JP5662234B2 - Phenolic resin, curable composition containing the same, and cured product - Google Patents

Description

  The present invention relates to a novel phenol resin having an anthracene skeleton, a curable composition containing the phenol resin, and a cured product.

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

  As a technique relating to such an anthracene derivative, for example, a photo-curing polymer (acting as a sensitizer for photo radical polymerization by introducing a (meth) acrylate group at the 9th and 10th positions of anthracene to form a polymerizable monomer ( Japanese Laid-Open Patent Publication No. 2007-99637) and a technique for obtaining a polymer having ultraviolet absorbing ability and flame retardancy (see Japanese Laid-Open Patent Publication No. 2008-1637) have been proposed. Also in the field of photoresists, anthracene derivatives are radiation-sensitive resin compositions having advantages such as high sensitivity, high resolution, high etching resistance, and low sublimation (see JP 2005-346024 A), Further, utilization 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).

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

  Examples of highly functional novolak-type phenol resins include flame retardant resin raw materials (see JP 2003-226727 A) that have improved heat resistance by introducing a rigid skeleton such as a fluorene skeleton, and methylol. Introducing a photosensitive resin material with excellent heat resistance and etching resistance (see Japanese Patent Application Laid-Open No. 2008-273844), a biphenyl skeleton, a naphthalene skeleton, an anthracene skeleton, etc. Excellent thermo-resin molding material with improved heat resistance and mechanical strength (see JP 2009-286888), excellent optical characteristics using cresol novolac with a biphenyl skeleton having a high refractive index as the base material An epoxy resin (Japanese Patent Laid-Open No. 2006-2139) has been proposed.

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

  As described above, various types of novolac type phenol resins having improved heat resistance and the like by introducing a rigid structure into the skeleton have been studied. Even in the case of these novolac type phenol resins, the IT field has begun. There is still room for improvement in various functions such as high heat resistance, high refractive index, and fluorescence characteristics when applied to various applications.

JP 2007-99637 A JP 2008-1637 A JP 2005-346024 A JP-A-7-82221 JP 2009-40765 A JP-A-6-295151 JP 2003-226727 A JP 2008-273844 A JP 2009-286888 A JP 2006-2139 A Special Table 2002-542389

  The present invention has been made in view of such circumstances, and has high functionality such as high carbon density, high heat resistance, high refractive index, and fluorescent properties, and can be applied in various technical fields. It aims at providing resin, the curable composition containing this, and hardened | cured material.

The invention made to solve the above problems is
A phenol resin (novolak type phenol resin) obtained by polymerizing a compound having a phenolic hydroxyl group using a crosslinking agent in the presence of an acidic catalyst,
The compound is represented by the following formula (1).
(In formula (1), X and Y each independently represent a hydroxyaryl group.)

  Since the phenol resin has an anthracene skeleton, it has various characteristics peculiar to anthracene, such as a high refractive index and fluorescence performance with respect to ultraviolet rays, and the optical function can be adjusted by arbitrarily selecting a crosslinking agent. Further, the phenol resin has a refractive index, a residual carbon ratio (high carbon density), and a glass transition temperature (heat resistance) that are equal to or higher than those of a phenol resin having a bisphenol skeleton such as bisphenol fluorene. Therefore, according to the phenol resin, high versatility such as being able to be used for various resin raw materials having high functionality, curing agents and the like can be exhibited.

  The phenol resin preferably has a weight average molecular weight of 800 or more and a refractive index of 1.63 or more. When the phenol resin has the molecular weight and the refractive index, the functionality can be further improved.

  The cross-linking agent may be at least one selected from the group consisting of aldehydes, dimethylol compounds, alkenes, and ketones. By appropriately selecting these crosslinking agents, the optical function and the like of the obtained phenol resin can be easily adjusted.

  Among the crosslinking agents, aldehydes are preferable. The phenol resin can exhibit particularly high refractive index, heat resistance, and the like by being polymerized using aldehydes, and can be efficiently produced.

  In the phenol resin, X and Y may be a hydroxyphenyl group. By making the said X and Y into a hydroxyphenyl group, the said phenol resin can exhibit especially a high refractive index, heat resistance, etc.

  The curable composition of the present invention is a composition containing the phenol resin. The curable composition can be used as a resin raw material composition having high versatility and added value.

  The cured product of the present invention is a cured product obtained by curing the curable composition. The cured product has a low crosslink density and high heat resistance because the resin component has an anthracene skeleton, such as low expansion, low absorption rate, high refractive index, high melting point, high residual carbon rate, fluorescence performance, etc. It can have various performances and can be used as a cured product applicable to many fields.

  As described above, the phenolic resin of the present invention has a high refractive index and various characteristics unique to anthracene, such as high heat resistance, low expansion, low absorption rate, high carbon density, and fluorescence performance with respect to ultraviolet rays. Can be provided. Furthermore, since the phenol resin has various characteristics peculiar to anthracene and has a phenolic hydroxyl group, it exhibits high versatility such as being usable for various resin raw materials such as epoxy resins and curing agents. be able to.

  Therefore, the phenolic resin of the present invention, the curable composition containing the phenolic resin, and the cured product are extremely effective in enhancing the functionality of the material and imparting new characteristics, and have high versatility and added value, for example, Epoxy resin raw materials, epoxy resin curing agents, polycarbonate resin raw materials, acrylic resin raw materials, laminate materials, coating materials such as paints, optical materials such as lenses and optical sheets, recording materials such as hologram recording materials, organic photoreceptors, photoresists It can be applied in various technical fields as materials, anti-reflective films, highly functional materials such as semiconductor encapsulants, magnetic materials such as molecular magnetic memory, organic solar cells, and organic EL elements.

1 is a diagram showing a ¹ H-NMR chart of a target product of Synthesis Example 1. FIG. 1 is a diagram showing a ¹³ C-NMR chart of a target product of Synthesis Example 1. FIG. It is a figure which shows the GPC chart of the target object of Example 1. FIG. It is a figure which shows the GPC chart of the target object of the comparative example 1. It is a figure which shows the GPC chart of the target object of the comparative example 1.

  Hereinafter, embodiments of the present invention will be described in detail with respect to a phenol resin, a curable composition using the phenol resin, and a cured product.

<Phenolic resin>
The phenolic resin of the present invention is a phenolic resin (novolak type phenolic resin) obtained by polymerizing a compound having a phenolic hydroxyl group using a crosslinking agent in the presence of an acidic catalyst, wherein the compound is represented by the following formula (1): It is represented by. Since the phenol resin has an anthracene skeleton in the main chain, the carbon density per unit structure is higher than that of a novolac-type phenol resin condensed using a general phenol or bisphenol and a crosslinking agent such as formaldehyde. , High heat resistance, high refractive index, fluorescence performance against ultraviolet rays, etc.

(Compound represented by the above formula (1))
The hydroxyaryl group represented by X and Y in the above formula (1) is at least one hydroxyl group and one hydrogen from an aromatic ring of an aromatic hydrocarbon which may have other substituents. It is a substituent excluding. Specific examples of the hydroxyaryl group include a hydroxyphenyl group, a hydroxynaphthyl group, a dihydroxyphenyl group, a dihydroxynaphthyl group and the like, and a hydrogen atom on these aromatic rings is an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an amino group. And those substituted with a substituent such as a group or a mercapto group. In addition, although the substituent on the said aromatic ring may be plural, in order to maintain the reactivity of an aromatic ring, it is preferable that all the hydrogen atoms on an aromatic ring are not substituted.

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

Examples of the alkoxy group include linear, branched, monocyclic or condensed polycyclic alkoxy groups. Specific examples of these alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy , Isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, tert-butoxy group, sec-pentyloxy group, tert-pentyloxy group, te
rt-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decylcyclohexyloxy group, etc. Can be mentioned.

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

  Examples of the alkenyl group include straight chain, branched chain, monocyclic or condensed polycyclic alkenyl groups, and these may have a plurality of carbon-carbon double bonds in the structure. Specific examples As, vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butene 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.

  A phenol resin using a compound having a hydroxyaryl group having a substituent as described above as the hydroxyaryl group can further add or adjust the function while maintaining the characteristics of the anthracene structure.

  Among these hydroxyaryl groups, hydroxyphenyl group and hydroxynaphthyl group are preferable, and hydroxyphenyl group is more preferable from the viewpoint of high refractive property, high heat resistance, high carbon density, rigidity, and reactivity with a crosslinking agent. A hydroxyphenyl group having a hydroxyl group at the para position relative to the bond with the anthracene skeleton side is most preferable.

  X and Y may be different from each other, but are preferably the same from the viewpoint of high photorefractive property, ease of production, and the like.

(Method for producing compound represented by the above formula (1))
The said compound is manufactured by the method which has the process of making phenols and anthracene-9-carbaldehyde react in presence of a non-reactive oxygen-containing organic solvent and an acid catalyst.

  The above phenols refer to compounds having a hydroxy group on the aromatic ring, such as phenolic compounds and naphtholic compounds. The phenolic compound refers to phenol in which hydrogen on the aromatic ring is substituted with other substituents. Examples of this substituent include an alkyl group and a hydroxy 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 at the para position of a hydroxy group from the reactivity with anthracene-9-carbaldehyde.

  Examples of phenolic compounds include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, and 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, reso Shin, 2-methyl resorcinol, catechol, 4-methyl catechol, hydroquinone, pyrogallol.

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

  The phenols are not particularly limited, and are appropriately selected according to the desired structure of the compound. For example, a compound in which X and Y in the above formula (1) are hydroxyphenyl 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 phenols is less than the above lower limit, a large amount of energy is required for purification because a higher-order condensate of the raw material is formed. Conversely, if the upper limit is exceeded, enormous energy is required to remove unreacted phenols. Both are uneconomical.

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

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

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

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

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

  The non-reactive oxygen-containing organic solvent is not limited to the above examples, and each may be used alone or in admixture of two or more. The lower limit of the amount of the non-reactive oxygen-containing organic solvent is preferably 1 part by mass, more preferably 5 parts by mass, and particularly preferably 10 parts by mass with respect to 100 parts by mass of the phenols. Moreover, as an upper limit of the compounding quantity of a non-reactive oxygen-containing organic solvent, 1,000 mass parts is preferable with respect to 100 mass parts of phenols, 500 mass parts is further more preferable, and 10 mass parts is especially preferable. When the blending amount of the non-reactive oxygen-containing organic solvent is less than the above lower limit, the production of reaction by-products becomes remarkable, and the productivity may be reduced. On the other hand, when the blending amount of the non-reactive oxygen-containing organic solvent exceeds the above upper limit, the reaction rate is lowered and the productivity may be lowered.

  Acid catalysts used in the production of the above compounds 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, and strong acidic ion exchange Examples include strong acids such as resin acids such as resins. 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 set in an amount that does not cause the reaction to be radical and dangerous and is not too small for the purpose of promoting the reaction. ˜20 mass%.

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

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

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

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

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

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

(Crosslinking agent)
The crosslinking agent used for polymerization of the phenol resin is not particularly limited, and for example, aldehydes, dimethylol compounds (compounds having two or more methylol groups), alkenes, ketones and the like can be appropriately used. In addition, aldehydes and dimethylol compounds are preferred when importance is attached to the refractive index, heat resistance, and molecular weight of the obtained phenol resin, and alkenes are preferred when importance is attached to light transmittance in a short wavelength region of 250 nm or less. Ketones are preferred when emphasizing (remaining carbon ratio).

  Examples of the aldehydes include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, paraaldehyde, propionaldehyde, parapropionaldehyde, salicylaldehyde, benzaldehyde, naphthalene aldehyde, anthracene aldehyde, bis (3-formyl-4-hydroxyphenyl) methane. Bis (4-hydroxy-2,5-dimethylphenyl) formylmethane, α, α-bis (4-hydroxy-2,5-dimethylphenyl) -4-formyltoluene, α, α-bis (4,5- And dihydroxy-2-methylphenyl) -4-formyltoluene. Among these, formaldehyde, formalin and paraformaldehyde which can obtain a high molecular weight phenol resin are preferable.

  Examples of the dimethylol compounds include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, 2,6-dihydroxymethyl-3,4-dimethylphenol, 4,6-dihydroxy. Methyl-2,3-dimethylphenol, 4-tert-butyl-2,6-dihydroxymethylphenol, 4-cyclohexyl-2,6-dihydroxymethylphenol, 2-cyclohexyl-4,6-dihydroxymethylphenol, 2,6 -Dihydroxymethyl-4-ethylphenol, 4,6-dihydroxymethyl-2-ethylphenol, 4,6-dihydroxymethyl-2-isopropylphenol, 6-cyclohexyl-2,4-dihydroxymethyl-3-methylphenol, bis (2-hydroxy -3-hydroxymethyl-5-methylphenyl) methane, bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylphenyl) methane Bis (4-hydroxy-5-hydroxymethyl-2,3-dimethylphenyl) methane, bis (2-hydroxy-3-hydroxymethyl-4,5-dimethylphenyl) methane, 2,2-bis (4-hydroxy) -3,5-dihydroxymethylphenyl) propane and the like. Moreover, as a commercial item of this dimethylol compound, Asahi Organic Materials Co., Ltd. TM-BIP-A (tetramethylol body of bisphenol A) etc. can be mentioned.

  Examples of the alkenes include ethylene, propylene, butene, pentene, cyclopropane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, cyclopentadiene, And dicyclopentadiene. Among them, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and cyclopentadiene are highly reactive because they have two double bonds, and can efficiently produce a phenol resin. Dicyclopentadiene is preferred.

  Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, adamantanone, fluorenone, acetophenone, propiophenone, butyrophenone, valerophenone, and the like. Among these, fluorenone is preferable because a phenol resin having a high carbon density can be obtained.

  Any of these cross-linking agents is not limited to examples, and may be used alone or in combination of two or more in order to adjust optical performance such as refractive index and transmittance.

  The use ratio of the crosslinking agent relative to the above compound is usually used by blending the crosslinking agent in the range of 0.05 mol or more and less than 1.00 mol, preferably 0.10 mol or more and 0 mol per 1 mol of the compound. Less than 90 mol, more preferably 0.30 mol or more and less than 0.80 mol.

(Acid catalyst)
The acid catalyst used in the polymerization of the phenol resin is not particularly limited, and a known one can be used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, paratoluenesulfonic acid, trifluoromethanesulfonic acid, and the like. These acid catalysts may be used alone or in combination of two or more. The amount of the acid catalyst used may be set in an amount that does not cause the reaction to be extreme and dangerous and is not too small for the purpose of promoting the reaction. -50 mass%.

(Reaction conditions)
The reaction conditions in the polymerization for obtaining the phenol resin are, for example, as follows. In addition, this reaction is normally performed in a solvent.

  The reaction temperature is determined in consideration of the type and mixing ratio of the reactants, the type and amount of the solvent, the type and amount of the acid catalyst, and other reaction requirements, but is generally in the range of 40 to 200 ° C. The temperature is preferably 50 to 180 ° C. More preferably, the temperature is 50 to 120 ° C. when aldehydes or dimethylol compounds are used as the crosslinking agent, and 140 to 180 ° C. when alkenes or ketones are used.

  The reaction time may be appropriately adjusted according to the reaction temperature and reaction requirements, but is generally about 1 to 30 hours. The reaction environment is preferably normal pressure, but the reaction may be performed under pressure or under reduced pressure.

  The solvent may be any solvent that dissolves the compound represented by the above formula (1), and examples thereof include alcohols, ethers, polyhydric alcohol ethers, cyclic ethers, and lactones. These can specifically illustrate those described above as the solvent used in the method for producing the compound.

  The solvent is preferably a water-soluble solvent that can be removed by washing with water in a later step. Examples of such a water-soluble solvent include 1,4-dioxane and 1,4-lactone. .

(Physical properties of phenol resin, etc.)
Although it does not specifically limit as a weight average molecular weight of the said phenol resin, 800 or more are preferable and 1,000 or more and 30,000 or less are more preferable. By setting the weight average molecular weight within the above range, functions such as low expansion and heat resistance can be exhibited more effectively.

  The phenol resin is obtained from the compound represented by the above formula (1), has a high refractive index, heat resistance (glass transition temperature) and carbon density, and has fluorescence characteristics. For example, the refractive index of the phenol resin is about 1.63 or more and 1.70 or less. Moreover, as a glass transition temperature of the said phenol resin, they are about 100 degreeC or more and 200 degrees C or less. Moreover, the phenol resin has a high carbon density, and the residual carbon ratio of the phenol resin is about 20% to 50%.

  Since the phenol resin is obtained from a compound having the above structure, it is used for various purposes, directly or as a reaction intermediate, for example, as various synthetic resin raw materials such as novolac type epoxy resin raw materials, acrylic resin raw materials, polycarbonate resin raw materials, etc. Can be used. In addition to the synthetic resin raw material, it can be used as a novolak resin for a photoresist or a fluorescent paint by utilizing optical characteristics.

<Curable composition>
The said curable composition contains the phenol resin of this invention. As this curable composition, the composition containing the novolak-type phenol resin containing the said phenol resin and a hardening | curing agent, and also containing the other arbitrary component is mentioned, for example. The method for preparing the curable composition is not particularly limited. For example, the novolac type phenol resin and the curing agent may be melt-mixed or pulverized, or may be dissolved and mixed in the presence of a solvent. . Moreover, in the said curable composition, the phenol resin of this invention may contain as a hardening | curing agent which hardens another main component.

  Examples of the novolak-type phenol resin include the phenol novolak resin of the present invention, a phenol novolak resin not containing an anthracene structure, a cresol novolak resin, a xylenol novolak resin, and the like. The structure of these resins includes a random novolak. Both types and high ortho novolak types can be used. In addition, a part of phenolic hydroxyl group which novolak-type phenol resin has may be glycidyl etherified.

  Examples of the curing agent include methylol compounds and hexamine. Examples of the methylol compound include monomeric dimethylol compounds such as 2,6-dimethylol-p-cresol, dimer dimethylol compounds such as bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, and 2,2- And tetramethylol compounds such as bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane.

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

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

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

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

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

  The cured product is, for example, a building material, a friction material, a grindstone, a recording material, a photoresist material, an antireflection film, an electronic material such as a semiconductor sealing material, an optical material, an organic EL material, a magnetic material such as a molecular magnetic memory, etc. Can be used.

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

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

<Molecular weight (weight average molecular weight)>
The weight average molecular weight was measured using Tosoh HLC-8220 GPC, detector (RI), TSK GelG4000HXL + G2000HXL (7.8 mmφ × 300 mm) column, and tetrahydrofuran as a developing solvent at 1.00 ml / min. The weight average molecular weight (Mw) in terms of polystyrene was determined.

<HPLC purity>
HPLC purity and reaction end point confirmation were performed using HPLC Promince series manufactured by Shimadzu Corporation, UV detector SPD-20A (246 nm), ODS-3 (4.6 mmφ × 250 mm) column manufactured by GL Science, and water / acetonitrile = 40 as a developing solvent. The liquid was fed at / 60, and was 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 is measured by dissolving in propylene glycol monomethyl ether acetate (PGMEA) at concentrations of 1, 5 and 10% by mass at 25 ° C. using a RA-520N refractometer manufactured by Kyoto Electronics Industry. And the converted refractive index at 100% by mass was determined.

<Fluorescence spectrum>
The presence or absence of fluorescence was observed by irradiating 365 nm ultraviolet rays using a handy UV lamp SLUV-4 manufactured by ASONE in a liquid state in which a sample (1 g) was dissolved in PGMEA (9 g).

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

<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.

[Synthesis Example 1] Synthesis of bisphenol anthracene 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 obtain 48.3 g (yield 53.3%) of pale yellow 9- (4-hydroxybenzyl) -10- (4-hydroxyphenyl) anthracene.

The obtained crystal had a GPC purity of 100%, an HPLC purity of 99.4%, a melting point of 238 ° C., a converted refractive index of 1.701 (25 ° C.), and emitted blue light when irradiated with a UV lamp (365 nm). It was confirmed visually. ^{1 H-NMR (400MHz, DMSO} -d6, δ, ppm / 4.9,2H, -C H 2 - / 6.6,6.9,7.1,7.2,8H, Phenyl- H / 7 .3,7.5,7.7,8.4,8H, Anthryl- H /9.2,9.8,2H,-O H) and ^{13 C-NMR (400MHz, DMSO} -d6, δ, ppm _{/32.1,- C H 2 - / 115.4,115.6,128.8,129.1,131.4,132.3,155.7,157.1,} - Phenyl /125.2, 125.3, 125.8, 127.5, 129.7, 130.2, 131.4, 132.8, 136.6, -Anthryl ) 9- (4-hydroxybenzyl) -10- (4 -Hydroxyphenyl) anthracene (in the above formula (1), X Fine Y was identified as a compound) para-hydroxyphenyl groups. FIG. 1 shows a ¹ H-NMR chart, and FIG. 2 shows a ¹³ C-NMR chart.

[Example 1]
Synthesis of phenol resin (bisphenolanthracene / formaldehyde) Crystals of the compound obtained in Synthesis Example 1 (30.0 g, 0.08 mol), 1,4-lactone (90.0 g) and para. Toluenesulfonic acid (6.0 g) was added. The mixture was heated with stirring and completely dissolved, and then 92% paraformaldehyde (2.08 g, 0.06 mol) was added thereto and reacted at an internal temperature of 80 ° C. for 6 hours. Next, PGMEA (128.0 g) was added and dissolved by stirring. The pure water 128g was thrown in, it left still after stirring, the upper layer was removed, and it repeated until the waste liquid pH became 4 or more. After performing atmospheric pressure dehydration to 170 ° C., the pressure was reduced at 180 ° C., and the remaining solvent was removed to obtain the phenol resin (25.9 g) of Example 1.

  The phenol resin of Example 1 had a molecular weight (Mw) of 5,387, a glass transition temperature of 175.6 ° C., a residual carbon ratio of 46.50%, and a converted refractive index of 1.704 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. FIG. 3 shows a GPC chart of the phenol resin of Example 1.

[Comparative Example 1]
Synthesis of phenol resin (bisphenolfluorene / formaldehyde) In Example 1, BPAF [trade name: JFE Chemical Co., Ltd.] is a commercial product of bisphenolfluorene instead of the crystals (30.0 g, 0.08 mol) obtained in Synthesis Example 1. 92% paraformaldehyde (2.24 g) instead of 9 / 9-bis (4-hydroxyphenyl) fluorene] (52.6 g, 0.15 mol), 92% paraformaldehyde (2.08 g, 0.06 mol) Except that 0.06 mol) was used, the same operation as in Example 1 was performed to obtain a phenol resin (23.2 g) of Comparative Example 1.

  The phenol resin of Comparative Example 1 had a molecular weight (Mw) of 4,838, a glass transition temperature of 169.8 ° C., a residual carbon ratio of 44.41%, and a converted refractive index of 1.661 (25 ° C.). Moreover, the light emission at the time of UV lamp (365 nm) irradiation was not able to be confirmed visually. FIG. 4 shows a GPC chart of the phenol resin of Comparative Example 1.

[Comparative Example 2]
Synthesis of phenol resin (bisphenol A / formaldehyde) In Example 1, instead of the crystals (30.0 g, 0.08 mol) obtained in Synthesis Example 1, bisphenol A (30.0 g, 0.13 mol), 92% para The same procedure as in Example 1 was performed except that 92% paraformaldehyde (3.43 g, 0.10 mol) was used instead of formaldehyde (2.08 g, 0.06 mol). 23.7 g) was obtained.

  The phenol resin of Comparative Example 2 had a molecular weight (Mw) of 3,486, a glass transition temperature of 87.6 ° C., a residual carbon ratio of 21.51%, and a converted refractive index of 1.611 (25 ° C.). Moreover, the light emission at the time of UV lamp (365 nm) irradiation was not able to be confirmed visually. FIG. 5 shows a GPC chart of the phenol resin of Comparative Example 2.

  Table 1 shows the evaluation results of the phenol resin of Example 1 (bisphenolanthracene / formaldehyde) and the phenol resins of Comparative Example 1 and Comparative Example 2 using formaldehyde as a cross-linking agent in the same manner as in Example 1. Show.

  The phenol resin obtained in Example 1 is refracted when compared with a phenol resin (phenol resin of Comparative Example 1 and Comparative Example 2) produced using bisphenol-A and bisphenol fluorene, which are binuclear phenol derivatives. It was shown that it has excellent characteristics in all of the ratio, glass transition temperature, residual carbon ratio, and fluorescence characteristics.

  Next, it shows about the phenol resin at the time of using except aldehydes as a crosslinking agent.

[Example 2]
Synthesis of phenol resin (bisphenolanthracene / tetramethylol bisphenol A) In Example 1, instead of 92% paraformaldehyde (2.08 g, 0.06 mol), TM-BIP-A (trade name) which is a tetramethylol body of bisphenol A : Asahi Organic Materials Co., Ltd./6.9 g, 0.02 mol) was used in the same manner as in Example 1 to obtain the phenol resin of Example 2 (15.3 g).

  The phenol resin of Example 2 had a molecular weight (Mw) of 4,705 and a converted refractive index of 1.695 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually.

[Example 3]
Synthesis of phenol resin (bisphenolanthracene / fluorenone) In Example 1, 9-fluorenone (11.5 g, 0.06 mol) was used instead of 92% paraformaldehyde (2.08 g, 0.6 mol), and the reaction temperature was 80. The phenol resin (28.1g) of Example 3 was obtained by performing the same operation as in Example 1 except that the temperature was changed from 170C to 170C.

  The phenol resin of Example 3 had a molecular weight (Mw) of 1,633 and a converted refractive index of 1.6361 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually.

[Example 4]
Synthesis of phenol resin (bisphenolanthracene / dicyclopentadiene) In Example 1, dicyclopentadiene (10.5 g, 0.06 mol) was used instead of 92% paraformaldehyde (2.08 g, 0.6 mol), and the reaction temperature was changed. Was changed from 80 ° C. to 170 ° C., and the same operation as in Example 1 was performed to obtain a phenol resin (29.1 g) of Example 4.

  The phenol resin of Example 4 had a molecular weight (Mw) of 1,576 and a converted refractive index of 1.650 (25 ° C.). Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually.

  The phenol resins (phenol resins of Example 1, Example 2, Example 3 and Example 4) obtained using the compound (bisphenolanthracene) obtained in Synthesis Example 1 as raw materials all have fluorescent properties, It was shown to have a high refractive index.

  The phenol resin of the present invention is, for example, a molded product, a laminated product, a shell mold, a building material, an adhesive material, a friction material, a paint, a grindstone, an electronic material, a thermal paper, a pressure sensitive paper, an epoxy resin curing agent, an epoxy resin matrix, a photo It can be used for resist materials, antireflection films, semiconductor encapsulants, recording materials and the like.

Claims (7)

A phenol resin obtained by polymerizing a compound having a phenolic hydroxyl group using a crosslinking agent in the presence of an acidic catalyst,
The said compound is represented by following formula (1), The phenol resin characterized by the above-mentioned.
(In formula (1), X and Y each independently represent a hydroxyaryl group.)   The phenol resin according to claim 1, wherein the weight average molecular weight is 800 or more and the refractive index is 1.63 or more.   The phenol resin according to claim 1 or 2, wherein the crosslinking agent is at least one selected from the group consisting of aldehydes, dimethylol compounds, alkenes, and ketones.   The phenol resin according to claim 3, wherein the crosslinking agent is an aldehyde.   The phenol resin according to any one of claims 1 to 4, wherein the X and Y are hydroxyphenyl groups.   The curable composition containing the phenol resin of any one of Claims 1-5.   A cured product obtained by curing the curable composition according to claim 6.