JP6430235B2 - (Meth) acrylate compound having anthracene skeleton and cured product thereof - Google Patents

Description

  The present invention relates to a bifunctional (meth) acrylate compound having a 9,9'-bianthryl skeleton for a polymer material having a high refractive index.

  Diacrylates of bisphenols (bisphenol A, etc.) or bisphenols ethylene oxide adducts for use as optical materials such as optical overcoat agents, hard coat agents, antireflection films, spectacle lenses, optical fibers, optical waveguides, holograms, etc. Etc. are used (Patent Document 1, etc.). Such polyfunctional acrylates are required to have improved properties such as moisture resistance, heat resistance, and high refractive index.

  As a method for improving the heat resistance of the polyfunctional acrylate, for example, Patent Document 2 reports di (meth) acrylate having a fluorene skeleton.

  However, since various properties are required for use in optical materials, it is still desired to provide a novel monomer for imparting excellent physical properties to a polymer compound.

Japanese Patent Laid-Open No. 2003-137938 JP 2009-173645 A

  An object of this invention is to provide the novel (meth) acrylate compound which can provide the outstanding physical property (especially refractive index) to acrylate hardened | cured material. Another object of the present invention is to provide a cured product having a high refractive index obtained by using a novel (meth) acrylate compound.

  As a result of intensive studies, the present inventors have found that a cured product having a high refractive index can be obtained by using a (meth) acrylate compound having a 9,9′-bianthryl structure as a monomer. The present invention has been completed.

  That is, this invention relates to the compound as described in the following item, its manufacturing method, the curable composition containing the said compound, and its hardened | cured material.

  Item 1. The following general formula (1):

（式中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ及びＲ^２ｂは、同一又は異なって、炭化水素基、基：−ＯＲ^５ａ、基：−ＳＲ^５ｂ、基：−（ＣＯ）−Ｒ^５ｃ、基：−（ＣＯ）−Ｏ−Ｒ^５ｄ、ハロゲン原子、ニトロ基、シアノ基、又は置換アミノ基を示す。Ｒ^５ａ、Ｒ^５ｂ、Ｒ^５ｃ及びＲ^５ｄは、炭化水素基を示す。ｍ１ａ、ｍ１ｂ、ｍ２ａ及びｍ２ｂは同一又は異なって、０〜４の整数を示す。Ｒ^３ａ及びＲ^３ｂは、同一又は異なって、アルキレン基を示す。ｎａ及びｎｂは同一又は異なって１以上の整数を示す。Ｒ^４ａ及びＲ^４ｂは、同一又は異なって、水素又はメチル基を示す。）
で表される化合物。

(Wherein R ^1a , R ^1b , R ^2a and R ^2b are the same or different and are a hydrocarbon group, group: —OR ^5a , group: —SR ^5b , group: — (CO) —R ^5c , group: -(CO) -O-R ^{5d represents} a halogen atom, a nitro group, a cyano group, or a substituted amino group, R ^5a , R ^5b , R ^5c and R ^5d represent a hydrocarbon group, m1a, m1b, m2a. And m2b are the same or different and represent an integer of 0 to 4. R ^3a and R ^3b are the same or different and represent an alkylene group, na and nb are the same or different and represent an integer of 1 or more R ^4a And R ^4b are the same or different and each represents hydrogen or a methyl group.
A compound represented by

  Item 2. The following general formula (2):

（式中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１ａ、ｍ１ｂ、ｍ２ａ、ｍ２ｂ、ｎａ及びｎｂは、上記と同じ）
で表される化合物と、（メタ）アクリル酸又はその誘導体とを反応させる工程を含む、前記項１に記載の化合物の製造方法。

(In the formula, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m1a, m1b, m2a, m2b, na and nb are the same as above)
The manufacturing method of the compound of said claim | item 1 including the process with which the compound represented by (meth) acrylic acid or its derivative (s) is made to react.

  Item 3. A curable composition comprising the compound according to item 1.

  Item 4. Hardened | cured material which hardened the curable composition of the said claim | item 3.

  The compound of the present invention can be used as a precursor of a cured product. Moreover, the refractive index of the cured product obtained using the compound of the present invention is expected.

    Hereinafter, the present invention will be described in detail.

1. The (meth) acrylate represented by the general formula (1) The present invention is represented by the general formula (1):

（式中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ及びＲ^２ｂは、同一又は異なって、炭化水素基、基：−ＯＲ^５ａ、基：−ＳＲ^５ｂ、基：−（ＣＯ）−Ｒ^５ｃ、基：−（ＣＯ）−Ｏ−Ｒ^５ｄ、ハロゲン原子、ニトロ基、シアノ基、又は置換アミノ基を示す。Ｒ^５ａ、Ｒ^５ｂ、Ｒ^５ｃ及びＲ^５ｄは、炭化水素基を示す。ｍ１ａ、ｍ１ｂ、ｍ２ａ及びｍ２ｂは同一又は異なって、０〜４の整数を示す。Ｒ^３ａ及びＲ^３ｂは、同一又は異なって、アルキレン基を示す。ｎａ及びｎｂは同一又は異なって１以上の整数を示す。Ｒ^４ａ及びＲ^４ｂは、同一又は異なって、水素又はメチル基を示す。）
で表される、（メタ）アクリレートに関する。

(Wherein R ^1a , R ^1b , R ^2a and R ^2b are the same or different and are a hydrocarbon group, group: —OR ^5a , group: —SR ^5b , group: — (CO) —R ^5c , group: -(CO) -O-R ^{5d represents} a halogen atom, a nitro group, a cyano group, or a substituted amino group, R ^5a , R ^5b , R ^5c and R ^5d represent a hydrocarbon group, m1a, m1b, m2a. And m2b are the same or different and represent an integer of 0 to 4. R ^3a and R ^3b are the same or different and represent an alkylene group, na and nb are the same or different and represent an integer of 1 or more R ^4a And R ^4b are the same or different and each represents hydrogen or a methyl group.
It is related with (meth) acrylate represented by these.

R ^1a , R ^1b , R ^2a and R ^2b are the same or different and each represents a hydrocarbon group, group: —OR ^5a , group: —SR ^5b , group: — (CO) —R ^5c , group: — (CO ) —O—R ^5d , a halogen atom, a nitro group, a cyano group, or a substituted amino group.

  Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a cycloalkenyl group, and an alkynyl group.

  Examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably an alkyl group having 1 to 8 carbon atoms.

  Examples of the cycloalkyl group include cycloalkyl groups having 5 to 8 carbon atoms such as a cyclohexyl group.

  Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

  Examples of the aralkyl group include an alkyl group having 1 to 4 carbon atoms having an aryl group having 6 to 10 carbon atoms such as a benzyl group and a phenethyl group.

  Examples of the alkenyl group include alkenyl groups having 1 to 12 carbon atoms such as ethenyl group, propenyl group and 1-butenyl group, preferably alkenyl groups having 1 to 8 carbon atoms.

  As a cycloalkenyl group, C5-C8 cycloalkenyl groups, such as a cyclohexenyl group, can be mentioned.

  Examples of the alkynyl group include alkynyl groups having 1 to 12 carbon atoms such as ethynyl group, propynyl group and 1-octynyl group, preferably alkynyl groups having 1 to 8 carbon atoms.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferable from the viewpoint of heat resistance.

  Examples of the substituted amino group include an amino group substituted with 1 or 2 (preferably 2) groups such as an alkyl group such as an ethyl group.

  m1a, m1b, m2a and m2b are the same or different and represent an integer of 0 to 4. Preferably it is an integer of 0-2, More preferably, it is 0 or 1.

R ^5a , R ^5b , R ^5c and R ^5d represent a hydrocarbon group. Examples of the hydrocarbon group in R ^5a , R ^5b , R ^5c and R ^5d include the hydrocarbon groups exemplified in the above R ^1a , R ^1b , R ^2a and R ^2b .

R ^3a and R ^3b are the same or different and each represents an alkylene group. R ^3a and R ^3b are preferably alkylene groups having 2 to 6 carbon atoms such as ethylene group, propylene group, trimethylene group, 1,2-butadiyl group, tetramethylene group, etc., and alkylene groups having 2 to 4 carbon atoms. It is more preferable that it is C2-C3 alkylene group, and it is especially preferable that it is ethylene group.

  na and nb are the same or different and represent an integer of 1 or more. Preferably it is an integer of 1-14, More preferably, it is an integer of 1-10.

  The compound represented by the general formula (1) of the present invention has a 9,9′-bianthracene skeleton, and when used for the production of a cured product, the physical properties such as the refractive index of the obtained cured product. It is expected to improve.

  Further, the 9,9'-bianthracene skeleton has a characteristic structure in which two anthracene sites are orthogonal to each other, and is predicted to have a dense packing structure in the crystal. Therefore, the polymer compound using the compound of the general formula (1) of the present invention is expected to exhibit high heat resistance.

2. (Meth) acrylate Production Method The (meth) acrylate represented by the general formula (1) is, for example, the following formula (2):

（式中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１ａ、ｍ１ｂ、ｍ２ａ、ｍ２ｂ、ｎａ及びｎｂは、上記と同じ）
で表される化合物と、（メタ）アクリル酸又はその誘導体とを反応させることにより製造できる。

(In the formula, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m1a, m1b, m2a, m2b, na and nb are the same as above)
It can manufacture by making the compound represented by (meth) acrylic acid or its derivative (s) react.

  In the (meth) acrylic acid or derivative thereof used for the reaction with the compound represented by the formula (2), examples of the (meth) acrylic acid derivative include (meth) acrylic acid lower alkyl ester (for example, (meth) ) Methyl acrylate, ethyl (meth) acrylate, C1-4 alkyl (meth) acrylate such as butyl (meth) acrylate), (meth) acrylic acid halide (for example, (meth) acrylic acid chloride, etc.), ( And (meth) acrylic anhydride.

  The ratio of (meth) acrylic acid or a derivative thereof is, for example, 2 to 20 mol, preferably 2.2 to 10 mol, more preferably 2.5 to 1 mol of the compound represented by the following formula (2). About 5 mol may be sufficient.

In the reaction, a catalyst (an acid catalyst, a base catalyst, etc.) may be appropriately used. The acid catalyst is not particularly limited as long as it is an esterification acid catalyst. For example, inorganic acid (sulfuric acid, hydrochloric acid, phosphoric acid, etc.), organic acid [sulfonic acid (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, etc.) And alkane sulfonic acid, arene sulfonic acid such as p-toluene sulfonic acid) etc.], etc., and solidified acid [supporting acid (inorganic acid such as sulfuric acid, phosphoric acid, heteropoly acid, organic acid) supported on the carrier] Solid acid (solid phosphoric acid etc.)], cation exchange resin, metal oxide (ZnO etc.), metal halide (CuCl ₂ etc.), metal salt catalyst [metal sulfate (NiSO ₄ etc.), metal phosphorus salt (Zr, phosphate of a transition metal such as Ti, etc.), metal nitrate _{(Zn (NO 3) 2 ·} 6H 2 O , etc.), etc.], natural minerals (acid clay, bentonite, kaolin, montmorillonite, etc.), etc. A solid acid catalyst is also included. The acid catalysts may be used alone or in combination of two or more.

  Examples of the base catalyst include metal carbonates (alkali metals such as sodium carbonate or alkaline earth metal carbonates, alkali metals such as sodium hydrogen carbonate or alkaline earth metal hydrogen carbonates), carboxylic acid metal salts (sodium acetate, etc. Inorganic such as alkali metal acetate or alkaline earth metal salt such as calcium acetate), metal hydroxide (alkali metal hydroxide such as sodium hydroxide, alkaline earth metal hydroxide such as calcium hydroxide) Bases; amines [for example, tertiary amines (trialkylamines such as triethylamine, triisopropylamine and tributylamine, aromatic tertiary amines such as N, N-dimethylaniline, and heterocyclic thirds such as pyridine) Organic bases such as secondary amine) and the like. The base catalysts may be used alone or in combination of two or more.

  The amount of catalyst (acid catalyst, base catalyst, etc.) used depends on the type of catalyst, but for example 0.01 to 10 moles, preferably 1 mole relative to 1 mole of the compound represented by the formula (2). May be about 0.05 to 5 mol, more preferably about 0.1 to 3 mol.

  Moreover, you may perform the said reaction in presence of a polymerization inhibitor (thermal polymerization inhibitor) as needed. Polymerization inhibitors include hydroquinones (eg, hydroquinone; hydroquinone monoalkyl ethers such as hydroquinone monomethyl ether (methoquinone)), catechols (eg, alkyl catechols such as t-butylcatechol), amines (eg, diphenylamine) Etc.), 2,2-diphenyl-1-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethylpiperazine-1-oxyl and the like. The polymerization inhibitors may be used alone or in combination of two or more.

  The amount of the polymerization inhibitor used is, for example, 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of (meth) acrylic acid or a derivative thereof. It may be about 5 parts by weight.

  The reaction may be performed in the absence of a solvent or in a solvent. Solvents (organic solvents) include hydrocarbons (aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.) And carbon tetrachloride), ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, anisole and the like), ketones (dialkyl ketones such as acetone and methyl ethyl ketone), and the like. The solvents may be used alone or in combination of two or more. In addition, when the said catalyst is a liquid, you may use the said catalyst as a solvent.

  The reaction temperature and reaction time can be appropriately selected according to the type of (meth) acrylic acid or its derivative used. The reaction time is, for example, 30 minutes to 48 hours, usually 1 to 36 hours, preferably about 2 to 24 hours.

  The reaction may be performed while refluxing, or may be performed while removing by-product water and alcohols. The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), and may be performed under normal pressure, increased pressure, or reduced pressure. In particular, when the reaction is performed under reduced pressure, coloring can be reduced and the reaction time can be shortened.

  Although the compound represented by the said Formula (2) is not specifically limited, For example, following Reaction Formula:

（式中、Ｘはハロゲン原子を示し、Ｒ^３はＲ^３ａ又はＲ^３ｂを示し、ｎはｎａ又はｎｂを示す。Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１ａ、ｍ１ｂ、ｍ２ａ、ｍ２ｂ、ｎａ及びｎｂは前記に同じ。）
の反応のように、一般式（３）で表される化合物と一般式（４）で表される化合物とを、不活性雰囲気下、塩基存在下、反応させることにより、一般式（２）で表される化合物を製造することができる。特に、一般式（２）においてｎａ＝ｎｂ＝１の化合物（ＡＤ−ＥＯ）では、原料の入手容易性から当該方法が好ましい。なお、一般式（３）で表される化合物は、特開２０１３−１０７８４７号公報に記載された方法等により公知化合物から製造することができる。

(In the formula, X represents a halogen atom, R ³ represents R ^3a or R ^3b , n represents na or nb. R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m1a, m1b, m2a, m2b, na and nb are the same as above.)
As in the reaction of (2), the compound represented by the general formula (3) and the compound represented by the general formula (4) are reacted in the presence of a base in an inert atmosphere to obtain a general formula (2) The compounds represented can be produced. In particular, in the case of the compound (AD-EO) in which na = nb = 1 in the general formula (2), this method is preferable from the viewpoint of availability of raw materials. In addition, the compound represented by General formula (3) can be manufactured from a well-known compound by the method etc. which were described in Unexamined-Japanese-Patent No. 2013-107847.

  As a base used in the reaction, an organic base and an inorganic base are used in combination. In the present invention, by using an organic base and an inorganic base in combination, the reaction can be advanced in preference to the dehydrohalogenation reaction of the compound of the general formula (4), which is a side reaction.

  As the organic base, alkylamines such as trialkylamine (triethylamine and the like), nitrogen-containing aromatic bases such as pyridine and the like are preferable, and triethylamine is particularly preferable. As the inorganic base, alkali metal hydroxides such as sodium hydroxide and alkali metal hydrides such as sodium hydride are preferable, and sodium hydroxide is particularly preferable.

  The halogen atom represented by X is preferably a chlorine atom or a bromine atom.

  The reaction may or may not use a solvent. Specific examples of the solvent used in the reaction include hydrocarbon solvents such as toluene, ether solvents such as tetrahydrofuran, halogenated hydrocarbon solvents such as dichloromethane, and aprotic polar solvents such as dimethyl sulfoxide. it can.

  The reaction is performed under an inert atmosphere. For example, the reaction can be performed in an argon atmosphere, a nitrogen atmosphere, or the like. If necessary, it is preferable that an inert gas is bubbled in a liquid raw material or solvent to remove air remaining in the liquid in advance.

  The usage-amount of the compound represented by General formula (4) in the said reaction should just be 2 mol or more with respect to 1 mol of compounds of General formula (3), and may use an excess amount. When the compound of the general formula (4) is a liquid, the amount of the compound of the general formula (3) can also be used.

  The usage-amount of the organic base in the said reaction should just be 2 mol or more with respect to 1 mol of compounds of General formula (3), and may use an excess amount. Specifically, it is preferably 5 to 100 mol, more preferably 5 to 20 mol, per 1 mol of the compound of the general formula (3).

  The usage-amount of the inorganic base in the said reaction should just be 2 mol or more with respect to 1 mol of compounds of General formula (3), and may use an excess amount. Specifically, the amount is preferably 5 to 50 mol, more preferably 10 to 30 mol, relative to 1 mol of the compound of the general formula (3).

  The reaction temperature in the said reaction can be performed at room temperature-100 degreeC, for example. The reaction time only needs to be such that the reaction proceeds sufficiently.

  The compound represented by the general formula (4), the organic base and the inorganic base may be added at once, but may be added stepwise over a plurality of times.

  In the general formula (1) of the present invention, a compound in which na and / or nb is 2 or more may be produced using a compound represented by the corresponding general formula (2) as in the above reaction. Moreover, after obtaining the compound whose na and nb are 1 in General formula (1), it can obtain also by extending | stretching an alkylene glycol chain.

  As a method for extending the alkylene glycol chain, a known method may be used. Specifically, for example, a method described in JP-A-2001-139651 can be exemplified.

  The produced compound (the compound represented by the formula (1) and / or the compound represented by the formula (2)) can be obtained by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization, Separation and purification may be performed by separation means such as column chromatography or a combination of these.

3. (Meth) acrylic resin and cured product thereof The compound of the present invention is expected to have a high refractive index. Therefore, a heat or photocurable (meth) acrylic resin having a high refractive index is produced using the compound of the present invention. The heat or photocurable resin may usually constitute a resin composition containing a polymerization initiator or the like. The present invention also includes a resin composition containing such a compound.

  The heat or photocurable (meth) acrylic resin (heat or photocurable (meth) acrylic resin component) of the present invention may be composed of only the compound of the general formula (1). It may be used in combination with a polyfunctional (meth) acrylate. When the heat- or photo-curable (meth) acrylic resin is composed only of the compound of the present invention, the 9,9'-bianthryl skeleton can be introduced into the cured product at a high concentration. Other polyfunctional (meth) acrylates include, for example, bifunctional (meth) acrylate {alkylene glycol di (meth) acrylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4- C2-10 alkylene glycol di (meth) acrylate such as butanediol di (meth) acrylate], polyalkylene glycol di (meth) acrylate [di to tetraethylene glycol di (meth) acrylate (in the following, for example, “ "Di to tetraethylene glycol" includes diethylene glycol, triethylene glycol and tetraethylene glycol), polyethylene glycol di (meth) acrylate, di to tetrapropylene glycol di (meth) acrylate. Rate, poly (C2-4 alkylene glycol di (meth) acrylate) such as polytetramethylene glycol di (meth) acrylate, etc.], di (meth) acrylate of bisphenol A (or its C2-3 alkylene oxide adduct)}, trifunctional Polyfunctional (meth) acrylates [for example, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate Tri or tetraol tri or tetra (meth) acrylate; ditrimethylolpropane tetra (meth) acrylate; dipentaerythritol tetra to hexa (meth) acrylate, etc.], urethane (meth) acrylate Polyfunctional (meth) acrylate having a fluorene skeleton that does not belong to the category of the rate, epoxy (meth) acrylate, polyester (meth) acrylate, and the compound represented by the formula (1) {9,9-bis (4- ( 9,9-bis ((meth) acryloyloxyphenyl) fluorenes such as (meth) acryloyloxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy-3-methylphenyl) fluorene; 9,9-bis [(meth) acryloyloxy (poly) ethoxyphenyl] fluorenes etc.] such as bis [4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl] fluorene} and the like. These other polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  The ratio of the other polyfunctional (meth) acrylate is, for example, 1 to 100 parts by weight, preferably 2 to 60 parts by weight, more preferably 5 to 100 parts by weight of the compound represented by the formula (1). About 30 parts by weight may be used.

  In addition, the said resin composition may contain the polymerization initiator, the diluent, etc. as needed.

  The polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator. You may combine a thermal-polymerization initiator and a photoinitiator. Examples of thermal polymerization initiators include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (lauroyl peroxide, etc.), dialoyl peroxide (benzoyl peroxide). Oxides, etc.], peroxyesters (t-butyl peracetate, etc.), organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis ( Isobutyronitrile) and the like, and azo compounds such as azoamide compounds and azoamidine compounds. You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include benzoins (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin alkyl ethers such as benzoin isopropyl ether), and acetophenones (acetophenone, 2-hydroxy-2-methyl-1-phenyl). Propan-1-one, etc.), aminoacetophenones {2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1 etc.}, anthraquinones (anthraquinone, 2-methylanthraquinone, etc.), Thioxanthones (2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyldimethyl ketal, etc.), benzophenones (benzopheno Etc.), xanthones and the like. These photopolymerization initiators may be used alone or in combination of two or more.

  Moreover, you may combine a photoinitiator with a photosensitizer. As photosensitizers, tertiary amines {for example, trialkylamines, trialkanolamines (triethanolamine, etc.), ethyl N, N-dimethylaminobenzoate [ethyl p- (dimethylamino) benzoate, etc.] N, N-dimethylaminobenzoic acid amyl [p- (dimethylamino) benzoic acid amyl etc.] and other dialkylaminobenzoic acid alkyl esters, 4,4-bis (diethylamino) benzophenone (Michler's ketone) and other bis (dialkylamino) Conventional photosensitizers such as benzophenone and dialkylaminobenzophenone such as 4- (dimethylamino) benzophenone}. The photosensitizers may be used alone or in combination of two or more.

  The amount of the polymerization initiator (and the total amount of the photosensitizer) used is 0.1 to 30 parts by weight (for example, 1 to 30 parts by weight) with respect to 100 parts by weight of the heat or photocurable (meth) acrylic resin. 1 to 20 parts by weight (for example, 5 to 15 parts by weight), more preferably about 1.5 to 10 parts by weight. Moreover, the usage-amount of a photosensitizer is 5-200 weight part with respect to 100 weight part of polymerization initiators (photoinitiator), Preferably it is 10-150 weight part, More preferably, it is about 20-100 weight part. It may be.

  Diluents include reactive diluents and non-reactive diluents (solvents). The reactive diluent is not particularly limited, and is a polymerizable monomer such as alkyl (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. Meth) acrylic acid C1-20 alkyl, preferably (meth) acrylic acid C1-10 alkyl and the like], methacrylic acid cycloalkyl [(meth) acrylic acid cyclohexyl and other (meth) acrylic acid C5-8 cycloalkyl etc.], Aryl (meth) acrylate [phenyl (meth) acrylate, etc.], hydroxyalkyl (meth) acrylate [(2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate) Hydroxy C2-10 alkyl (meth) acrylate, etc.], (poly) o Sialkylene glycol mono (meth) acrylate ((poly) oxy C2-6 alkylene glycol mono (meth) acrylate such as diethylene glycol mono (meth) acrylate, methoxytetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate) , Alkoxyalkyl (meth) acrylate [2-methoxyethyl (meth) acrylate, (meth) acrylic acid C1-4 alkoxyalkyl such as 3-methoxybutyl, etc.], N-substituted (meth) acrylamide ( N, N-diC1-4 alkyl (meth) acrylamide such as N, N-dimethyl (meth) acrylamide, N-hydroxy C1-4 alkyl (meth) acrylamide such as N-methylol (meth) acrylamide), (Meth) acrylic monomers such as noalkyl (meth) acrylate (N, N-dimethylaminoethyl acrylate), glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and non- (meth) acrylic monomers (for example, aromatic A vinyl group monomer (such as styrene) can be suitably used, etc. These compounds may be used alone or in combination of two or more.

  The ratio of the reactive diluent is, for example, 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, and more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the heat or photocurable (meth) acrylic resin. It may be a degree.

  Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; halogenated hydrocarbons such as chloroform, dichloroethane, and 1,1,2,2-tetrachloroethane; ketones such as ethyl methyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene and xylene; glycol ethers such as cellosolve, methyl cellosolve, carbitol, methyl carbitol, propylene glycol monomethyl ether; carboxylic acid esters (methyl acetate, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve) Acetates such as acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, etc.), esters such as carbonate esters (propylene carbonate, etc.); , Petroleum naphtha, petroleum solvents such as solvent naphtha may be cited. A solvent can be used individually or in combination of 2 or more types.

  The ratio of the solvent can be selected from the range of 1 to 500 parts by weight, for example, 10 to 400 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the heat or photocurable (meth) acrylic resin. Part, more preferably about 30 to 200 parts by weight.

  In addition, heat or photocurable (meth) acrylic resin compositions can be prepared by using conventional additives such as colorants, stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents. , A flame retardant, a flame retardant aid, a leveling agent, a silane coupling agent, a polymerization inhibitor (or a thermal polymerization inhibitor) and the like may be included. You may use an additive individually or in combination of 2 or more types.

  The present invention also includes a compound represented by the formula (1) (including the mixture, the same applies hereinafter) or a cured product of the resin composition. Such a cured product can be produced by curing the compound represented by the formula (1) or a resin composition thereof. For example, a film-like cured product is applied to the base material by applying the compound represented by the formula (1) or a resin composition thereof to form a coating film (or thin film) and then performing a curing treatment. You may manufacture by. In addition, the thickness of a film-form coating film (or thin film) can be selected according to a use, for example, 0.1-1000 micrometers, Preferably it is 1-500 micrometers, More preferably, about 5-300 micrometers may be sufficient. In addition, a cured product having a three-dimensional shape (for example, a lens shape) can be manufactured by using cast molding or the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  Various characteristics were measured and evaluated by the following methods.

(NMR)
The NMR spectrum was measured using AVANCE III HD (300 MHz) manufactured by Bruker BIOSPIN.

(HPLC)
Using an HPLC system manufactured by Shimadzu Corporation,
Column: manufactured by Tosoh Corporation _{TSKgel ODS-80T M (TOSOH)} 4.6 mm X 25 cm
Measurement conditions: Water / acetonitrile = 20/80, temperature 40 ° C, flow rate 1.0 mL / min
The measurement was performed under the following conditions.

Reference example 1
Production of 10,10′-di- (2-hydroxyethoxy) -9,9′-bianthryl (hereinafter referred to as “AD-EO”) In a 1 L separable flask equipped with a stirrer, argon inlet and thermometer 9,9′-Bianthracene-10,10 ′ (9H, 9′H) -dione (15.2 g, 0.039 mol) and 2-chloroethanol (300 mL) were bubbled with argon for 30 minutes. Thereafter, triethylamine (30 mL) and sodium hydroxide (granule, 20.0 g) were added with stirring under an argon atmosphere, and the mixture was heated at 50 ° C. for 40 minutes. Then, after heating at 70 ° C. for 2 hours, additional 2-chloroethanol (50 mL), triethylamine (5 mL) and sodium hydroxide (10 g) were added, and the mixture was heated and stirred for 1 hour. Chloroethanol (50 mL), triethylamine (5 mL) and sodium hydroxide (10 g) were added, and the mixture was stirred with heating for 15 hr. 400 mL of water was added to the reaction mixture, the precipitate was collected by filtration, washed with methanol (100 mL), and the resulting solid was dried in vacuo. The solid after drying using toluene was recrystallized to obtain AD-EO (13.3 g, yield 71%, light yellow solid).

The ¹ H-NMR spectrum of AD-EO is as follows.
¹ H NMR (300 MHz, CDCl ₃ ) δ2.54 (t, J = 5.9 Hz, 2H), 4.33 (m, 4H), 4.56 (t, J = 4.2 Hz, 4H), 7.12 (d, J = 8.6 Hz, Ar, 4H) 7.20 (t, J = 7.5 Hz, Ar, 4H), 7.50 (t, J = 7.5 Hz, Ar, 4H), 8.52 (d, J = 8.6 Hz, Ar, 4H).

Example 1
Production of 10,10'-di- (2-acryloylethoxy) -bianthryl (hereinafter referred to as "AD-EO-A")

温度計、メカニカルスターラーを備えた１Lセパラブルフラスコ中で、AD-EO（9.50 g, 20.0 mmol）及びトリエチルアミン（7.1 g, 70 mmol）のTHF（500 mL）溶液を室温で調製した。この溶液を氷水浴で冷却し、塩化アクリロイル（5.4 g, 60 mmol）を、反応温度が１０℃を超えない速度で滴下した。滴下が完了した後、氷水浴を外し、さらに２６時間撹拌した。追加の塩化アクリロイル（2.7 g, 30 mmol）及びトリエチルアミン（3.1 g, 31 mmol）を加え、さらに１８時間撹拌した。反応混合物に水（500 mL）を加え、ロータリーエバポレータにて、ＴＨＦを留去した。生じた固体をろ取し、真空オーブン中、60℃で終夜乾燥させ、AD-EO-A（淡黄色固体、１０．１g, 収率 87%：ＨＰＬＣ純度 ９２％）を得た。

In a 1 L separable flask equipped with a thermometer and a mechanical stirrer, a THF (500 mL) solution of AD-EO (9.50 g, 20.0 mmol) and triethylamine (7.1 g, 70 mmol) was prepared at room temperature. The solution was cooled in an ice-water bath and acryloyl chloride (5.4 g, 60 mmol) was added dropwise at a rate such that the reaction temperature did not exceed 10 ° C. After completion of the dropwise addition, the ice-water bath was removed and the mixture was further stirred for 26 hours. Additional acryloyl chloride (2.7 g, 30 mmol) and triethylamine (3.1 g, 31 mmol) were added and stirred for an additional 18 hours. Water (500 mL) was added to the reaction mixture, and THF was distilled off with a rotary evaporator. The resulting solid was collected by filtration and dried overnight at 60 ° C. in a vacuum oven to obtain AD-EO-A (pale yellow solid, 10.1 g, yield 87%: HPLC purity 92%).

The ¹ H-NMR spectrum of AD-EO-A is as follows.
¹ H NMR (300 MHz, CDCl ₃ ) δ4.69 (dd, J = 3.5, 5.4 Hz, 4H), 4.83 (dd, J = 3.5, 5.4 Hz, 4H), 6.00 (dd, J = 1.4, 10.4 Hz , 2H), 6.35 (dd, J = 10.4, 17.3 Hz, 2H), 6.58 (dd, J = 1.4, 17.3 Hz, 2H), 7.10 (d, J = 8.6 Hz, Ar, 4H) 7.16 (t, J = 7.5 Hz, Ar, 4H), 7.48 (t, J = 7.5 Hz, Ar, 4H), 8.50 (d, J = 8.6 Hz, Ar, 4H).

Example 2
Production of 10,10'-di- (2-methacryloylethoxy) -bianthryl (hereinafter referred to as "AD-EO-MA")

メカニカルスターラー、Dean-Starkトラップを備えた500 mLセパラブルフラスコ中にて、トルエン(250 mL)中、AD-EO(4.74 g, 10 mmol)、メタクリル酸（8.60 g, 100 mmol）、p-トルエン酸一水和物(0.88 g, 4.6 mmol)及びモノメチルヒドロキノン(ミクロスパーテル １さじ)の混合物を、水を共沸させ除きながら、４時間還流した。追加のメタクリル酸（4.70 g, 55 mmol）を加え、さらに４時間還流した。加熱をやめ、放冷し、不溶物をろ過にて除いた。得られたろ液を、200 mLの10%NaOH水溶液（200 mL）にて洗浄した。有機層を硫酸マグネシウムで乾燥し、ろ過した。そのろ液を濃縮し、白色の固体を得た。この固体を2-プロパノール／トルエン（5/1 v/v, 150 mL）にて再結晶し、結晶をろ取した。この結晶を真空乾燥（70℃）し、AD-EO-MA（白色固体、 5.00 g, 収率 82%)を得た。

In a 500 mL separable flask equipped with a mechanical stirrer and Dean-Stark trap, AD-EO (4.74 g, 10 mmol), methacrylic acid (8.60 g, 100 mmol), p-toluene in toluene (250 mL) A mixture of acid monohydrate (0.88 g, 4.6 mmol) and monomethylhydroquinone (one spoonful of microspartel) was refluxed for 4 hours while removing water azeotropically. Additional methacrylic acid (4.70 g, 55 mmol) was added and refluxed for an additional 4 hours. Heating was stopped, the mixture was allowed to cool, and insoluble materials were removed by filtration. The obtained filtrate was washed with 200 mL of 10% NaOH aqueous solution (200 mL). The organic layer was dried over magnesium sulfate and filtered. The filtrate was concentrated to give a white solid. This solid was recrystallized with 2-propanol / toluene (5/1 v / v, 150 mL), and the crystals were collected by filtration. The crystals were vacuum-dried (70 ° C.) to obtain AD-EO-MA (white solid, 5.00 g, yield 82%).

The ¹ H-NMR spectrum of AD-EO-MA is as follows.
¹ H NMR (300 MHz, CDCl ₃ ) δ2.07 (s, 6H), 4.68 (dd, J = 3.2, 5.4 Hz, 4H), 4.79 (dd, J = 3.2, 5.4 Hz, 4H), 5.69 (t , J = 1.5 Hz, 2H), 6.28 (s, 2H), 7.07 (d, J = 8.6 Hz, Ar, 4H) 7.12 (t, J = 7.5 Hz, Ar, 4H), 7.46 (t, J = 7.5 Hz, Ar, 4H), 8.50 (d, J = 8.6 Hz, Ar, 4H).
(Preparation of thin film)
AD-EO-A (0.20 g) was dissolved in 1,1,2,2-tetrachloroethane (9.80 g). Irgacure 184 (BASF) (5 mg) was added to this solution. This solution was spin-coated (500 rpm, 5 seconds, then 1000 rpm, 5 seconds) on a drained glass substrate to form a thin film.

(Production of cured film)
The thin film was irradiated with light at 500 mJ / cm ² using a UV irradiation machine (H015-L31: manufactured by Eye Graphics Co., Ltd.) to prepare a cured film.

  When the film thickness and refractive index of the cured film were measured using FE-3000 manufactured by Otsuka Electronics Co., Ltd., the film thickness was 400-700 μm, and the refractive index at 589 nm was 1.673.

Claims (4)

The following general formula (1):

(In the formula, R ^1a , R ^1b , R ^2a and R ^2b are the same or different and each represents a hydrocarbon group, group: —OR ^5a , group : — (CO) —R ^5c , or group: — (CO) — Represents O—R ^{5 d} , R ^5a , R ^5c and R ^5d represent a hydrocarbon group, and m1a, m1b, m2a and m2b are the same or different and represent an integer of 0 to 4. R ^3a and R ^3b Are the same or different and each represents an alkylene group, na and nb are the same or different and each represents an integer of 1 or more, and R ^4a and R ^4b are the same or different and represent hydrogen or a methyl group.
A compound represented by The following general formula (2):

(In the formula, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m1a, m1b, m2a, m2b, na and nb are the same as above)
The manufacturing method of the compound of Claim 1 including the process with which the compound represented by (meth) acrylic acid or its derivative (s) is made to react. A curable composition comprising the compound according to claim 1. A cured product obtained by curing the curable composition according to claim 3.