound can be suitably used as an intermediate for obtaining the anthracene derivative of the present invention.

  Examples of the basic compound in the second step B include those exemplified in the second step A. This reaction is also usually carried out in a solvent, and examples of this solvent include those exemplified in the second step A.

  Examples of the halogenated alcohol include chloromethanol, 2-chloro-1-ethanol, 3-chloro-1-propanol, and 3-bromo-1-propanol.

  Examples of the alkylene carbonate include ethylene carbonate and propylene carbonate.

  Examples of the alkylene oxide include ethylene oxide and propylene oxide.

  The compounding quantity of halogenated alcohol, alkylene carbonate, and alkylene oxide is 2-30 mol with respect to 1 mol of anthracene derivatives (bisphenol anthracene compound etc.) represented by the said Formula (8), Preferably, it is 2. 5 to 10 moles.

  The reaction time in the above reaction is, for example, about 1 hour to 12 hours.

  The compound represented by the above formula (9) obtained as described above is separated and purified by a known method.

  Next, the compound represented by the above formula (9) is reacted with at least one selected from the group consisting of acrylic acid, methacrylic acid, halogenated acrylic, halogenated methacrylic, glycidyl acrylate and glycidyl methacrylate.

  Examples of the halogenated acrylic and halogenated methacrylic acid include those exemplified in the second step A.

  The above reaction is also usually performed in a solvent. The solvent is not particularly limited as long as no side reaction occurs, and examples thereof include toluene.

  When using acrylic acid and methacrylic acid, etc., under an acidic catalyst such as inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, organic acid such as oxalic acid, paratoluenesulfonic acid, methanesulfonic acid, phenolsulfonic acid, etc. Preferably it is done. Moreover, it is preferable to react by adding a polymerization inhibitor such as p-methoxyphenol into the solvent.

  The reaction time in the above reaction is, for example, about 1 hour to 12 hours, and the reaction temperature is about 10 ° C. to 80 ° C.

  The anthracene derivative represented by the above formula (1 ″) obtained as described above can be separated and purified by a known method.

  In addition, the anthracene derivative of the present invention other than the anthracene derivative represented by the above formula (1 ′) or (1 ″) can also be produced by a method according to the second step A and the second step B.

<Curable composition>
The curable composition of this invention contains the polymer obtained from the anthracene derivative represented by the said Formula (1) and / or this anthracene derivative. In the curable composition, the anthracene derivative represented by the above formula (1) and / or the polymer obtained from this anthracene derivative can function as an auxiliary component such as a main component or a photosensitizer. The composition has curability, has properties unique to compounds having an anthracene skeleton such as fluorescent properties, and is suitable for resin raw materials, adhesives, paints, etc. that synthesize various resins with high versatility and added value. Can be used. Examples of the polymer obtained from the anthracene derivative include a polymer obtained by crosslinking the anthracene derivative with light or heat, and a copolymer of the anthracene derivative with another monomer.

  In the said curable composition, other components other than the polymer obtained from the said anthracene derivative and / or this anthracene derivative may be included, and these other components are used when manufacturing each resin. The well-known thing is mentioned. Examples of the other components include other monomers, polymerization initiators, solvents, inorganic fillers, pigments, thixotropic agents, fluidity improvers, and the like.

<Hardened product>
The cured product of the present invention is obtained by curing the curable composition. The cured product can be used as various resins. The cured product can be used for various applications as a highly versatile material having various characteristics such as a high melting point, a high refractive index, and fluorescence performance derived from an anthracene skeleton. In addition, the said hardened | cured material can be obtained by using the well-known method corresponding to each composition, such as light irradiation to the said curable composition, a heating.

  These cured products make use of functionality, such as optical materials such as lenses and optical sheets, recording materials such as hologram recording materials, organic photoreceptors, photoresist materials, antireflection films, semiconductor encapsulants, etc. It can be used as a material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by this Example. In addition, the measurement of the obtained anthracene derivative was performed with the following measuring apparatus 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>
The HPLC purity and reaction end point confirmation was performed using Shimadzu HPLC Promince series, UV detector SPD-20A (246 nm), GL Science ODS-3 (4.6 mmφ × 250 mm) column, and water / acetonitrile as the developing solvent. Depending on the compound, the solution was fed at a specified ratio and determined by the area ratio of the target peak.

<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.

<Refractive index>
The refractive index of the compound is measured by dissolving it in propylene glycol monomethyl ether acetate (PGMEA) at concentrations of 1, 5 and 10% by mass at 25 ° C. using an RA-520N refractometer manufactured by Kyoto Electronics Industry, A calibration curve was created to obtain the converted refractive index at 100% by mass.

  The refractive index of the cured product was measured at 25 ° C. using an Abbe refractometer manufactured by Atago Co., Ltd. The dimensions of the test piece were 25 mm × 10 mm × 50 μm, and the refractive index was determined using 1-bromonaphthalene as the contact liquid.

^<1 H-NMR and ¹³ C-NMR>
¹ H-NMR and ¹³ C-NMR were measured with DMSO-d ₆ solvent or chloroform-d ₁ using UNITY-INOVA 400 MHz manufactured by Varian and TMS as a reference substance.

<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] Synthesis of bisphenolanthracene Phenol (112.8 g, 1.20 mol), anthracene-9-carbaldehyde (49.4 g, 0.24 mol) and methanol (11.3 g) 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 give 48.3 g (yield) of pale yellow 9- (4-hydroxybenzyl) -10- (4-hydroxyphenyl) anthracene (compound represented by the following formula). 53.3%).

[Synthesis Example 2] Synthesis of biscresol anthracene In a 300 mL reaction vessel with a reflux tube, o-cresol (108.1 g, 1.00 mol), anthracene-9-carbaldehyde (41.3 g, 0.20 mol) and methanol (54 0.0 g) was added and dissolved at 40 ° C. 35% hydrochloric acid (10.8 g) was added, and the reaction was performed at 40 ° C. for 24 hours. Next, the reaction solution was dissolved in methyl isobutyl ketone (216.0 g), and washed with distilled water (216.0 g) several times to remove the catalyst. After distilling off methyl isobutyl ketone and phenol under reduced pressure, xylene (324.3 g) and hexane (21.5 g) were added and stirred at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to give pale yellow 9- (3-methyl-4-hydroxybenzyl) -10- (3-methyl-4-hydroxyphenyl) anthracene (represented by the following formula). Compound) 45.1 g (yield 55.7%) was obtained.

[Example 1] Acrylation reaction of bisphenol anthracene A bisphenol anthracene compound (15.05 g, 0.04 mol) obtained in Synthesis Example 1, methyl isobutyl ketone (30.1 g), triethylamine ( 10.1 g, 0.1 mol) was added and dissolved by stirring. Acryloyl chloride (7.24 g, 0.08 mol) was added at 30 ° C. or lower and then heated and reacted at 60 ° C. for 1 hour. After cooling to 40 ° C. or lower, methanol (15.0 g) and 10% aqueous NaCl (90.3 g) were added, and the mixture was allowed to stand after stirring. After removing the lower layer, it was repeatedly washed with distilled water (90.3 g) until the waste liquid pH became 7. After concentration under reduced pressure, the mixture was cooled, methanol (300.0 g) was added, and crystallization was performed at 20 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 2.8 g of pale yellow crystals.

The obtained crystal had a GPC purity of 97.9%, an HPLC purity of 97.0%, a melting point of 126.9 ° C., and a converted refractive index of 1.644 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. ^{1 H-NMR (400MHz, DMSO} -d 6, δ, ppm / 5.1,2H, -C H 2 - / 6.1~6.3,6.4~6.5,6.6~6. _{7,4H, -CH = C H 2 /6.3~6.4,6.4~6.5,2H,-C} H = CH 2 /7.0,7.2,7.4,8H, Phenyl- H / 7.4, 7.5, 7.6, 8.4, 8H, Anthryl- H ) and ¹³ C-NMR (400 MHz, DMSO-d ₆ , δ, ppm / 32.2, -C H _{2 - / 164.4, -O- C O} -vinyl / 127.8,127.9,135.5,136.2, - vinyl /121.9,122.2,129.7,129.8, 133.7,134.0,148.5,149.9, - Phenyl /125.3,125.7,126.2,127 1, 129.1, 132.3, 132.7, 138.9, -Anthryl )) and 9- (4-hydroxybenzyl) -10- (4-hydroxyphenyl) anthracene diacrylate (represented by the following formula) Anthracene derivatives). 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: 380 nm).

[Example 2] Acrylation reaction of biscresol anthracene A biscresol anthracene compound (10.1 g, 0.025 mol) obtained in Synthesis Example 2 in a 300 mL reaction vessel with a reflux tube, methyl isobutyl ketone (30.3 g), Triethylamine (6.3 g, 0.06 mol) was added and dissolved by stirring. Acryloyl chloride (5.2 g, 0.057 mol) was added at 30 ° C. or lower and then heated and reacted at 40 ° C. for 3 hours. Methanol (10.1 g) and 10% aqueous NaCl (90.6 g) were added, and the mixture was allowed to stand after stirring. After removing the lower layer, it was repeatedly washed with distilled water (90.6 g) until the waste liquid pH became 7. After concentration under reduced pressure, the mixture was cooled, methanol (61.3 g) was added, and crystallization was performed at 10 ° C. The precipitated crystals were separated by filtration and then dried under reduced pressure to obtain 3.1 g of light yellow crystals.

  The obtained crystal had a GPC purity of 95.1%, an HPLC purity of 98.6%, and a converted refractive index of 1.636 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. The obtained compound is presumed to be an anthracene derivative represented by the following formula.

[Example 3] EO addition reaction of bisphenolanthracene bisphenolanthracene compound (56.4 g, 0.15 mol) obtained in Synthesis Example 1, ethyl cellosolve (169.2 g), sodium hydroxide in a 500 mL reaction vessel with a reflux tube (3.0 g, 0.075 mol) was added and dissolved by stirring at 50 ° C. Ethylene carbonate (39.6 g, 0.45 mol) was added, and the mixture was heated and refluxed for 6 hours. After cooling to 100 ° C. or lower, methyl isobutyl ketone (169.0 g) was added and dissolved by stirring. After cooling to 30 ° C. or lower, the mixture was neutralized with 20% aqueous sulfuric acid (20.6 g) and washed three times with distilled water (169.0 g). After concentration under reduced pressure, toluene (339.0 g) was added and crystallized at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 62.8 g of pale yellow crystals.

The obtained crystals had a GPC purity of 99.5%, an HPLC purity of 99.9%, a melting point of 143.4 ° C., and a converted refractive index of 1.649 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. ^{1 H-NMR (400MHz, DMSO} -d 6, δ, ppm / 4.9,2H, -C H 2 - / 3.6,3.8~3.9,4.1,8H, - Ethylene - / 4.8,5.0,2H, -O H /6.7,7.0,7.1,7.2,8H,Phenyl- H /7.3,7.4,7.6,8. 3,8H, Anthryl- H) and ^{13 C-NMR (400MHz, DMSO} -d 6, δ, ppm / 32.0, - C H 2 - / 59.8,59.9,69.6,69.8 , - Ethylene - / 114.6,114.7,129.7,130.1,132.8,133.1,157.1,158.4, - Phenyl /125.3,125.9,127. 3, 129.1, 130.4, 132.3, 136.2, -Anthryl )) 9- (4-hydroxybenzyl) -10- (4-hydroxyphenyl) anthracene bisethanol (compound represented by the following formula: bisphenolanthracene EO adduct). FIG. 5 shows a ¹ H-NMR chart, and FIG. 6 shows a ¹³ C-NMR chart. Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. FIG. 7 shows an absorption spectrum, and FIG. 8 shows a fluorescence spectrum (excitation wavelength: 380 nm).

[Example 4] Acrylation reaction of bisphenolanthracene EO adduct The bisphenolanthracene EO adduct obtained in Example 3 (13.9 g, 0.03 mol) and acrylic acid (5.4 g) in a 300 mL reaction vessel with a reflux tube. 0.075 mol), toluene (55.6 g), methanesulfonic acid (0.612 g) and p-methoxyphenol (0.06 g) were added and dissolved with stirring. After heating and refluxing for 3 hours, additional toluene (55 g) was added. After cooling to 40 ° C. or lower, 10% aqueous NaOH (9.4 g) was added and neutralized, and then repeatedly washed with distilled water (110.0 g) until the waste liquid pH became 7. After concentration under reduced pressure, toluene (40.3 g) and methanol (161.3.0 g) were added and crystallized at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 5.0 g of light yellow crystals.

The obtained crystals had a GPC purity of 95.5%, an HPLC purity of 95.8%, a melting point of 125.1 ° C., and a converted refractive index of 1.630 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. ¹ H-NMR (400MHz, chloroform _{-d 1, δ, ppm / 5.0,2H} , -C H 2 - / 5.7,5.9,6.4,6.5,4H, -CH = C _{H 2 /6.1~6.2,6.2~6.3,2H,-C H = CH 2 /4.1,4.3,4.4,4.6,8H,-} Ethylene - / 6.7, 7.1-7.2, 7.3, 8H, Phenyl- H / 7.3-7.4, 7.4-7.5, 7.7, 8.2, 8H, Anthryl- H ) and ¹³ C-NMR (400 MHz, chloroform-d ₁ , δ, ppm / 32.8, -C H _2- / 166.0, -O- C O-vinyl / 128.0, 131.7, 131 .9, - vinyl /62.8,62.9,65.8,65.9,- Ethylene - / 114.4,114.6,1 0.0,130.4,132.4,133.5,156.7, - Phenyl /124.7,125.5,127.7,131.3,131.4,136.4,- Anthryl) ) To 9- (4-hydroxybenzyl) -10- (4-hydroxyphenyl) anthracene diethyl acrylate (anthracene derivative represented by the following formula). FIG. 9 shows a ¹ H-NMR chart, and FIG. 10 shows a ¹³ C-NMR chart. Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. FIG. 11 shows an absorption spectrum, and FIG. 12 shows a fluorescence spectrum (excitation wavelength: 380 nm).

[Example 5] Methacrylation reaction of bisphenolanthracene EO adduct The same operation as in Example 4 except that in Example 4, acrylic acid (5.4 g) was changed to methacrylic acid (7.7 g, 0.09 mol). To obtain 7.9 g of light tan crystals.

The obtained crystals had a GPC purity of 97.5%, an HPLC purity of 97.9%, a melting point of 139.1 ° C., and a converted refractive index of 1.621 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. ¹ H-NMR (400MHz, chloroform _{-d 1, δ, ppm / 5.0,2H} , -C H 2 - / 1.9,2.0,6H, -C H 3 /5.5,5.6 _{, 6.1,6.2,4H, -C (CH 3)} = C H 2 /4.1,4.3,4.5,4.6,8H,- Ethylene - / 6.7,7. 0,7.1,7.3,8H, Phenyl- H /7.3~7.4,7.4~7.5,7.7,8.2,8H,Anthryl- H) and ¹³ C- NMR (400 MHz, chloroform _{-d 1, δ, ppm / 32.8} , - C H 2 - / 18.2,18.3, - C H 3 /167.2,167.3,-O- C O- vinyl / 126.0,126.1,135.9, - vinyl /63.0,63.2,65.8,65.9,- Ethylene - / 114.5,114.6,130.0,130.4,132.4,133.4,156.7,157.9, - Phenyl /124.7,125.5,131.6,131 8), 136.4, -Anthryl )), it was confirmed that it was 9- (4-hydroxybenzyl) -10- (4-hydroxyphenyl) anthracene diethyl methacrylate (anthracene derivative represented by the following formula). FIG. 13 shows a ¹ H-NMR chart, and FIG. 14 shows a ¹³ C-NMR chart. Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. FIG. 15 shows an absorption spectrum, and FIG. 16 shows a fluorescence spectrum (excitation wavelength: 380 nm).

[Example 6] Glycidyl methacrylate reaction of bisphenolanthracene A bisphenolanthracene compound (56.5 g, 0.15 mol), methyl isobutyl ketone (226.0 g), triethylamine obtained in Synthesis Example 1 in a 300 mL reaction vessel with a reflux tube (1.13 g), glycidyl methacrylate (51.2 g, 0.36 mol) and p-methoxyphenol (0.11 g) were added and dissolved by stirring. The reaction was carried out at 80 ° C. for 24 hours after heating. After cooling to 50 ° C. or lower, pure water (100.0 g) was added, and after stirring and standing, the lower layer was removed. 15% NaCl water (100.0 g) was added, and after stirring and standing, the lower layer was removed. Distilled water (100.0 g) was used for repeated washing until the waste liquid pH reached 7. After concentration under reduced pressure, propylene glycol monomethyl ether acetate was added to adjust the solution concentration to 30% and discharged. The yield was 200 g (30% concentration solution).

  The compound in the obtained solution had a GPC purity of 87.6% and a converted refractive index of 1.609 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. The obtained compound is presumed to be an anthracene derivative represented by the following formula.

[Example 7] Cured product of bisphenolanthracene acrylic body 2.0 g of the anthracene derivative obtained in Example 1, 3.0 g of ditrimethylolpropane tetraacrylate (trade name: Miramer M410, manufactured by Miwon), and then light 0.1 g of 1-hydroxycyclohexyl phenyl ketone (product name: IRGACURE 184, manufactured by Ciba Specialty) as a polymerization initiator was added to obtain a uniform composition. This composition was applied on a polyester film (trade name: Lumirror, 100 μm in thickness, manufactured by Toray Industries, Inc.) having a 50 μm-thick Spencer mold adhered thereto, and covered with the same polyester film to prevent bubbles from entering and sealed. . Using a 100 mW ultra-high pressure mercury lamp (irradiation intensity: 3 mW / cm ² ), light irradiation was performed from the surface for 10 minutes to obtain a film-like cured product. Although the obtained hardened | cured material was immersed in the toluene solvent for 1 hour, since it was not melt | dissolving and the shape was maintained, it was confirmed that the composition is polymerizing.

  The obtained cured product had a refractive index of 1.574 (25 ° C.), and blue light emission during UV lamp (365 nm) irradiation was visually confirmed.

[Comparative Example 1]
It was 1.476 (25 degreeC) when the conversion refractive index of ditrimethylol propane tetraacrylate (the product made by Miwon, brand name: Miramer M410) which is a commercial item of bifunctional acrylate was measured. Moreover, although UV lamp (365 nm) irradiation was performed, light emission was not able to be confirmed visually.

[Comparative Example 2]
Example 7 was the same as Example 7 except that the anthracene derivative (2.0 g) obtained in Example 1 was not added and ditrimethylolpropane tetraacrylate (3.0 g) was changed to (5.0) g. Operation was performed to obtain a photopolymerized cured product. Although the obtained hardened | cured material was immersed in the toluene solvent for 1 hour, since it was not melt | dissolving and the shape was maintained, it was confirmed that the composition is polymerizing. The obtained cured product had a refractive index of 1.511 (25 ° C.), and no light emission was confirmed when irradiated with a UV lamp (365 nm).

[Comparative Example 3]
It was 1.456 (25 degreeC) when the conversion refractive index of the 1, 6- bis (acryloyloxy) hexane reagent (made by Tokyo Chemical Industry) which is a commercial item of bifunctional acrylate was measured. Moreover, although UV lamp (365 nm) irradiation was performed, light emission was not able to be confirmed visually.

[Comparative Example 4]
Example 7 and Example 7 except that the anthracene derivative (2.0 g) obtained in Example 1 was changed to the 1,6-bis (acryloyloxy) hexane reagent (2.0 g) measured in Comparative Example 3. The same operation was performed to obtain a photopolymerized cured product. Although the obtained hardened | cured material was immersed in the toluene solvent for 1 hour, since it was not melt | dissolving and the shape was maintained, it was confirmed that the composition is polymerizing. The obtained cured product had a refractive index of 1.508 (25 ° C.), and no light emission was confirmed when irradiated with a UV lamp (365 nm).

[Comparative Example 5]
It was 1.537 (25 degreeC) when the conversion refractive index of the bisphenol A-EO modified | denatured diacrylate (the product made by Miwon, product name: Miramer M2100) which is a commercial item of bifunctional acrylate was measured. Moreover, although UV lamp (365 nm) irradiation was performed, light emission was not able to be confirmed visually.

[Comparative Example 6]
The same operation as in Example 7 was performed except that the anthracene derivative (2.0 g) obtained in Example 1 in Example 7 was changed to the bisphenol A-EO-modified diacrylate (2.0 g) measured in Comparative Example 5. And a photopolymerized cured product was obtained. Although the obtained hardened | cured material was immersed in the toluene solvent for 1 hour, since it was not melt | dissolving and the shape was maintained, it was confirmed that the composition is polymerizing. The obtained cured product had a refractive index of 1.537 (25 ° C.), and no light emission was confirmed when irradiated with a UV lamp (365 nm).

[Example 8] Cured product of bisphenolanthracene acrylic body Ditrimethylolpropane tetraacrylate (manufactured by Miwon, trade name: Miramer M410) 2.0 g, photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty, (Product name: IRGACURE 184) 0.01 g was weighed, and then the compound (0.01 g) obtained in Example 1 was added to obtain a uniform composition. This composition was applied on a polyester film (trade name: Lumirror, 100 μm in thickness, manufactured by Toray Industries, Inc.) having a 50 μm-thick Spencer mold adhered thereto, and covered with the same polyester film to prevent bubbles from entering and sealed. . Light irradiation was performed from the surface using an ultraviolet LED (center wavelength: 395 nm, irradiation intensity: 0.5 mW / cm ² ). The light irradiation time until stickiness disappeared was 15 seconds.

[Comparative Example 6]
Except for not adding the compound obtained in Example 1 (0.01 mg), a composition exactly the same as in Example 8 was prepared, and an ultraviolet LED (center wavelength: 395 nm, irradiation intensity: 0.5 mW / cm ² ) was prepared. When light was irradiated from the surface, stickiness did not disappear even after 5 minutes, and it did not cure.

  As shown in this example, the anthracene derivative having a polymerizable functional group according to the present invention synthesized in Examples 1 to 6 has a higher refractive index and fluorescence characteristics with respect to ultraviolet rays than other bifunctional polymerizable compounds. And a photosensitizing effect. As can be seen from a comparison between Example 8 and Comparative Example 6, the anthracene derivative of the present invention has curability by ultraviolet rays.

  The anthracene derivative of the present invention can provide a curable composition having characteristics such as high photorefractive properties and fluorescence performance. Further, the curable composition containing the anthracene derivative is, for example, an adhesive, a paint, a laminate, a molding material, a casting material, a semiconductor sealing material, a printed board insulating material, a coating material, an optical material, a structural material, a photoresist. It can be used as a raw material.

Claims (7)

An anthracene derivative 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. The aromatic group may have a substituent, n ₁ and n ₂ are each independently an integer of ^{1 to 3.} R ¹ and R ² are each independently Z ¹ and Z ² are each independently a group represented by —O— (R—O) _m —, where R is a divalent hydrocarbon group. The hydrocarbon group may have a hydroxyl group.m is an integer of 0 or more. When m is 2 or more, a plurality of R may be the same or different.) ^2. The anthracene derivative according to claim ^1, wherein Z ¹ and Z ² in the formula (1) are each independently a group represented by any one of the following formulas (2) to (7).

(In formula (3), m ₁ and l ₁ are each independently an integer of 1 to 4.
In formula (4), one of R ³ and R ⁴ is a methyl group and the other is a hydrogen atom. l ₂ is an integer of 1 to 4.
In formula (6), m ₂ and l ₃ are each independently an integer of 1 to 4.
In formula (7), one of R ⁵ and R ⁶ is a methyl group and the other is a hydrogen atom. l ₄ is an integer of 1 to 4.
* Represents a bonding site with X or Y. ) The anthracene derivative according to claim 1 or ₂ , wherein X and Y in the formula (1) are phenylene groups and n ₁ and n ₂ are 1.   A curable composition comprising the anthracene derivative according to claim 1, 2 or 3, and / or a polymer obtained from the anthracene derivative.   Hardened | cured material obtained by hardening | curing the curable composition of Claim 4. In the presence of a basic compound, the anthracene derivative represented by the following formula (8) is reacted with at least one selected from the group consisting of acrylic acid, methacrylic acid, halogenated acrylic, halogenated methacrylic, glycidyl acrylate and glycidyl methacrylate. The manufacturing method of the anthracene derivative represented by following formula (1 ') which has a process to make.

(In Formula (8), 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 (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. And n ₁ and n ₂ are each independently an integer of ^{1 to 3.} R ¹ and R ² are each independently a group. Z ¹ and Z ² are each independently a group represented by the following formula (2) or (5).

In the presence of a basic compound, the anthracene derivative represented by the following formula (8) is reacted with at least one selected from the group consisting of halogenated alcohols, alkylene carbonates and alkylene oxides, and then acrylic acid, methacrylic acid, A method for producing an anthracene derivative represented by the following formula (1 ″), comprising a step of reacting at least one selected from the group consisting of halogenated acrylic, halogenated methacrylic, glycidyl acrylate and glycidyl methacrylate.

(In Formula (8), 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 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. And n ₁ and n ₂ are each independently an integer of ^{1 to 3.} R ¹ and R ² are each independently a group. Z ¹ and Z ² are each independently a group represented by the following formula (3), (4), (6) or (7).

(In formula (3), m ₁ and l ₁ are each independently an integer of 1 to 4.
In formula (4), one of R ³ and R ⁴ is a methyl group and the other is a hydrogen atom. l ₂ is an integer of 1 to 4.
In formula (6), m ₂ and l ₃ are each independently an integer of 1 to 4.
In formula (7), one of R ⁵ and R ⁶ is a methyl group and the other is a hydrogen atom. l ₄ is an integer of 1 to 4.
* Represents a bonding site with X or Y. )

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