JP5007942B2 - Polymerizable composition and polymer thereof - Google Patents

Description

  The present invention relates to a polymer obtained by polymerizing a 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound in the presence of a radical polymerization initiator, and a polymerizable composition containing the anthracene compound and the radical polymerization initiator. Related to things.

  A polymer of an acrylate compound having an aromatic skeleton is known to exhibit excellent physical properties such as a high heat resistance and a high refractive index as compared with a polymer of an alicyclic acrylate. Some examples of phenoxyethyl acrylate compounds having a phenyl group are known (see Patent Documents 1 and 2).

On the other hand, there are few reports on acrylate compounds having a naphthalene skeleton and anthracene skeleton, which are expected to have higher heat resistance and higher refractive index than the benzene skeleton, and for anthracene compounds, a copolymer of vinyl anthracene and acrylate ester It is only known. (See Patent Documents 3, 4, and 5)
Special table 2002-511012 Special table 2002-511598 JP 06230224 JP 2006-350290 A Patent 02507889

  Therefore, the problem to be solved by the present invention is to provide a polymer having an anthracene skeleton that is expected to have high heat resistance and high refractive index.

  In order to solve the above-mentioned problems, the present inventor has conducted extensive studies on the structure and polymerizability of an anthracene compound having an acrylic group, and as a result, 9,10-di ((meth) acryloyloxyalkoxy) represented by the following formula (1): The inventors have found that anthracene compounds are easily polymerized in the presence of a radical polymerization initiator, and completed the present invention.

  That is, the gist of the present invention is the gist of the following.

  The first gist of the present invention resides in a polymer obtained by polymerizing a 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound represented by the following formula (1) in the presence of a radical polymerization initiator. .

{In Formula (1), n represents an integer of 1 to 10, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, an alkyl group, an aryl group, an alkoxymethyl group, an aryloxymethyl group, or Represents any of allyloxymethyl groups, X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; In addition, the substituent X on the anthracene ring occupies any position among the 5 to 8 positions, and similarly, Y occupies any position among the 1 to 4 positions. }

  The second gist of the present invention is the copolymerization of the 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound represented by the above formula (1) and other radical polymerizable monomers in the presence of a radical polymerization initiator. It exists in the polymer obtained.

  The third gist of the present invention resides in the polymer described in the first or second gist, wherein the radical polymerization initiator is a thermal radical polymerization initiator.

  The fourth gist of the present invention resides in the polymer described in the first or second gist, wherein the radical polymerization initiator is a photo radical polymerization initiator.

  The fifth gist of the present invention resides in a polymerizable composition comprising a 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound represented by the above formula (1) and a radical polymerization initiator.

  The sixth gist of the present invention resides in a polymerizable composition comprising the above-described polymerizable composition and further containing another radical polymerizable monomer.

  A seventh aspect of the present invention resides in a polymer obtained by polymerizing the polymerizable composition described in the fifth or sixth aspect.

  The 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound of the present invention is easily polymerized in the presence of a radical polymerization initiator, and the polymer obtained by polymerization exhibits a high refractive index. A film, sheet or block made of a polymer obtained by polymerizing the (meth) acryloyloxyalkoxyanthracene compound thus obtained exhibits a high refractive index, and from its structure, it absorbs ultraviolet rays and has high hardness. It is an industrially useful composition that can be expected to have a high gloss rate and high hydrophobicity.

  The polymer of the present invention is a polymer obtained by polymerizing the 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound represented by the above formula (1) in the presence of a radical polymerization initiator.

In the 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound represented by the above formula (1), n represents an integer of 1 to 10, R ¹ represents a hydrogen atom or a methyl group, and R ² represents hydrogen. An atom, an alkyl group, an aryl group, or an alkoxymethyl group is shown, and X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. R ¹ is preferably a methyl group, and n is preferably an integer of 1 to 3, and more preferably 1.

  Examples of the 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound represented by the above formula (1) include the following.

  That is, 9,10-di (2-acryloyloxyethoxy) anthracene, 9,10-di (2-methacryloyloxyethoxy) anthracene, 2-methyl-9,10-di (2-acryloyloxyethoxy) anthracene, 2- Methyl-9,10-di (2-methacryloyloxyethoxy) anthracene, 2-methoxy-9,10-di (2-acryloyloxyethoxy) anthracene, 2-methoxy-9,10-di (2-methacryloyloxyethoxy) Anthracene, 2-chloro-9,10-di (2-acryloyloxyethoxy) anthracene, 2-chloro-9,10-di (2-methacryloyloxyethoxy) anthracene, 2-chloro-9,10-di (2- Ethylacryloyloxyethoxy) anthracene, 9,10-di ( -Acryloyloxypropoxy) anthracene, 9,10-di (2-methacryloyloxypropoxy) anthracene, 2-methyl-9,10-di (2-acryloyloxypropoxy) anthracene, 2-methyl-9,10-di (2) -Methacryloyloxypropoxy) anthracene, 2-methoxy-9,10-di (2-acryloyloxypropoxy) anthracene, 2-methoxy-9,10-di (2-methacryloyloxypropoxy) anthracene, 2-chloro-9,10 -Di (2-acryloyloxypropoxy) anthracene, 2-chloro-9,10-di (2-methacryloyloxypropoxy) anthracene and the like.

  Furthermore, 9,10-di (2-acryloyloxybutoxy) anthracene, 9,10-di (2-methacryloyloxybutoxy) anthracene, 2-methyl-9,10-di (2-acryloyloxybutoxy) anthracene, 2- Methyl-9,10-di (2-methacryloyloxybutoxy) anthracene, 2-methoxy-9,10-di (2-acryloyloxybutoxy) anthracene, 2-methoxy-9,10-di (2-methacryloyloxybutoxy) Anthracene, 2-chloro-9,10-di (2-acryloyloxybutoxy) anthracene, 2-chloro-9,10-di (2-methacryloyloxybutoxy) anthracene, 9,10-di (2- (2-acryloyl) Oxyethoxy) ethoxy) anthracene, 9,10-di (2- 2-methacryloyloxyethoxy) ethoxy) anthracene, 2-methyl-9,10-di (2- (2-acryloyloxyethoxy) ethoxy) anthracene, 2-methyl-9,10-di (2- (2-methacryloyloxy) Ethoxy) ethoxy) anthracene, 2-methoxy-9,10-di (2- (2-acryloyloxyethoxy) ethoxy) anthracene, 2-methoxy-9,10-di (2- (2-methacryloyloxyethoxy) ethoxy) Anthracene, 2-chloro-9,10-di (2- (2-acryloyloxyethoxy) ethoxy) anthracene, 2-chloro-9,10-di (2- (2-methacryloyloxyethoxy) ethoxy) anthracene, 2- Chloro-9,10-di (2- (2-ethylacryloyloxyethoxy Ethoxy) anthracene, and the like.

  In addition, 9,10-di (2- (2- (2-acryloyloxyethoxy) ethoxy) ethoxy) anthracene, 9,10-di (2- (2- (2-methacryloyloxyethoxy) ethoxy) ethoxy) anthracene), 2-methyl-9,10-di (2- (2- (2-acryloyloxyethoxy) ethoxy) ethoxy) anthracene, 2-methyl-9,10-di (2- (2- (2-methacryloyloxyethoxy)) Ethoxy) ethoxy) anthracene, 2-methoxy-9,10-di (2- (2- (2-acryloyloxyethoxy) ethoxy) ethoxy) anthracene, 2-methoxy-9,10-di (2- (2- ( 2-methacryloyloxyethoxy) ethoxy) ethoxy) anthracene, 2-chloro-9,10-di (2- (2- (2-act Royloxyethoxy) ethoxy) ethoxy) anthracene, 2-chloro-9,10-di (2- (2- (2-methacryloyloxyethoxy) ethoxy) ethoxy) anthracene, 2-chloro-9,10-di (2- (2- (2-ethylacryloyloxyethoxy) ethoxy) ethoxy) anthracene and the like.

  Among the 9,10-bis ((meth) acryloyloxyalkoxy) anthracene compounds, 9,10-bis (methacryloyloxyalkoxy) anthracene compounds are preferable, and in particular, 9,10-bis (methacryloyloxyethoxy) anthracene, 9,10 -Bis (methacryloyloxypropoxy) anthracene is preferred.

  Representative compounds include those having the following structures.

The 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound of the present invention is represented by the structural formula (4) by reacting a 9,10-dihydroxyanthracene compound with an alkylene oxide in the presence of a basic compound. The first reaction with the 9,10-di (hydroxyalkoxy) anthracene compound and the 9,10-di (hydroxyalkoxy) anthracene compound obtained by the first reaction are further converted into acryloyl chloride or chloride in the presence of a basic compound. It can be obtained from the second reaction of reacting with methacryloyl. {In the following reaction formula, each R ^1, R ^2, X, Y and n have the same meaning as the R ^1, R ^2, X, Y and n in the formula (1)}

  As the 9,10-dihydroxyanthracene compound used as a raw material in the first reaction, 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, 2-methoxy-9,10-dihydroxyanthracene, 2-chloro- 9,10-dimethoxyanthracene and the like can be mentioned. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like. The alkylene oxide is added in an amount of 2 mol times to 20 mol times with respect to the 9,10-dihydroxyanthracene compound. If it is less than 2 mole times, unreacted 9,10-dihydroxyanthracene compound remains, which is not preferable. In addition, when the addition amount of alkylene oxide is 2 mol times or more, for example, when the addition amount exceeds 5 mol times, in the 9,10-di (hydroxyalkoxy) anthracene compound obtained by the first reaction, n is Two or more compounds are produced. Mainly generated compounds are compounds of n = 2 to 3 in addition to those of n = 1. Furthermore, since the range of n is increased by increasing the addition amount, the addition amount of alkylene oxide is appropriately selected from the above range according to the target range of n.

  Examples of the basic compound include organic bases such as trimethylamine, triethylamine, and pyridine, and inorganic bases such as sodium hydroxide, potassium hydroxide, and sodium carbonate. The addition amount of the basic compound is preferably 2 to 3 times the mol of the hydroxyalkoxyanthracene compound. The reaction is usually performed in the presence of a solvent. Solvents used include alcohol solvents such as methanol, ethanol, n-propyl alcohol, ethylene glycol and dimethoxyethanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as benzene, toluene, xylene and chlorobenzene. Group solvents, halogen solvents such as dichloromethane, dichloroethane and dichloroethylene, ether solvents such as tetrahydrofuran and 1,4-dioxane, and amide solvents such as dimethylformamide and dimethylacetamide are used.

The reaction temperature is preferably 0 ° C. or higher and 80 ° C. or lower. If it is less than 0 ° C., the reaction is slow, and if it exceeds 80 ° C., by-products due to side reactions increase, which is not preferable. The reaction time depends on the reaction temperature, but is usually 0.5 to 2 hours. As the reaction proceeds, the 9,10-di (hydroxyalkoxy) anthracene compound with n = 1 becomes insoluble in the solvent and precipitates. On the other hand, products with n = 2 or more remain dissolved in the solvent, and the reaction product with n = 1 can be isolated by suction filtration of the precipitate. On the other hand, products with n = 2 or more can be obtained by concentrating the filtrate obtained by filtering the reaction mixture and excluding the product with n = 1. If necessary, it can be dissolved in a soluble solvent such as toluene and purified by recrystallization with a poor solvent such as n-hexane. , 10-di (hydroxyalkoxy) anthracene compound can be converted into a 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound by a second reaction in which acryloyl chloride or methacryloyl chloride is reacted with a basic compound. Examples of the basic compound include organic amine compounds such as trimethylamine, triethylamine, piperidine, and pyridine.

  The reaction is usually performed in the presence of a solvent. Solvents used include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic solvents such as benzene, toluene, xylene, and chlorobenzene, halogen solvents such as dichloromethane, dichloroethane, and dichloroethylene, tetrahydrofuran, 1,4- Ether solvents such as dioxane and amide solvents such as dimethylformamide and dimethylacetamide are used.

  The acryloyl chloride or methacryloyl chloride is added in an amount of 2 to 3 moles with respect to the 9,10- (hydroxyalkoxy) anthracene compound. The addition amount of the basic compound is preferably 2 to 3 times the mol of the 9,10-di (hydroxyalkoxy) anthracene compound. If it is less than 2 mol times, an unreacted hydroxyalkoxyanthracene compound remains, and if it exceeds 3 mol times, the isolated yield of the product is lowered, which is not preferable. The reaction temperature is preferably 0 ° C. or higher and 80 ° C. or lower. If it is less than 0 ° C., the reaction is slow, and if it exceeds 80 ° C., by-products due to side reactions increase, which is not preferable. Usually, the reaction proceeds without problems at room temperature. As the reaction proceeds, the hydrochloride of the basic compound is precipitated. When a water-soluble ketone or a water-soluble ether is used as a solvent, the precipitated hydrochloride of the basic compound is dissolved by adding water, and then water is further added to precipitate the product. The precipitate can be filtered and dried to obtain the corresponding 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound. When a water-insoluble solvent is used as the reaction solvent, water is added after the completion of the reaction to dissolve the hydrochloride of the basic compound to form two layers, and the aqueous layer is separated by a liquid separation operation. Next, the organic layer is concentrated, and a poor solvent such as n-hexane or cyclohexane is added to precipitate the product.

  The thus-obtained 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound (hereinafter sometimes simply referred to as anthracene derivative) is a radical polymerization initiator of thermal decomposition type, redox decomposition type, photodecomposition type, etc. In the presence or absence of water, polymerization can be carried out by applying, in addition to thermal energy, active energy rays such as ultraviolet rays, electron beams, and microwaves, and mechanical energy. In addition, since it superposes | polymerizes rapidly to superpose | polymerize in presence of a radical polymerization initiator, it is preferable. These polymerization initiations are known in the literature. (For example, Takayuki Otsu “Chemistry of Revised Polymer Synthesis” (Chemical Doujin 1979)) Suitable radical polymerization initiators for polymerization of the anthracene derivatives of the present invention include thermal radical polymerization initiators and photoradical polymerization initiators. It is done.

  As the thermal radical polymerization initiator, either an organic peroxide or an azo compound can be used. Examples of the organic peroxide include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy-2-ethylhexanoate, t-butyl peroxy-3.5-trimethylhexanoate, and t-butylperoxide. Peroxyesters such as oxyisopropyl carbonates, peroxyketals such as 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, diacyl peroxides such as lauroyl peroxide, etc. Can do. Examples of the azo compound initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1- And azonitriles such as (carbonitrile).

  The addition concentration of the thermal radical polymerization initiator is selected from the range of 0.1 to 10% by weight, preferably 1 to 3% by weight, based on the total weight of the anthracene derivative and the radical polymerizable monomer used together as necessary. It is. If it is less than 0.1% by weight, the curing rate is slow, and if it is more than 10% by weight, the physical properties of the polymer are deteriorated.

  The thermal radical polymerization carried out in the presence of a thermal radical polymerization initiator is usually carried out in the presence of a solvent, but it can also be heated and polymerized in a molten state. When a solvent is used, examples of the solvent include aromatic solvents such as toluene, xylene, t-butylbenzene, chlorobenzene, and chloronaphthalene, ether solvents such as tetrahydrofuran and 1,4-dioxane, cyclohexanone, and mail ethyl ketone. , Ketone solvents such as methyl-i-butyl ketone, and amide solvents such as dimethylacetamide and dimethylformamide are used. The polymerization temperature is usually between 50 ° C and 150 ° C. If it is 50 ° C. or lower, the polymerization is too slow, which is not preferable, and if it is 150 ° C. or higher, the polymer is unfavorably colored. More preferably, it is in the range of 80 ° C to 120 ° C. When a solvent is used, as the polymerization proceeds, the polymer becomes insoluble and precipitates. This precipitate is filtered and dried to obtain a polymer obtained by polymerizing 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound. The polymer obtained does not melt even when heated above the melting point of the starting monomer 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound, and 9,10-di ((meth) acryloyloxy). Alkoxy) Anthracene compound was not dissolved in toluene, acetone, tetrahydrofuran, etc., which are good solvents, and was confirmed to be a polymer.

  In the case of melting and polymerizing, after heating and melting above the melting point of 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound, a predetermined amount of thermal radical polymerization initiator is added, and nitrogen is added. Continue heating under atmosphere. As time progresses, the melt hardens and polymerizes. The heating time is usually several minutes to several tens of minutes.

  The polymer obtained in this way does not melt even when heated above the melting point of the starting monomer 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound, and 9,10-di ((meta It was confirmed that the polymer was not dissolved in toluene, acetone, tetrahydrofuran, etc., which are good solvents for the) acryloyloxyalkoxy) anthracene compound.

In addition, the 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound can be polymerized by irradiation with active energy rays. Examples of active energy rays that can be used include visible light, UV light, and electron beams. First, polymerization by visible light and UV light will be described.

  The 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound can be polymerized by light irradiation in the presence of a photoradical polymerization initiator. As the photopolymerization initiator, an acyl phosphine oxide photopolymerization initiator can be suitably used. Examples include trimethylbenzoyl-diphenyl-phosphine oxide known by the trade name DAROCUR TPO manufactured by Ciba Specialty, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide known by the trade name IRGACURE 819. . Furthermore, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) known under the trade name IRGACURE 784 manufactured by Ciba Specialty Company -Phenyl) titanium is also effective. Furthermore, 6,12- (bis) trimethylsilyloxy-1,11-naphthacenequinone compounds, which are naphthacenequinone compounds, can also be used. Of these photoradical polymerization initiators, preferably bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) known by the trade name IRGACURE784. 1-yl) -phenyl).

  The addition concentration of the radical photopolymerization initiator used in radical photopolymerization is 0 with respect to the total weight of the 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound and the radical polymerizable monomer used in combination as necessary. It is selected from the range of 1 to 5% by weight, preferably 0.3 to 1% by weight. If it is less than 0.1% by weight, the curing rate is slow, and if it is more than 5% by weight, the physical properties of the polymer are deteriorated. The 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound of the present invention can be easily cured by irradiation with light containing light having a wavelength corresponding to the absorption wavelength of the photoradical polymerization initiator used. it can. A preferred wavelength range is 380 to 500 nm. If the wavelength range of the irradiation light is outside this range, it is not preferable because sufficient curing cannot be performed. Specifically, it can be cured using a light source such as a lamp capable of irradiating light in this wavelength range. Specific examples include light sources such as UV-LEDs, blue LEDs, and white LEDs. In addition, light sources such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, and metal halide lamps can be used. However, the wavelength range is adjusted with an absorption filter to improve the operability in photocuring and the properties of the cured product. May be. The use of sunlight is also possible.

  As a specific embodiment of radical photopolymerization, both polymerization in a solution state using a solvent and polymerization in a bulk state without using a solvent are possible. The solvent that can be used in solution polymerization using the former solvent is not particularly limited as long as it has no polymerization inhibiting effect. Among them, aromatic solvents such as toluene, xylene, t-butylbenzene, chlorobenzene, chloronaphthalene, halogenated carbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxane, etc. An ether solvent is preferably used. In the polymerization method in a solution state, the polymer becomes insoluble and precipitates with light irradiation. This can be filtered and dried to obtain a polymer of 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound. The polymer obtained in this way does not melt even when heated above the melting point of the starting monomer 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound, and 9,10-di ((meta It was confirmed that the polymer was not dissolved in toluene, acetone, tetrahydrofuran, etc., which are good solvents for the) acryloyloxyalkoxy) anthracene compound.

  In addition, in the case of photopolymerization without using a solvent, there are a case where polymerization is performed in a lump according to a target shape, and a case where curing is performed and polymerization is performed in a film form. When radical radical polymerization is performed in the form of a mass, it is heated to a melting point of 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound or melted, or 9,10-di ((meth) acryloyloxyalkoxy). A mixture obtained by adding another radical polymerizable monomer to the anthracene compound is heated and melted, and a predetermined photoradical initiator is added and dissolved therein, and light irradiation is performed in a molten state.

  The light source used for light irradiation is the same as the light source used in the solution state. As the light is irradiated, the melt or solidified product is cured and polymerized. The light irradiation time is usually between several minutes and 10 minutes. The polymer does not melt even when heated above the melting point of the starting monomer 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound, and the 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound This was not dissolved in toluene, acetone, tetrahydrofuran, etc., which are good solvents, and was confirmed to be a polymer.

  Next, in the case of photopolymerization without using a solvent, when polymerizing in the form of a film, it is performed as follows. The film is prepared by, for example, preparing a composition containing 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound and a photoradical initiator prepared as described above on a substrate such as a polyester film, an aluminum foil, or a metal plate. It is applied by using a bar coater to make a coating film with a film thickness of about 200 μm. Similarly, a sheet-like composition having a thickness of about 1 mm to 10 mm can be cured. A polymerized film or sheet can be obtained by irradiating the coated material with light using the lamp described above. The obtained film or sheet does not melt even when heated above the melting point of the starting monomer 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound, and 9,10-di ((meth) acryloyl). It was confirmed that the oxyalkoxy) anthracene compound was not dissolved in toluene, acetone, tetrahydrofuran, etc., which are good solvents, and was a polymer. As a result of measuring the refractive index, a refractive index higher than that of the monomer was obtained, indicating that the film or sheet was polymerized.

  It is also possible to use known techniques such as literature in these photopolymerizations. (For example, Radtech Study Group “Latest Trends in UV / EB Curing Technology” (CMC Publishing Co., Ltd., 2006)) Polymerization by irradiation of electron beams among active energy rays is also possible. In this case, the polymerization can be performed without using a radical polymerization initiator. For example, in the case of performing electron beam curing in a film state, curing / polymerization is performed by irradiation with an electron beam for 2 minutes at an acceleration voltage of 150 kV and a K value of 99 Film can be obtained. The obtained film does not melt even when heated above the melting point of the starting monomer 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound, and 9,10-di ((meth) acryloyloxyalkoxy). ) It was not dissolved at all in toluene, acetone, tetrahydrofuran, etc., which are good solvents for anthracene compounds, and was confirmed to be a polymer. As a result of measuring the refractive index, a refractive index higher than that of the monomer was obtained, indicating that the film was polymerized.

  In the polymerization of the present invention, not only the above-mentioned anthracene derivative, that is, (meth) acryloyloxyalkoxyanthracene compound is used as a single monomer, but also other radical polymerizable monomers other than (meth) acryloyloxyalkoxyanthracene compound are added for copolymerization. It is also possible to use a polymerizable polymer. Other radical polymerizable monomers include, for example, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, Further, styrene acrylate, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, methacrylic acid ester and the like can be mentioned. When these other radical polymerizable monomers are used, although depending on the compatibility with the (meth) acryloyloxyanthracene compound, other radical polymerizable monomers are added to 10 parts by weight of the (meth) acryloyloxyalkoxyanthracene compound. It is preferably used in the range of 1 to 90 parts by weight. Use of other radically polymerizable monomers in excess of 90 parts by weight is not preferable because performances such as heat resistance and refractive index of the polymer are lowered.

  It is also possible to add additives other than the radical polymerization initiator before these polymerization operations. Additives such as polymerization inhibitors, antioxidants, light (ultraviolet) absorbers, light stabilizers, anti-aging agents, fire proofing agents, etc., to prevent the deterioration and deterioration of the polymer. Pigments, dyes, glossy materials, etc., plasticizers, slip agents, mold release agents, gelling agents, etc. for improving processability, flame retardants, antistatic agents, antibacterials, etc. Agents, deodorants, fragrances and the like.

  The polymer obtained by polymerizing the (meth) acryloyloxyalkoxyanthracene compound in the presence or absence of the radical polymerization initiator has been described above. As can be seen from the above description, the (meth) acryloyloxy of the present invention is described. It is also useful to make a polymerizable composition comprising an alkoxyanthracene compound and a radical polymerization initiator. A polymer can be obtained by polymerizing the polymerizable composition by the method described above. That is, by preparing a polymerizable composition prepared in advance, after processing this polymerizable composition into an arbitrary shape, a polymer having a target shape can be obtained by irradiation with thermal energy or active energy rays. . Furthermore, it is also useful to make a polymerizable composition further containing another radical polymerizable monomer other than the (meth) acryloyloxyalkoxyanthracene compound. In this case, a copolymerizable polymer can be obtained. .

  Applications of the polymer of the present invention include optical functional materials such as lenses, diffraction gratings, filters and reflectors, sealants, resists, insulating materials, electronic materials such as capacitor materials, energy-related materials such as capacitors and solar cells. Separation functional materials such as ion exchange resins, biomaterials such as dental materials, medical functional materials, high-strength materials, aviation such as adhesives, automobile materials, etc., paints, adhesives, etc., widely introduced in the literature . (For example, the Polymer Materials / Technology Directory Editorial Committee “Polymer Materials / Technology Overview” (Industrial Technology Service Center, 2004), Optical Technology / Material Dictionary Editorial Committee “Optical Technology / Material Dictionary” (stock) (Industry Technical Service Center, 2006) In the field of optical materials, the higher the refractive index, the thinner the lens, and the higher the refractive index, the better the resolution. The rate indicates that the refractive index of the D line at room temperature is 1.55 or more.

  The present invention is illustrated by the following examples which are not intended to limit the scope of the invention.

<Thermal polymerization of 9,10-bis (2-methacryloyloxyethoxy) anthracene>
A 200 ml three-necked flask equipped with a thermometer and a stirrer was charged with 2.0 g (4.6 mmol) of 9,10-di (2-methacryloyloxyethoxy) anthracene under a nitrogen atmosphere, and then 40 g of toluene was added. 40 mg of azobisisobutyronitrile was added. When the internal temperature was kept at 106 ° C. and heated, a large amount of yellow precipitate was formed after 5 minutes. The mixture was further heated for 10 minutes and cooled to obtain a yellow slurry. 150 ml of methanol was added, stirred sufficiently, suction filtered and dried to obtain 1.8 g of a yellow powdery polymer. The isolation yield was 90 mol%. This was heated to a melting point of 105 ° C. or higher of the starting material 9,10-di (2-methacryloyloxyethoxy) anthracene but not melted at all, and a good solvent for 9,10-di (2-methacryloyloxyethoxy) anthracene It was confirmed that the polymer was not dissolved at all in toluene, dichloromethane, and dimethylformamide.

<Thermal polymerization of 9,10-di (2-methacryloyloxypropoxy) anthracene>
A 200 ml three-necked flask equipped with a thermometer and a stirrer was charged with 2 g (4.3 mmol) of 9,10-di (2-methacryloyloxypropoxy) anthracene under a nitrogen atmosphere, and then 30 g of toluene was added, and azobis, a polymerization initiator, was added. 40 mg of isobutyronitrile was added. When the internal temperature was kept at 106 ° C. and heated, a large amount of yellow precipitate was formed after 5 minutes. The mixture was further heated for 10 minutes and cooled to obtain a yellow slurry. 150 ml of methanol was added, sufficiently stirred, suction filtered and dried to obtain 1.9 g of a yellow powdery polymer. The isolation yield was 95 mol%. This product was heated to 121 ° C. or higher, which is the melting point of the starting material 9,10-di (2-methacryloyloxypropoxy) anthracene, but did not melt at all, and good 9,10-di (2-methacryloyloxypropoxy) anthracene. It was confirmed that the solvent was not dissolved at all in toluene, dichloromethane, and dimethylformamide, and polymerization was performed.

<Photopolymerization of 1,4-di (2-methacryloyloxypropoxy) anthracene>
As a monomer, 100 parts by weight of 9,10-di (2-methacryloyloxypropoxy) anthracene and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- () as an initiator are used. 1 part by weight of 1H-pyrrol-1-yl) -phenyl) titanium (manufactured by Ciba Specialty, trade name: Irgacure 784) was added to obtain a uniform polymerizable composition. This polymerizable composition was applied to the surface of a polyester film (trade name: Lumirror, film thickness 100 μm, manufactured by Toray Industries, Inc.) with a bar coater so as to have a film thickness of 300 μm. Next, a blue LED (Luxeon, center wavelength: 460 nm, 3 W) was irradiated in a nitrogen atmosphere. After one spectral irradiation, a smooth film in which 9,10-di (2-methacryloyloxypropoxy) anthracene was polymerized was obtained.

This was heated on a hot plate to 121 ° C. or higher, which is the melting point of the raw material 9,10-di (2-methacryloyloxypropoxy) anthracene, but did not melt at all. Further, when the IR spectrum of the obtained film was measured, it was confirmed that absorption at 1620 cm ⁻¹ due to the methacryl group disappeared. Further, the refractive index of the film was measured to be 1.611 (n _D), the refractive index of the monomer 1.593 (n _D) are higher than, it was confirmed that the polymerization.

<Photocopolymerization of 1,4-di (2-methacryloyloxypropoxy) anthracene and tricyclodecane dimethanol diacrylate>
9,10-di (2-methacryloyloxypropoxy) anthracene as a monomer, 50 parts by weight of tricyclodecane dimethanol diacrylate, and bis (η5-2,4-cyclopentadien-1-yl)-as an initiator Uniform polymerizable composition by adding 1 part by weight of bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (trade name: Irgacure 784, manufactured by Ciba Specialty) It was. This polymerizable composition was applied to the surface of a polyester film (trade name: Lumirror, film thickness 100 μm, manufactured by Toray Industries, Inc.) with a bar coater so as to have a film thickness of 300 μm.
Next, a blue LED (Luxeon, center wavelength: 460 nm, 3 W) was irradiated in a nitrogen atmosphere. A smooth film was obtained after one spectral irradiation.

This was heated on a hot plate to 121 ° C. or higher, which is the melting point of the raw material 9,10-di (2-methacryloyloxypropoxy) anthracene, but did not melt at all. Further, the refractive index of this film was measured to be 1.563 (n _D ), which was higher than the refractive index of the polymer of tricyclodecane dimethanol diacrylate, 1.536 (n _D ), and copolymerized. It was suggested that

Claims (7)

A polymer obtained by polymerizing a 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound represented by the following formula (1) in the presence of a radical polymerization initiator.

{In Formula (1), n represents an integer of 1 to 10, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, an alkyl group, an aryl group, an alkoxymethyl group, an aryloxymethyl group, or Represents any of allyloxymethyl groups, X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; In addition, the substituent X on the anthracene ring occupies any position among the 5 to 8 positions, and similarly, Y occupies any position among the 1 to 4 positions. } A polymer obtained by copolymerizing a 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound represented by the following formula (1) and another radical polymerizable monomer in the presence of a radical polymerization initiator.

{In Formula (1), n represents an integer of 1 to 10, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, an alkyl group, an aryl group, an alkoxymethyl group, an aryloxymethyl group, or Represents any of allyloxymethyl groups, X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; In addition, the substituent X on the anthracene ring occupies any position among the 5 to 8 positions, and similarly, Y occupies any position among the 1 to 4 positions. } The polymer according to claim 1 or 2, wherein the radical polymerization initiator is a thermal radical polymerization initiator. The polymer according to claim 1 or 2, wherein the radical polymerization initiator is a photo radical polymerization initiator. A polymerizable composition comprising a 9,10-di ((meth) acryloyloxyalkoxy) anthracene compound represented by the following formula (1) and a radical polymerization initiator.

{In Formula (1), n represents an integer of 1 to 10, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, an alkyl group, an aryl group, an alkoxymethyl group, an aryloxymethyl group, or Represents any of allyloxymethyl groups, X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; In addition, the substituent X on the anthracene ring occupies any position among the 5 to 8 positions, and similarly, Y occupies any position among the 1 to 4 positions. } The polymerizable composition according to claim 5, further comprising another radical polymerizable monomer. A polymer obtained by polymerizing the polymerizable composition according to claim 5.