JP2000281627A - Acrylic acid ester derivative and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new acrylic acid ester derivative having high transparency, mechanical properties and heat-resistance and low water-absorption and useful as a material for optical parts requiring low birefringence such as an optical disk base. SOLUTION: The objective compound is expressed by formula I (R1 is an alkyl, an alkoxy, nitro or the like; R2 is H or methyl; R3 to R5 are each hydroxy or fluorine atom; (m) is 0-3; (n) is 0-10) such as the compound of formula II. The objective compound can be produced by reacting an epoxy acrylate derivative of formula III with a fluorination agent such as trifluorodimethylamino sulfur in the absence of solvent or in a solvent inert to the reaction such as n-hexane at a reaction temperature of -78 to +80 deg.C for about several minutes to 100 hr and optionally further preventing the polymerization of the product by using a polymerization inhibitor such as methoquinone and converting the hydroxyl group in the molecule into fluorine atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an acrylate derivative. Furthermore, the present invention relates to a polymerizable composition containing the acrylic acid derivative, a polymer obtained by polymerizing the same, and an optical component obtained using the polymer. The optical component of the present invention has excellent transparency, mechanical strength, and heat resistance, and has low birefringence, and various plastic lenses represented by an optical disc substrate, a pickup lens, and a plastic substrate for a liquid crystal cell. It is useful as an optical fiber coating material and the like.

[0002]

2. Description of the Related Art Inorganic glass is used in a wide range of fields as a transparent material because of its excellent properties such as excellent transparency and small optical anisotropy. However,
There are problems such as being heavy and easy to break, poor productivity, and the like. In recent years, development of a transparent polymer in place of inorganic glass has been actively conducted. As a transparent polymer, for example,
Polymethyl methacrylate, polycarbonate, and the like are excellent in transparency and mechanical properties (for example, impact resistance, etc.), and are excellent in workability and moldability. Therefore, they are an alternative field of inorganic glass, for example, transparent parts and lenses for automobiles. Etc. are used.

[0003] On the other hand, sound, images,
The use of optical disks for recording and reproducing information such as characters has been rapidly expanding in recent years. However, in an optical disk used as an information recording medium, not only is it transparent because a laser beam passes through the disk body, but optical uniformity is strongly required in order to reduce information reading errors. . That is, for example, conventionally known polymers (for example, polycarbonate and the like)
In the case of using, the thermal stress generated during the cooling and flowing process of the resin during the molding of the disk substrate, molecular orientation, residual stress due to volume change near the glass transition point, etc.
Birefringence occurs when the laser beam passes through the disk substrate. The large optical non-uniformity caused by the birefringence is a fatal defect for an optical component such as an optical disc substrate, for example, an error in reading recorded information occurs. In optical components such as the optical disk substrate, a material having higher optical characteristics, that is, a material having low birefringence and excellent transparency and heat resistance is required.

One of the methods for solving the above-mentioned problems is a low-birefringence polycarbonate using a spiro compound, such as a spirobiindanol alone or a copolymerization type polycarbonate of spirobiindanol and bisphenol A. (JP-A-63-31423)
No. 5). However, although the former polycarbonate has a low birefringence, the molded product is easily cracked or cracked, and is very brittle and substantially impossible to injection-mold. There was a problem with transparency. Also, the latter polycarbonate,
By increasing the bisphenol A component, mechanical properties and transparency are improved, but the birefringence is increased, and there is a problem that the range of use as an optical component is limited,
It has been strongly desired to solve these conflicting problems.

Although polymethyl methacrylate has good optical properties among organic materials and is widely used as an optical polymer, heat resistance, water absorption, It was hard to say that it had sufficient performance in terms of properties. In the use as various optical components including the above-mentioned optical disc substrate,
Has high optical properties, that is, low birefringence, and
There has been a demand for a novel polymer material having good performance in terms of water absorption, heat resistance, mechanical properties, and the like.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems and to provide an optical component having good transparency, mechanical properties and heat resistance, low water absorption and low birefringence. And an acrylic ester derivative useful as a material for the optical component and a polymer thereof.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies with the aim of solving the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to an acrylate derivative represented by the general formula (1). The present invention also relates to a polymerizable composition containing the above acrylate derivative, a polymer obtained by polymerizing the polymerizable composition, and an optical component obtained using the polymer.

[0008]

Embedded image (Wherein, R ₁ independently represents an alkyl group, an alkoxy group, a nitro group or a halogen atom, R ₂ represents a hydrogen atom or a methyl group, R ₃ and R ₄ each represent a hydroxy group or a fluorine atom, R ₅ each independently represents a hydroxy group or a fluorine atom, m independently represents an integer of 0 to 3, and n represents an integer of 0 to 10, provided that all of R ₃ , R ₄ and R ₅ are It is not a hydroxy group at the same time.)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The acrylic ester derivative of the present invention is represented by the general formula (1). In the general formula (1),
R ₁ each independently represents an alkyl group, an alkoxy group, a nitro group or a halogen atom, preferably a straight-chain, branched or cyclic alkyl group which may have a substituent, Represents a straight-chain, branched or cyclic alkoxy group, nitro group or halogen atom, and more preferably has 1 to 2 carbon atoms which may have a substituent.
0 represents a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, a nitro group or a halogen atom.

Specific examples of the substituent R ₁ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, te
rt-butyl group, n-pentyl group, n-hexyl group, 2
-Ethylhexyl group, n-octyl group, n-decyl group,
n-dodecyl group, n-tetradecyl group, n-octadecyl group, cyclopentyl group, cyclohexyl group, 4-te
rt-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclohexylmethyl group, cyclohexylethyl group, tetrahydrofurfuryl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-butoxyethyl group, 3-methoxy Propyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-n-butoxypropyl group, 3-n-hexyloxypropyl group,
2-methoxyethoxyethyl group, 2-ethoxyethoxyethyl group, 2-phenoxymethyl group, 2-phenoxyethoxyethyl group, chloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 2,2,2-trichloroethyl Group, methoxy group, ethoxy group, n-propoxy group,
Isopropoxy group, n-butoxy group, isobutoxy group,
sec-butoxy group, n-pentyloxy group, n-hexyloxy group, 2-ethylhexoxyl group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, n-tetradecyloxy group, n -Octadecyloxy group, cyclopentyloxy group, cyclohexyloxy group, 4-tert-butylcyclohexyloxy group,
Cycloheptyloxy group, cyclooctyloxy group, cyclohexylmethyloxy group, cyclohexylethyloxy group, 2-methoxyethyloxy group, 2-ethoxyethyloxy group, 2-n-butoxyethyloxy group, 3-
Methoxypropyloxy group, 3-ethoxypropyloxy group, 3-n-propoxypropyloxy group, 3-n-
Butoxypropyloxy group, 3-n-hexyloxypropyloxy group, 2-methoxyethoxyethyloxy group, 2-phenoxymethyloxy group, 2-phenoxyethoxyethyloxy group, chloromethyloxy group, 2-
Chloroethyloxy group, 3-chloropropyloxy group,
Examples thereof include a 2,2,2-trichloroethyloxy group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituent R ₁ is more preferably an unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms, an unsubstituted straight-chain or branched alkoxy group having 1 to 10 carbon atoms,
A fluorine atom or a chlorine atom, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, Isopropoxy group, n-butoxy group, isobutoxy group, te
It is an rt-butoxy group, a fluorine atom or a chlorine atom.
A methyl group or a fluorine atom is particularly preferred as the substituent R ₁ .

In the general formula (1), the substituent R ₂ represents a hydrogen atom or a methyl group. In the general formula (1), the substituents R ₃ and R ₄ each represent a hydroxy group or a fluorine atom, and the substituents R ₅ each independently represent a hydroxy group or a fluorine atom. However, all of R ₃ , R ₄ and R ₅ are not simultaneously a hydroxy group. In the general formula (1), m is each independently 0 to 3
And is preferably 0, 1 or 2, more preferably 0 or 1. As m, the integer 0 is particularly preferred. In the general formula (1), n represents an integer of 0 to 10, preferably an integer of 0 to 8, and more preferably an integer of 0 to 5.

In the compound represented by the general formula (1) of the present invention, the substitution position of the substituent containing an acrylate group may be 4, 5, 6 or 7 on the benzene ring in the spirobiindane structure. And the substitution position of the other substituent containing an acrylate group is the 4 ′, 5 ′, 6 ′ or 7 ′ position. Among the compounds represented by the general formula (1), an acrylate derivative represented by the following formula (1-a) (formula 3) is more preferable.

[0014]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m and n are the same as above)

In the acrylate derivative represented by the general formula (1) of the present invention, as described later, a plurality of compounds having different fluorine atom contents in the molecule are produced simultaneously depending on the conditions at the time of production. In some cases. When the acrylate derivative represented by the general formula (1) of the present invention is used for the polymerizable composition of the present invention, a polymer obtained by polymerizing the polymerizable composition, or an optical component, a mixture thereof is used. Can be used as it is without separation and purification.

The acrylate derivative represented by the general formula (1) can be prepared by adding various known fluorinating agents to the epoxy acrylate derivative represented by the general formula (2) (formula 4).
Dimethylamino sulfur trifluoride, diethylamino sulfur trifluoride, morpholino sulfur trifluoride, (2-chloro-1,
1,2-trifluoroethyl) diethylamine, tris (dimethylamino) sulfonium difluorotrimethyl silicate and the like to convert a hydroxy group in a molecule into a fluorine atom by a functional group represented by the general formula (2). The hydroxy group in the molecule of the epoxy acrylate derivative is converted to a bromine atom, a chlorine atom, a methanesulfonic acid ester group, a trifluoromethanesulfonic acid ester group, a p-toluenesulfonic acid ester group or the like by a known synthetic chemical method. The product is further treated with an inorganic fluorine compound such as potassium fluoride, sodium fluoride, etc. on the product to obtain the functional group (bromine atom, chlorine atom, methanesulfonic acid ester group, Romethanesulfonic acid ester group or p-toluenes Such as sulfonic acid ester group) into fluorine atom step by step.
Various known synthetic chemical functional group conversion methods using these as representative methods [for example, methods described in Experimental Chemistry Lecture, 4th Edition, edited by The Chemical Society of Japan (1992), Vol. 19, pp. 384-392]. , Are preferably manufactured.

[0017]

Embedded image (Wherein, R ₁ each independently represents an alkyl group, an alkoxy group, a nitro group or a halogen atom, R ₂ represents a hydrogen atom or a methyl group, m each independently represents an integer of 0 to 3, and n represents Represents an integer of 0 to 10)

Among the above-mentioned methods, the former method [the epoxy acrylate derivative represented by the general formula (2) is reacted with a fluorinating agent such as diethylaminosulfur trifluoride to form a hydroxy group into a fluorine group. The method of converting a functional group into an atom] is a preferable method in view of the advantage that the target product can be obtained in a short stage. The epoxy acrylate derivative represented by the general formula (2), which is a raw material,
It is a known compound described in JP-A-11-71316, and is suitably produced according to the method described in the patent.

Hereinafter, as the method for producing the acrylate derivative of the present invention, the epoxy acrylate derivative represented by the general formula (2) is compared with the epoxy acrylate derivative represented by the general formula (2) in the above-mentioned various production methods. The method for converting a hydroxy group into a fluorine atom by the action of an agent will be described in more detail. In such a reaction, the amount of the fluorinating agent to act on the epoxy acrylate derivative represented by the general formula (2) is usually 0.1 to 10 equivalents per equivalent of the hydroxyl group of the raw material epoxy acrylate derivative. And preferably 0.
2 to 5 equivalents, more preferably 0.8 to 1.2 equivalents.
Double equivalent.

The reaction may be carried out without a solvent or in a solvent inert to the reaction. Such solvents include, for example, hydrocarbon solvents such as n-hexane, benzene or toluene, ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone, ester solvents such as ethyl acetate or butyl acetate,
Examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane, and halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and perchrene. Two or more of these solvents may be used in combination.

The reaction temperature is not particularly limited, but is a temperature at which the starting acrylate compound is not polymerized, and
It is preferable that the temperature is equal to or lower than the decomposition temperature of the fluorinating agent as a reactant (for example, the temperature is 90 ° C or lower when diethylaminosulfur trifluoride is used as the fluorinating agent),
Usually, it is -78 ° C to 80 ° C, preferably, -78 ° C to
It is 50 degreeC, More preferably, it is -78 degreeC-25 degreeC. The reaction time depends on the reaction temperature, but is usually several minutes to
It is 100 hours, preferably 30 minutes to 50 hours, more preferably 1 to 20 hours.

In producing the acrylate compound represented by the general formula (1), it is preferable to use a polymerization inhibitor in order to prevent polymerization of the product during or after the reaction. . Examples of such a polymerization inhibitor include various known compounds such as methoquinone, hydroquinone, and phenothiazine. The amount of the polymerization inhibitor used is not particularly limited, but is usually 0.01 to 0.01% based on the raw material mixture or the reaction product in the reaction system.
5%, preferably 0.05-3%.

After completion of the reaction, the resulting acrylate derivative represented by the general formula (1) is post-treated by a known operation and treatment method (eg, washing with water, liquid separation, solvent extraction, neutralization, etc.). Isolated. Further, if necessary, the acrylate derivative represented by the general formula (1) is separated and purified by a known method (for example, distillation, recrystallization or chromatography, etc.), and isolated as a high-purity compound. You can also. Further, the acrylate derivative represented by the general formula (1) of the present invention may be used as it is as a mixture of a plurality of different derivatives.

Next, the polymerizable composition of the present invention will be described in detail. The polymerizable composition of the present invention contains, as an essential component, the acrylate derivative represented by the general formula (1) of the present invention, and further contains a light and / or thermal polymerization initiator. In this case, the acrylate derivative may be used alone, or a plurality of different acrylate derivatives may be used in combination. The amount of the acrylate derivative represented by the general formula (1) contained in the polymerizable composition is not particularly limited, but is usually 10% by weight or more based on the weight of the entire polymerizable composition. ,
Preferably, it is at least 20% by weight, more preferably,
It is at least 30% by weight, more preferably at least 50% by weight.

The polymerization initiator used in the polymerizable composition of the present invention is not particularly limited, and various known thermal polymerization initiators or photopolymerization initiators can be used. As the photopolymerization initiator, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-
2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2
-Morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone ,
2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone And the like.
These can be used alone or in combination of two or more.

The amount of the photopolymerization initiator used is determined by the general formula (1)
It is 0.001 to 50 parts by weight with respect to 100 parts by weight of the acrylate derivative represented by the formula, preferably,
0.01 to 30 parts by weight, more preferably 0.1 to 30 parts by weight.
10 to 10 parts by weight, more preferably 0.2 to 5 parts by weight. Furthermore, the simultaneous use of one or more of these photopolymerization initiators and known photosensitizers is
It is a good thing. As the photosensitizer, for example,
N, N-dimethylaminobenzoic acid ethyl ester, N, N
Examples thereof include N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, and triethylamine.

Preferable combinations of the photopolymerization initiator and the photosensitizer include a combination of 2,4-diethylthioxanthone or 2-isopropylthioxanthone and N, N-dimethylaminobenzoic acid ethyl ester. Preferred combinations of the agents are 2
-Methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one and a combination of 2,4-diethylthioxanthone or 2-isopropylthioxanthone.

Examples of the thermal polymerization initiator include, for example, benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-
Examples include peroxides such as ethylhexyl peroxycarbonate and tert-butyl peroxypivalate, and azo compounds such as azobisisobutyronitrile. The amount of the thermal polymerization initiator used is represented by the general formula (1)
Is usually 0.001 to 50 parts by weight, preferably 0.01 to 30 parts by weight, more preferably 0.01 to 30 parts by weight, based on 100 parts by weight of the acrylate derivative represented by
0.1 to 10 parts by weight, more preferably 0.2 to 10 parts by weight.
-5 parts by weight.

The polymerizable composition of the present invention contains, in addition to the acrylate derivative represented by the general formula (1),
If necessary, a generally known polymerizable compound (such as a photo- or thermo-polymerizable monomer or oligomer) may be contained as long as the desired effect is not impaired. Examples of such a polymerizable compound include methyl (meth) acrylate, butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, ethyl carbitol (meth) acrylate, lauryl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, Nn-butyl-O-
(Meth) acryloyloxyethyl carbamate, acryloyl morpholine, trifluoroethyl (meth) acrylate, tribromobenzyl (meth) acrylate,
Monofunctional (meth) acrylates such as perfluorooctylethyl (meth) acrylate;

Silicon-containing (meth) acrylates such as (meth) acryloxypropyltris (methoxy) silane; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate; Alkylene glycol di (meth) acrylates such as 1,6-hexanediol di (meth) acrylate; triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol Polyalkylene glycol di (meth) acrylates such as di (meth) acrylate; alkylenes of bisphenol derivatives such as bisphenol F, bisphenol A and hydrogenated bisphenol A Di (meth) acrylates of Kishido adduct; trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate,
Polyfunctional (meth) acrylates such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylol tetraacrylate, dipentaerythritol hexaacrylate;

Epoxy acrylates such as ethylene glycol diglycidyl ether di (meth) acrylate, propylene glycol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate; phenol novolak type epoxy resin, cresol novolak type Epoxy acrylates, which are reaction products of epoxy compounds such as epoxy resins, bisphenol type epoxy resins, and tris (2,3-epoxypropyl) isocyanurate with acrylic acid or methacrylic acid; N-vinylpyrrolidone, N-vinylcaprolactam, Monofunctional vinyl compounds; public compounds such as allyl group-containing compounds such as ethylene glycol diallyl carbonate, triallylic acid triallyl ester, and triallyl isocyanurate Polymerizable monomer; or, polyurethane (meth) acrylate, epoxy (meth) acrylates, polyester (meth) acrylate, various known polymerizable oligomers such as polyether (meth) acrylate and the like. The amount of each of these is the amount of the acrylate derivative 1 represented by the general formula (1) of the present invention.
The amount is usually 300 parts by weight or less, preferably 200 parts by weight or less, more preferably 100 parts by weight or less with respect to 00 parts by weight.

In producing the polymerizable composition, if necessary, an inorganic filler (for example, talc, silica, alumina, barium sulfate, magnesium oxide, etc.), a thixotropic agent (for example, Aerogel, etc.), melamine Resins (eg, hexamethoxymelamine, hexabutoxymelamine, etc.), leveling agents (eg, silicone, fluoropolymers, acrylic copolymers, etc.), coloring pigments (eg, cyanine green, cyanine blue, etc.), defoamers,
It is also possible to add various known additives such as an ultraviolet absorber, an antioxidant, and a flow regulator.

The polymer of the present invention is obtained by polymerizing a polymerizable composition containing an acrylate derivative represented by the general formula (1), and is obtained by curing with light or heat. Further, there is a material used as a thermoplastic material. Further, the optical component of the present invention is obtained by using the above-mentioned or the polymer. The optical component of the present invention has good transparency, mechanical strength, and heat resistance, and has low birefringence.For example, an optical recording medium substrate, an optical recording medium substrate such as a magneto-optical disk substrate,
Examples include optical lenses such as pickup lenses, plastic substrates for liquid crystal cells, and various optical components such as prisms.

Next, a method for producing an optical component obtained by using a polymer obtained by polymerizing the polymerizable composition containing the acrylic ester derivative of the present invention will be described in more detail. When the optical component of the present invention is manufactured using the above polymer, after preparing a polymerizable composition containing the acrylate derivative represented by the general formula (1), various known molding methods described below are used. Thereby, the optical component of the present invention can be suitably manufactured as a molded article of a polymer obtained by polymerizing the polymerizable product.

As a method of forming the base of an optical disk or a magneto-optical disk, for example, a polymerizable composition containing an acrylate derivative represented by the general formula (1) is injected into a disk base mold cavity, and A method of polymerizing by a radical polymerization method or the like and, if necessary, performing a post-heat treatment (Japanese Unexamined Patent Publication No.
8-130450, 58-137150, 62-280008), a method of photopolymerization in a double-sided glass mold (Japanese Patent Application Laid-Open No. 60-202557), after vacuum casting or after completion of liquid injection. Method of thermally polymerizing a liquid resin under pressure (Japanese Patent Application Laid-Open No. 60-203414)
For example, a conventionally known method can be used.

As a molding method of the optical lens, for example,
A lens can be suitably obtained by casting polymerization (for example, JP-A-60-135901). That is, the polymerizable composition containing the above acrylate derivative of the present invention, if necessary, after defoaming by an appropriate method, is poured into a mold, usually gradually from low temperature to high temperature. It can be suitably carried out by heating and polymerizing.

When the optical component of the present invention is produced using the above-mentioned polymer, the above-mentioned polymerizable composition is
After polymerization using various known polymerization methods such as bulk polymerization, solution polymerization, and suspension polymerization, in the presence of a polymerization initiator, by a known polymerization reaction (for example, radical polymerization, coordination polymerization, or transfer polymerization). The optical component of the present invention is molded by a known thermoplastic resin molding method (for example, injection molding, injection compression molding, extrusion molding, blow molding, etc.) as a thermoplastic material.

[0038]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples and Examples, but the present invention is not limited to these Production Examples and Examples. Reference Production Example 1 [(Method for producing epoxy resin represented by formula (2-1)] In a reaction vessel, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'- 308 g of spirobiindane (1.
00 mol) and 926 g of epichlorohydrin (10.
(0 mol) and heated to 95 ° C. to dissolve. A 40% aqueous sodium hydroxide solution 2 was added to the reaction mixture.
20 g was added dropwise over 3 hours, and the mixture was stirred at 90 to 100 ° C. for 2 hours. After cooling the reaction solution, 400 ml of methyl ethyl ketone was charged, and washing with water was repeated until the chlorine compound and the remaining sodium hydroxide were removed in trace amounts or less. The solvent and epichlorohydrin were distilled off from the organic layer under reduced pressure to obtain 422 g of an epoxy resin represented by the formula (3) (formula 5). The yield was 89%. As a result of analysis by liquid chromatography, the composition was 86% when n = 0,
8% for n = 1, 6% for n ≧ 2 (Area%, the same applies hereinafter)
Met. The epoxy equivalent was 238 g / eq, and the softening point was 50 ° C.

[0039]

Embedded image

Subsequently, 238 g of the obtained epoxy resin represented by the formula (3) and acrylic acid 7 were placed in a reaction vessel.
2 g (1.00 mol), triethylamine 0.9 g, hydroquinone 0.1 g and styrene 31 as a diluent
g, and stirred at 80 ° C. for 1 hour and then at 130 ° C. for 3 hours while blowing air into the reaction mixture to obtain a wax-like epoxy acrylate represented by the formula (2-1). 327 g of resin was obtained. The acid value of this compound (m
gKOH / g) was 3.0 and the ICI viscosity was 1.8 poise (100 ° C.).

[0041]

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Reference Production Example 2 [(Production Method of Epoxy Resin Represented by Formula (2-2)] In Reference Production Example 1, instead of 72 g of acrylic acid,
Reference Production Example 1 except that 86 g of methacrylic acid was used.
In the same manner as described in the above, an epoxy methacrylate resin represented by the following formula (2-2) (Formula 7) was obtained.

[0043]

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Production Example 1 (Synthesis of Acrylic Ester Derivative of the Present Invention) 56.47 g of the epoxy acrylate derivative represented by the formula (2-1) synthesized in Reference Production Example 1 and 60 g of methylene chloride were placed in a reaction vessel. A solution obtained by dissolving 32.24 g (0.20 mol) of diethylaminosulfur trifluoride in 50 g of methylene chloride at −78 ° C. under a nitrogen atmosphere was added to the solution obtained by weighing and mixing for 30 minutes. And dropped.
After the dropwise addition, the mixture was further stirred at the same temperature for 1 hour, heated to room temperature, and 100 g of ice water was added to the reaction mixture. After stirring for 30 minutes, the mixture was separated and washed three times with water. The lower methylene chloride layer was taken out and the solvent was distilled off to obtain 60 g of a colorless transparent liquid as a product. The crude product was separated and purified by silica gel column chromatography to obtain 40 g of the acrylic ester derivative of the present invention represented by the following formula (1-1) (Formula 8) as a viscous colorless transparent liquid.

[0045]

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The results of ¹ H-NMR (400 MHz) of a 1% by weight deuterated chloroform solution and high-resolution field ionization mass spectrometry of the above compound are shown below. ¹ H-NMR: δ (CDCl ₃ ); 1.3 (s, 12
H) 2.2-2.4 (m, 4H), 3.9-4.3
(M, 8H), 4.4 (m, 2H), 5.6-6.3
(M, 6H), 6.3 (s, 2H), 6.6-7.2
(M, 4H) FD-MS: 568.6 (M +)

Preparation Example 2 The procedure of Preparation Example 1 was repeated except that diethylaminosulfur trifluoride was used.
Performed in the same manner as described in Preparation Example 1 except that 29.01 g (0.18 mol) of diethylaminosulfur trifluoride was used instead of 24 g (0.20 mol), and the product was colorless. 58 g of a transparent liquid were obtained. The product was analyzed by liquid chromatography-mass spectrometry (LC-M
S, Micromass Co., Ltd., QUATTRO-2) was analyzed by the above formula (1-1) and the following formula (1-
2) to (1-6) (Formula 9).

[0048]

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The content of each component determined by high performance liquid chromatography analysis was as follows.

Component content (area%) in the product Compound represented by the formula (1-1) 70 Compound represented by the formula (1-2) 16 Compound represented by the formula (1-3) 6 Compound represented by Formula (1-4) 1 Compound represented by Formula (1-5) 0.7 Compound represented by Formula (1-6) 0.3 Others (n = 2 or more oligomers) 5.9 in the same manner as described in total 99.9% production example 1, of the mixture ¹ H-
NMR (400 MHz) is measured to determine the integral ratio between the peak of the hydrogen atom of the methylene carbon bonded to the hydroxy group and the peak of the hydrogen atom of the methylene carbon bonded to the fluorine atom, thereby converting the hydroxy group to a fluorine atom. When the ratio was determined, it was 80%.

Production Example 3 In Production Example 1, the compound of the above formula (2-1) was used as a starting compound.
Production Example 1 except that the epoxy methacrylate derivative represented by the formula (2-2) produced in Reference Production Example 2 was used instead of the epoxy acrylate derivative represented by
The methacrylate derivative of the present invention represented by the following formula (1-7) (Formula 10) was obtained as a colorless and transparent liquid.

[0052]

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The results of ¹ H-NMR (400 MHz) of a 1% by weight deuterated chloroform solution and high-resolution field ionization mass spectrometry of the above compound are shown below. ¹ H-NMR: δ (CDCl ₃ ); 1.3 (s, 12
H), 1.9 (s, 6H), 2.2 to 2.4 (m, 4
H) 3.9-4.3 (m, 8H), 4.4 (m, 2
H) 5.6-6.3 (m, 4H), 6.3 (s, 2
H), 6.6-7.2 (m, 4H) FD-MS: 596.7 (M +)

Examples 1 to 11 Using the acrylate derivatives obtained in Production Examples 1 to 3, polymerizable compositions were prepared by the following method. In addition, the following test evaluation was performed using a polymer molded product obtained by subjecting the polymerizable composition to light or / and thermal polymerization. (1) Preparation of Polymerizable Composition Using the acrylate derivatives obtained in Production Examples 1 to 3, various materials having the composition (numerical parts by weight) shown in Table 1 below are used. And a photo- or thermo-polymerizable composition was prepared.

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[Table 1]

The abbreviations in the table indicate the following compounds. -MMA: methyl methacrylate-EGDM: ethylene glycol dimethacrylate-TMPTA: trimethylolpropane triacrylate-PTA: pentaerythritol tetraacrylate-BPABM: bisphenol A bis (2-methacryloyloxypropyl ether)-I-907: Irgacure-907 Ciba Geigy Co., Ltd., photopolymerization initiator C-1173: Drocur-1173, Merck Co., Ltd.
Photopolymerization initiator DETX: Kayacure-DETX-S, manufactured by Nippon Kayaku Co., Ltd. Photopolymerization initiator t-BPEH: tert-butylperoxy-2-ethylhexanoate, thermal polymerization initiator BPO: Benzoyl peroxide, thermal polymerization initiator

(2) Production Method of Polymer Molded Product [Photopolymerization] Each of the polymerizable compositions in Table 1 was applied to a glass plate (100 mm ×
100mm x 5mm) and two pieces of silicone rubber (thickness 2.0
mm) into a mold made of a gasket, and irradiated with light for 3 minutes on each side using a high-pressure mercury lamp. After that, post-cure at 80 ° C for 3 hours in a hot blast stove.
A polymer molding was obtained. [Thermal polymerization] Each polymerizable composition was placed on a glass plate (100 mm ×
100mm x 5mm) and two pieces of silicone rubber (thickness 2.0
mm) into a mold made of a gasket, and heated in a hot blast stove from 60 ° C. to 100 ° C. for 6 hours.
Polymerization was carried out for a time to obtain a polymer molded product.

(3) Test Evaluation Method of Polymer Molded Product The polymer molded product obtained by curing the polymerizable composition by the above method was evaluated by the following method. The result is the second
The results are shown in the table (Table 2). Appearance: The surface state of the obtained test piece was visually observed and evaluated.

A: Colorless and transparent, excellent in surface state without cracks, cracks, etc. ×: Those in which cracks, cracks, etc. are observed Total light transmittance (hereinafter referred to as transmittance): ASTM
Measured according to the D-1003 method Birefringence: Precision strain gauge (SVP- manufactured by Toshiba Glass Co., Ltd.)
30-II) Heat resistance test: After leaving in a hot-air drying group at 120 ° C. for 6 hours, the molded product was taken out, visually observed and evaluated.

：: No coloring, surface distortion, cracks, etc. of the molded product ×: Coloring, surface distortion, cracks, etc. of the molded product are observed Saturated water absorption (hereinafter referred to as water absorption): ASTM
According to the D-770 method, the molded product was stored in water at 23 ° C. for one week, and the water absorption was measured to determine the amount.

Comparative Example 1 A general-purpose optical polymethyl methacrylate was used as a polymer and injection-molded at 230 ° C. to produce a dumbbell-shaped plate-like molded product (2.0 mm thick). Table 2 shows the results of test evaluation of this molded product according to the above method.

Comparative Example 2 An existing polycarbonate derived from bisphenol A was used as a polymer and injection-molded at 280 ° C. to produce a dumbbell-shaped plate-shaped product (2.0 mm thick). Table 2 shows the results of test evaluation of this molded product according to the above method.

Comparative Example 3 According to the method described in Example 7 of JP-A-63-314235, a copolymerized polycarbonate of bisphenol A and spirobiindanol was produced. The weight average molecular weight was 44,800. Using the obtained polycarbonate, injection molding was performed in the same manner as in Comparative Example 2 to prepare a dumbbell-shaped plate-like molded product (2.0 mm in thickness). Table 3 shows the results of test evaluation of this molded article according to the above-described method.

Comparative Example 4 In Example 1, the formula (1) of the present invention produced in Production Example 1 was used.
-1), except that the epoxy acrylate derivative represented by the formula (2-1) of Reference Production Example 1 is used instead of using the acrylate derivative represented by the formula (1). Similarly, a polymerizable composition was prepared and photopolymerized to obtain a polymer molded product. Table 3 shows the results of test evaluation of this molded product according to the above method.

Comparative Example 5 According to the method described in Example 9 of JP-A-63-314235, a homopolycarbonate of spirobiindanol was produced. The weight average molecular weight was 57000, and the glass transition temperature was 228 ° C. The melt viscosity at 300 ° C. was 4,500 poise. Using this polycarbonate, injection molded by the same method as the above method to produce a molded product, and to perform a test evaluation,
The obtained molded product was very brittle and easily cracked, and could not be substantially molded.

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[Table 2] As is clear from Table 2, the molded product composed of the polymer obtained by polymerizing the acrylate derivative represented by the general formula (1) of the present invention has a higher
It has excellent transparency, mechanical properties, and heat resistance, has a low water absorption, and has low birefringence, and is very useful as an optical component.

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According to the present invention, an optical component having good transparency, mechanical strength, and heat resistance, a low water absorption, and a low birefringence, and a material useful for the optical component. An acrylic ester derivative and a polymer thereof are provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4H006 AA01 AB46 BJ50 BN10 BP30 4J027 AE04 BA07 BA19 BA20 BA26 BA27 CD04 4J100 AG69Q AH06Q AL03Q AL04Q AL08Q AL62Q AL63Q AL66P AL66Q AL67Q AM21Q AQ06Q AQ08Q A03 BA03 BA04 BA11Q BA38Q BA41P BA77Q BB01P BB03P BB03Q BB05P BB07P BB18Q BC02P BC03P BC04P BC07Q BC12P BC43P BC43Q BC45Q BC48P BC54Q CA01 CA04 DA22 DA47 DA62 JA32 JA33 JA36

Claims (4)

[Claims] 1. An acrylate derivative represented by the general formula (1). Embedded image (Wherein, R ₁ independently represents an alkyl group, an alkoxy group, a nitro group or a halogen atom, R ₂ represents a hydrogen atom or a methyl group, R ₃ and R ₄ each represent a hydroxy group or a fluorine atom, R ₅ each independently represents a hydroxy group or a fluorine atom, m independently represents an integer of 0 to 3, and n represents an integer of 0 to 10, provided that all of R ₃ , R ₄ and R ₅ are It is not a hydroxy group at the same time.) 2. A polymerizable composition containing the acrylate derivative according to claim 1. 3. A polymer obtained by polymerizing the polymerizable composition according to claim 2. 4. An optical component obtained by using the polymer according to claim 3.