JP6537261B2 - Resin raw material, phenolic resin and method for producing anthracene derivative - Google Patents

Description

  The present invention relates to a novel anthracene derivative, a method for producing the anthracene derivative, a phenol resin, a composition for photoresist, and a luminescent agent.

  Anthracene has hitherto been used in various applications such as wood insecticides, storage stabilizers, paints and the like, as well as raw materials for producing epoxy resins and carbon black, synthetic raw materials for anthraquinone dyes, and the like.

  Further, since this anthracene is a fused polycyclic aromatic compound in which three benzene rings are condensed, it is irradiated with ultraviolet light in addition to the features such as structural hardness, high carbon density, high melting point, high refractive index It has useful properties such as the action of π electrons to emit fluorescence. In order to further utilize such properties as added value, various application developments of anthracene have been attempted. Until now, various anthracene derivatives have been developed as high-value-added materials in various technical fields.

  For example, a photocurable polymer (see JP-A-2007-99637) which acts as a sensitizer for photo radical polymerization by introducing a (meth) acrylate group at 9,10 of anthracene to form a polymerizable monomer, The polymer (refer Unexamined-Japanese-Patent No. 2008-1637) which has an ultraviolet absorptivity and a flame retardance can be obtained.

  Also in the field of photoresists, radiation sensitive resin compositions (see JP 2005-346024 A) using anthracene and having advantages such as high sensitivity, high resolution, high etching resistance, low sublimation and the like An antireflective film (see JP-A-7-82221) or the like which prevents intermixing with a resist resin can be obtained.

  Furthermore, the application of anthracene to applications such as organic photoreceptors (OPCs), organic electroluminescent devices, organic solar cells, organic light emitting diodes, etc. is also expected as an electron transport material or a light emitting agent (Japanese Patent Laid-Open No. 2009-40765) See the official gazette).

  Moreover, taking advantage of the feature that anthracene has a high refractive index, in addition to the use as an optical material, a high refractive index material, a low refractive index material, a sensitizing dye, etc. are mixed, and a hologram recording that records interference fringes by exposure. Utilization as a material is also performed (refer Unexamined-Japanese-Patent No. 6-295151).

  However, these anthracenes have insufficient diversity in the reaction.

JP 2007-99637A JP 2008-1637A JP, 2005-346024, A JP-A-7-82221 Unexamined-Japanese-Patent No. 2009-40765 JP-A-6-295151

  The present invention has been made on the background of such a situation, and has characteristics unique to anthracene (high carbon density, high melting point, high stability, high refractive index, fluorescence performance to ultraviolet light, etc.) and has various reaction diversity. Anthracene derivatives and methods for producing the same.

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

（式（１）中、Ｘは、ヒドロキシアリール基を示す。）

(In formula (1), X shows a hydroxy aryl group.)

  Since the anthracene derivative has an anthracene skeleton, it has various properties unique to anthracene, such as high carbon density, high refractive index, fluorescence performance against ultraviolet light, and a group having an aromatic ring at the 9th position of the anthracene skeleton. Have a melting point higher than that of anthracene.

  The anthracene derivative additionally has various reactivity because the above-mentioned substituent has a reactive hydroxyl group and an aromatic ring. Therefore, according to the said anthracene derivative, high versatility which can be used for various resin raw materials etc. can be exhibited.

  In addition, since the anthracene derivative has a structure in which anthracene and hydroxyaryl are single-bonded, the stability is superior to that of anthracene.

  In the anthracene derivative, X is preferably a hydroxyphenyl group. Thus, the anthracene derivative can exhibit particularly high melting point and refractive index, and can be efficiently produced.

  Another invention made to solve the above problems is a phenol resin obtained by reacting the anthracene derivative with an aldehyde. Since the said phenol resin is using the said anthracene derivative as a raw material, it has characteristics, such as a high melting point which the said anthracene derivative has, a high refractive index.

  The anthracene derivative and the phenol resin may be used for a photoresist composition. As described above, since the anthracene derivative and the phenol resin have high versatility, they can be suitably used as a photoresist composition.

  The anthracene derivative and the phenol resin may be used as a light emitting agent. As described above, since the anthracene derivative and the phenol resin have high versatility, they can be suitably used as a light-emitting agent.

（式（１）中、Ｘは、ヒドロキシアリール基を示す。） Still another invention made to solve the above-mentioned problems comprises the following formula (1) having a step of reacting phenols with anthracene-9-carbaldehyde in the presence of an acid catalyst in the absence of a solvent or in a hydrocarbon solvent. It is a manufacturing method of the anthracene derivative shown by these.

(In formula (1), X shows a hydroxy aryl group.)

  According to the said manufacturing method, generation | occurrence | production of a side reaction can be suppressed, and the said said anthracene derivative desired can be efficiently manufactured by selecting the kind of phenols. For example, by selecting phenol as the above-mentioned phenol, an anthracene derivative in which X in the above-mentioned formula (1) is a hydroxyphenyl group can be produced.

  Here, the “hydroxyaryl group” is a substituent obtained by removing one hydrogen from the aromatic ring of an aromatic hydrocarbon which has at least one hydroxy group and may have other substituents. "Phenols" refers to compounds having a hydroxy group on the aromatic ring.

  As described above, the anthracene derivative of the present invention has a melting point and stability equal to or higher than that of anthracene, and has various properties unique to anthracene, such as high carbon density, high refractive index, and fluorescence performance against ultraviolet light. ing. Furthermore, since the anthracene derivative exhibits various reactivity in addition to various characteristics unique to anthracene, it can exhibit high versatility such as being usable for various resin raw materials.

  Therefore, the anthracene derivative of the present invention is extremely effective in enhancing the function of materials and imparting new characteristics, and is a resin material having high versatility and added value, such as phenol resin material, epoxy resin material, polycarbonate material Acrylic resin raw materials, laminate materials, coating materials such as paints, lenses, optical materials such as optical sheets, recording materials such as hologram recording materials, organic photoreceptors, compositions for photoresists, antireflection films, semiconductor sealing materials, etc. It can be applied and developed in various technical fields as high-performance materials, magnetic materials such as molecular magnetic memory, organic solar cells, organic EL elements, and the like.

  Furthermore, according to the production method of the present invention, the desired anthracene derivative can be efficiently produced.

FIG. 5 is a view showing an HPLC chart after completion of the reaction of Example 1. FIG. 2 is a diagram showing an HPLC chart of the desired product of Example 1. FIG. 2 is a diagram showing a ¹ H-NMR chart of a target of Example 1. FIG. 2 is a view showing a ¹³ C-NMR chart of a target of Example 1. FIG. 7 is a view showing an HPLC chart after completion of the reaction of Example 2. FIG. 7 is a view showing an HPLC chart after completion of the reaction of Example 3.

  Hereinafter, embodiments of the present invention will be described in detail.

<Anthracene Derivative>
The anthracene derivative of the present invention is represented by the following formula (1).

  In the above formula (1), X represents a hydroxyaryl group.

  Specific examples of the hydroxyaryl group represented by X include, for example, a hydroxyphenyl group, a hydroxynaphthyl group and the like.

  In the above-mentioned hydroxyaryl group, one or more hydrogen atoms on the aromatic ring may be substituted by a substituent. Examples of this substituent include an alkyl group, a hydroxy group, an alkoxyl group, an aryl group, an alkenyl group, an amino group and a mercapto group.

  Examples of the alkyl group include linear, branched, monocyclic, and fused polycyclic alkyl groups; linear, branched, monocyclic, and fused polycyclic groups in which carbon is substituted with -O-. An alkyl group etc. are mentioned.

  Examples of the above-mentioned linear, branched, monocyclic and fused polycyclic alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl. Group, 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 Groups, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group, 4-decylcyclohexyl group and the like.

The linear and branched chain alkyl groups the carbon is replaced by -O-, for example _{-CH 2 -O-CH 3, -CH} 2 -CH 2 -O-CH 2 -CH 3, - _{CH 2 -CH 2 -CH 2 -O-} CH 2 -CH 3, - (CH 2 -CH 2 -O) n1 -CH 3 (n1 is an integer of 1 to _{8), - (CH 2 -CH 2} -CH _{2 -O)} m1 _-CH 3 (m1 is an integer of from 1 to _{5), - CH 2 -CH (CH} 3) -O-CH 2 -CH 3, -CH 2 -CH (OCH 3) 2 , and the like .

  Examples of the alkoxyl group include linear, branched, monocyclic and condensed polycyclic alkoxyl groups; linear, branched, monocyclic and condensed polycyclic which are interrupted by one or more -O- An alkoxyl group etc. are mentioned.

  Examples of the linear, branched, monocyclic and condensed polycyclic alkoxyl groups include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and the like. 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- And octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, bornyloxy group, 4-decylcyclohexyloxy group, etc. It is.

The linear and branched alkoxyl groups interrupted by the one or more -O-, for example _{-O-CH 2 -O-CH 3} , -O-CH 2 -CH 2 -O-CH _{2 -CH 3, -O-CH 2} -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n2 -CH 3 ( where n2 is 1-8 is an _{integer), - O- (CH 2 -CH} 2 -CH 2 -O) m2 -CH 3 ( wherein m2 is an integer of 1 to _{5), - O-CH 2 -CH} (CH 3) - _{OCH 2 -CH 3, -O-CH} 2 -CH (OCH 3) 2 , and the like.

  Examples of the aryl group include groups in which one hydrogen is removed from the aromatic ring which may have a substituent, and examples thereof include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 9- Anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl 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, 3,4, -Trimethoxyphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group Groups, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like.

  Examples of the alkenyl group include linear, branched, monocyclic, and fused polycyclic alkenyl groups, which may have a plurality of carbon-carbon double bonds in the structure. As such a group, for example, 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 And cyclopentadienyl groups.

  By providing a hydroxyaryl group having a substituent as the above-mentioned hydroxyaryl group, the anthracene derivative can further add or adjust the function while maintaining the characteristics of the anthracene derivative.

  For example, according to the anthracene derivative including a hydroxyaryl group having an alkyl group as a substituent, the refractive index, the melting point, and the like can be adjusted without reducing various reactivity of the anthracene derivative. The substituted alkyl group is preferably a low molecular weight from the viewpoint of the steric configuration stability of the anthracene derivative, specifically an alkyl group having 5 or less carbon atoms is more preferable, and a methyl group and an ethyl group are more preferable. Is more preferred.

  From the viewpoints of high refractive index, high melting point and reaction diversity, X is preferably an unsubstituted hydroxyphenyl group and an unsubstituted hydroxynaphthyl group, more preferably an unsubstituted hydroxyphenyl group, and a 4-hydroxyphenyl group. Is more preferred.

  As a lower limit of the melting point of the anthracene derivative, 218 ° C. is preferable, and 220 ° C. is more preferable. On the other hand, as an upper limit of the above-mentioned melting point, 300 ° C is preferred and 280 ° C is more preferred. The melting point of the anthracene derivative can be adjusted by selecting a substituent represented by X. Here, the melting point is a value determined by a peak top method using a differential scanning calorimeter and a temperature rising rate of 5 ° C./minute in a nitrogen atmosphere.

  The lower limit of the refractive index of the anthracene derivative is preferably 1.6, and more preferably 1.65. On the other hand, 2 is preferable as an upper limit of the said refractive index, and 1.9 is more preferable. The refractive index of the anthracene derivative can be adjusted by selecting a substituent represented by X. Here, the refractive index is the refractive index of anthracene solution dissolved in propylene glycol monomethyl ether acetate (PGMEA) at each concentration of 1 mass%, 5 mass% and 10 mass% at 25 ° C. using a refractometer. And the reduced refractive index at 100 mass% obtained by preparing a calibration curve.

<Advantage>
The anthracene derivative has an anthracene skeleton and thereby has high carbon density, high refractive index, fluorescence performance to ultraviolet light and the like which are characteristics unique to anthracene, and a substituent having an aromatic ring (hydroxyaryl group) is anthracene skeleton. Being introduced at position 9, it has a higher melting point than anthracene.

  The anthracene derivative further has various properties unique to anthracene, since the above-mentioned hydroxyaryl group has a reactive hydroxyl group and an aromatic ring, and has various reactivity. For example, the anthracene derivative can be used for reactions such as allylation, glycidylation, acrylation, methylolation, benzoxazination and the like.

  In addition, since the anthracene derivative has a structure in which anthracene and hydroxyaryl are single-bonded, the stability is superior to that of anthracene.

  Therefore, according to the said anthracene derivative, high versatility which can be used for various resin raw materials etc. can be exhibited. In particular, when the anthracene derivative is disposed at the 9-position of the anthracene ring, the anthracene derivative is able to be applied for excellent application such as being able to be introduced into a polymer main chain when used as a resin raw material. Become. In particular, since the anthracene derivative has a phenol skeleton at position 9 which is a short axis of the anthracene skeleton, the polymer has extremely high carbon density or crystallinity when introduced into the polymer main chain. It is expected to exhibit unique functions such as getting higher.

  Since the anthracene derivative of the present invention has the above structure, it can be used directly or as a reaction intermediate, as various synthetic resin raw materials such as phenolic resin raw materials, epoxy resin raw materials, polycarbonate raw materials, acrylic resin raw materials and the like. In addition to synthetic resin raw materials, for example, it can be used as an agricultural chemical intermediate or a pharmaceutical intermediate.

<Method for producing anthracene derivative>
The process for producing an anthracene derivative according to the present invention is an anthracene derivative represented by the following formula (1), which comprises a step of reacting a phenol with anthracene-9-carbaldehyde in the presence of an acid catalyst in a solventless or hydrocarbon solvent. Manufacturing method. Although the reaction mechanism between phenols and anthracene-9-carbaldehyde in the production method is not clear, the electron on a specific carbon of anthracene-9-carbaldehyde is localized in a solvent-free environment or by a hydrocarbon solvent. It is conceivable that a reaction with a phenolic compound may occur.

  In the above formula (1), X represents a hydroxyaryl group. The X is the same as that of the above-mentioned anthracene derivative.

  As said phenols, a phenol type compound, a naphthol type compound, etc. are mentioned.

  The said phenol type compound means the phenol by which hydrogen on an aromatic ring may be substituted by the other substituent. Examples of the substituent include an alkyl group and a hydroxy group. The number of the substituents is preferably 4 or less, more preferably 2 or less, and still more preferably 0, in view of the reactivity with anthracene-9-carbaldehyde. Further, in view of the reactivity with anthracene-9-carbaldehyde, it is preferable that no substituent is disposed at the para-position of the hydroxy group.

  Examples of the phenolic compounds 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 is a naphthol in which hydrogen on the aromatic ring may be substituted with another substituent. Examples of the substituent include an alkyl group and a hydroxy group. The number of substituents is preferably 6 or less, more preferably 2 or less, and still more 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 and 2,6-dihydroxynaphthalene. 2,7-dihydroxy naphthalene etc. are mentioned.

  The said phenols are not specifically limited to these, According to the structure of the said desired anthracene derivative, it selects suitably. For example, by selecting phenol as the above-mentioned phenol, an anthracene derivative in which X in the above-mentioned formula (1) is a hydroxyphenyl group can be produced. In addition, you may use these individually or in combination of 2 or more types.

  As a lower limit of the compounding quantity with respect to 1 mol of anthracene-9-carbaldehyde of the said phenols, 2 mol is preferable and 4 mol is more preferable. On the other hand, as an upper limit of the said compounding quantity, 100 mol is preferable, 50 mol is more preferable, and 30 mol is more preferable. When the compounding amount of phenols is less than the said minimum, since a high-order condensate of a raw material will be produced | generated, there exists a possibility that a lot of energy may be required for refinement | purification. On the contrary, when the said compounding quantity exceeds the said upper limit, there exists a possibility that a lot of energy may be required to remove unreacted phenols.

  In the present production method, a reaction solvent is not used or a hydrocarbon solvent is used. Examples of the hydrocarbon solvent include toluene, xylene, n-hexane, isohexane, cyclohexane, methylcyclohexane, n-heptane, isooctane, n-decane, solvent naphtha and the like, with preference given to toluene and cyclohexane. The hydrocarbon solvent is not limited to these, and may be used alone or in combination of two or more.

  As a minimum of compounding quantity of hydrocarbon solvent to 100 mass parts of phenols, 0 mass part is preferred, 5 mass parts is more preferred, and 10 mass parts is still more preferred. On the other hand, as an upper limit of the said compounding quantity, 1000 mass parts is preferable, 500 mass parts is more preferable, 100 mass parts is more preferable. If the blending amount of the hydrocarbon solvent exceeds the above upper limit, the reaction rate may be reduced, and the productivity may be reduced.

  Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and perchloric acid, organic acids such as oxalic acid, p-toluenesulfonic acid, methanesulfonic acid and phenolsulfonic acid, and resin acids such as strongly acidic ion exchange resins Among these, inorganic acids are preferred, and sulfuric acid is more preferred. These acid catalysts may be used alone or in combination of two or more. Further, a reaction co-catalyst such as mercaptoacetic acid may be used in combination.

  The amount of the acid catalyst used may be set in such a range that the reaction does not become radical and dangerous, and is not too small for promoting the reaction. It is 1 to 20 parts by mass.

  The synthesis of the above anthracene derivative is carried out by charging the above phenols, anthracene-9-carbaldehyde, acid catalyst and optionally a hydrocarbon solvent into a reaction vessel and stirring for a predetermined time to obtain phenols and anthracene-9-carbaldehyde It is done by reacting In addition, the injection | throwing-in order of the injection | throwing-in thing to the said reaction container does not matter.

  As a minimum of reaction temperature in a reaction process of the manufacturing method concerned, 0 ° C is preferred and 25 ° C is more preferred. On the other hand, as a maximum of the above-mentioned reaction temperature, 100 ° C is preferred and 60 ° C is more preferred. When the reaction temperature is less than the lower limit, the reaction time may be long. Conversely, if the reaction temperature exceeds the upper limit, the formation of reaction byproducts such as higher condensates and isomers is promoted, and the purity of the anthracene derivative may be reduced.

  The pressure in the reaction vessel in the reaction step of the production method is usually normal pressure, but may be performed under pressure or reduced pressure, and specifically, the internal pressure (gauge pressure) is -0.02 MPa or more 0 0.2 MPa or less is preferable.

  The reaction time in the reaction step of the production method depends on the types and amounts of phenols and hydrocarbon solvents used, the molar ratio, the reaction temperature, the pressure, etc., and can not be generally determined, but generally it is 1 hour It is preferably 48 hours or less.

  After completion of the reaction of the above-mentioned phenols with anthracene-9-carbaldehyde, it is preferable to carry out removal of the acid catalyst. As a method of removing the acid catalyst, for example, a method of dissolving the product in a water-insoluble organic solvent such as methyl ethyl ketone, methyl isobutyl ketone and the like and removing by washing with water, neutralizing the precipitated salt after filtration Other methods include direct filtration and removal of resin acids such as ion exchange resins, and methods in which the reaction solution is allowed to pass through a column packed with anion packing material.

  It is preferable to take out the said anthracene derivative by refinement | purification after the said acid catalyst removal. Generally, an organic solvent which acts as a poor solvent for the target substance and which acts as a good solvent is added to other by-products and unreacted raw materials, and then precipitated, followed by filtration and drying. The anthracene derivative which is an organic compound can be obtained.

<A compound obtained by using an anthracene derivative as an intermediate>
The compound obtained by using the anthracene derivative as an intermediate includes, for example, allylation of the anthracene derivative, glycidylation (for example, glycidylation using 9- (4-hydroxyphenyl) anthracene glycidyl ether, etc.), acrylation, methylolation, benzo An oxazinized thing etc. are mentioned.

  These compounds can be used as resin raw materials such as phenol resin raw materials, epoxy resin raw materials, acrylic resin raw materials and the like. Since these compounds obtained by using the anthracene derivative as an intermediate also have an anthracene skeleton, they have properties unique to anthracene such as high melting point, high refractive index, and fluorescence performance. Therefore, the resin obtained from the compound can also have additional added value such as having a function such as high refractive index and fluorescence performance.

<Composition>
The composition containing the anthracene derivative and / or the compound obtained by using the anthracene derivative as an intermediate, and the composition containing the compound obtained by using the phenol resin as an intermediate are phenol resin raw materials, epoxy resin raw materials, polycarbonate raw materials, It can be used for resin raw materials such as acrylic resin raw materials, light emitting agents, photoresist compositions, adhesives, paints, and the like. Other components in the composition include known ones used when producing each resin. As this other component, a solvent, an inorganic filler, a pigment, a thixotropic agent, a fluidity improver, another monomer etc. are mentioned, for example.

  As the above solvent, although it varies depending on composition constitution, for example, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol mono alkyl ether acetates, propylene glycol monoalkyl ether propio And aromatic hydrocarbons, ketones, esters and the like.

  Examples of the inorganic filler include spherical and crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina and the like.

  Examples of the pigment include organic and inorganic extender pigments and flake pigments.

  Examples of the thixotropic agent include silicone-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax and organic bentonite-based.

  Examples of the flowability improver include phenyl glycidyl ether and naphthyl glycidyl ether.

(Photoresist composition)
The photoresist composition contains the anthracene derivative, the phenol resin, and a compound obtained by using the anthracene derivative as an intermediate. The photoresist composition usually contains a photosensitizer such as a quinonediazide group-containing compound. Furthermore, in addition to the above components, this photoresist composition may contain, for example, known alkali-soluble novolak resins, solvents, surfactants, adhesion assistants, acid anhydrides and high boiling point solvents for finely adjusting the solubility in an alkali developer, and filling Agent, colorant, viscosity modifier, etc. may be contained.

<Cured product>
The cured product obtained by curing the above composition can be used as various resins. This cured product can be used in various applications as a highly versatile material that imparts various properties such as high melting point, 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 of light irradiation, heating, etc. of the said composition.

  The above-mentioned cured products are various synthetic resins such as epoxy resin, polycarbonate, acrylic resin, etc. Furthermore, taking advantage of the functionality, optical materials such as lenses, optical sheets, etc., recording materials such as hologram recording materials, organic photoreceptors, photoresists The composition can be used as a high performance material such as a composition, an antireflective film, and a semiconductor sealing material.

<Phenolic resin>
The said phenol resin is obtained by making the said anthracene derivative and aldehydes react. Moreover, you may further contain the said phenols used when manufacturing the said anthracene derivative as a raw material of the said phenol resin.

  Examples of the above aldehydes include aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde and valeraldehyde; vanillin, ethyl vanillin, salicylaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde and the like Aromatic aldehydes and the like can be mentioned. Among these, aliphatic aldehydes are preferred, and paraformaldehyde is more preferred.

  The reaction of the anthracene derivative with the aldehyde can be carried out in the presence of a catalyst. Examples of the catalyst include an acid catalyst, a base catalyst and the like.

  Examples of the acid catalyst include boric acid; organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; and inorganic acids such as hydrochloric acid and sulfuric acid. Examples of the base catalyst include hydroxides of alkali metals such as sodium hydroxide, lithium hydroxide and potassium hydroxide; tertiary amines such as aqueous ammonia and triethylamine; alkaline earth metals such as calcium, magnesium and barium Oxides or hydroxides; basic substances such as sodium carbonate and the like can be mentioned. Among these, acid catalysts are preferred as catalysts.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In addition, the measurement of the obtained anthracene derivative was performed with the following measuring instrument and measuring method.

<Purity obtained by gel permeation chromatography (GPC purity)>
GPC purity was measured using GPC (Tosoh “HLC-8220”), RI detector, column (Tosoh “TSK-Gel Super HZ 2000 + HZ1000 + HZ1000 (4.6 mmφ × 150 mm)”), and 0.35 mL of tetrahydrofuran as a developing solvent The solution was sent at a rate of 1 / minute, and the ratio was determined by the area ratio of the target peak to the total peak area.

<Purity (HPLC purity) obtained by high performance liquid chromatography>
HPLC purity and end point confirmation of reaction are HPLC ("Prominence series" by Shimadzu Corporation), UV detector ("SPD-20A (246 nm)" by Shimadzu Corporation), column ("ODS-3 (GL Science") Water / acetonitrile = 40/60 (volume ratio) was sent at 1.0 ml / min as a developing solvent using 4.6 mmφ × 250 mm))), and the ratio was determined by the area ratio of the target peak to the total peak area.

< ¹ H-NMR and ¹³ C-NMR>
¹ H-NMR and ¹³ C-NMR were measured in deuterated chloroform solvent with TMS as a reference substance using “UNITY-INOVA (400 MHz)” of Varian.

<Melting point>
The melting point was determined by a peak top method using a differential scanning calorimeter ("DSC 8230" manufactured by RIGAKU CO., LTD.) At a temperature rising rate of 5 ° C / minute in a nitrogen atmosphere.

<Refractive index>
The refractive index is propylene glycol monomethyl ether acetate (PGMEA) at a concentration of 1% by mass, 5% by mass and 10% by mass at 25 ° C. using a refractometer (“RA-520N” manufactured by Kyoto Denshi Kogyo Co., Ltd.) The refractive index of the dissolved anthracene solution was measured, a calibration curve was prepared, and the converted refractive index at 100% by mass was determined.

Example 1 (Solvent-free synthesis)
Phenol (94.1 g, 1.0 mol) and anthracene-9-carbaldehyde (10.3 g, 0.05 mol) were placed in a 500 mL reaction tube equipped with a reflux condenser and dissolved at 40 ° C. 98% concentrated sulfuric acid (2.8 g, sulfuric acid content 2.74 g) was charged into the reaction vessel, and the reaction was allowed to proceed at 40 ° C. for 15 hours. The HPLC chart after reacting for 15 hours is shown in FIG. Next, the reaction solution was dissolved in methyl isobutyl ketone (141 g), washed with distilled water (94 g) several times to remove the catalyst, and then methyl isobutyl ketone and phenol were distilled off under reduced pressure. Then, xylene (94 g) and cyclohexane (9.4 g) were added to the reaction product, and the precipitate obtained by stirring at 10 ° C. was separated by filtration to obtain crude crystals (8.6 g). The obtained crude crystals were added to a mixed solvent of ethyl acetate (4.3 g) and xylene (17.2 g), heated to 80 ° C., and then precipitated again at 10 ° C. The crystals were separated by filtration to obtain pale brown crystals. The HPLC chart of this pale brown crystal is shown in FIG.

The obtained crystals have a GPC purity of 94.7%, an HPLC purity of 92.6%, a melting point of 232 ° C., a conversion refractive index of 1.710 (25 ° C.), and ¹ H-NMR (400 MHz, CDCl ₃ , δ, ppm) /6.7, 1H, -OH / 7.1, 7.3, 4H, Phenyl- H / 7.3, 7.4, 7.7, 8.0, 8.5, 9H, Anthracene- H /) and ^{13 C-NMR (400MHz, CDCl} 3, δ, ppm / 115.3,130.4,132.3,155.5, - Phenyl /125.0,125.1,126.2,126. 9, 128.2, 130.3, 131.3, 136.8, -anthracene ) confirmed to be 9- (4-hydroxyphenyl) -anthracene. FIG. 3 shows a ¹ H-NMR chart, and FIG. 4 shows a ¹³ C-NMR chart. In addition, blue emission at the time of UV lamp (365 nm) irradiation was visually confirmed.

[Example 2] (Synthesis using a hydrocarbon solvent)
Phenol (94.1 g, 1.0 mol), anthracene-9-carbaldehyde (10.3 g, 0.05 mol) and cyclohexane (47.0 g) as a hydrocarbon solvent are charged into a 500 mL reaction vessel equipped with a reflux tube. , At 40 ° C. 98% concentrated sulfuric acid (4.7 g, sulfuric acid content: 4.61 g) was charged into the reaction vessel, and the reaction was allowed to proceed at 40 ° C. for 15 hours. The HPLC chart after completion of the reaction is shown in FIG.

[Example 3] (Synthesis using a hydrocarbon solvent)
The reaction was carried out in the same manner as in Example 2 except that toluene (47.0 g) was used as the hydrocarbon solvent. The HPLC chart after completion of the reaction is shown in FIG.

  As shown in this example, the anthracene derivative according to the present invention synthesized in Example 1 was shown to have the same ultraviolet fluorescence as anthracene. Moreover, according to the manufacturing method of the said anthracene derivative, it was shown that it can synthesize | combine efficiently under a non-solvent or hydrocarbon solvent.

  The anthracene derivative of the present invention can provide a highly versatile material that imparts various properties such as high carbon density, high melting point, high stability, high refractive index, and fluorescence performance. For example, phenolic resin raw materials, epoxy resin raw materials And polycarbonate raw materials and acrylic resin raw materials. The resin etc. which used the said anthracene derivative as a raw material, for example, coating materials, such as a laminated material and a coating material, optical materials, such as a lens and an optical sheet, recording materials, such as a hologram recording material, an organic photoreceptor, the composition for photoresists It can be used for high-performance materials such as light-emitting agents, anti-reflection films, semiconductor encapsulants, magnetic materials such as molecular magnetic memory, etc. These are used as materials for organic solar cells, organic EL elements, liquid crystal display elements etc. It can be used. Moreover, the anthracene derivative of the present invention can be used not only as a resin raw material but also as, for example, a pharmaceutical intermediate or a dye intermediate.

Claims (4)

Is represented by the following general formula (1), the resin raw material constituting the polymer main chain.

(In formula (1), X shows a hydroxy aryl group.) The resin raw material according to claim 1, wherein X in the formula (1) is a hydroxyphenyl group. A phenolic resin obtained by reacting the resin raw material according to claim 1 or 2 with an aldehyde. It is represented by the following formula (1) having a step of reacting a phenol with anthracene-9-carbaldehyde in the presence of an acid catalyst in a solvent-free or hydrocarbon solvent, and used as a resin material constituting a polymer main chain Method for producing anthracene derivatives.

(In formula (1), X shows a hydroxy aryl group.)

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