JPH03157410A - Polyalicyclic polyacrylic acid ester derivative - Google Patents

Abstract

PURPOSE:To obtain the title polymer suitable as a material such as optical lens, digital audio disc, etc., having transparency and strength of characteristic methacrylic resin, high glass transition temperature and low water absorption ratio, comprising a specific structure. CONSTITUTION:The objective polymer shown by formula I (R and R' are H or methyl; R1 is 1-4C chain alkyl; A is constituent unit derived from group copolymerizable with acrylic ester; l is 0.04-1; m is 0-0.96; n is 0-0.5, with the proviso that m+n+l=1 and when m is <=0.2, n is <=0.01) and having 5,000-1,000,000 molecular weight. The polymer is preferably obtained by homopolymerizing a monomer shown by formula II prepared by reacting 3,4- epoxyhydroxytricyolo[5.2.1.0<2.6>]decane with (meth)acryloylchoride or copolymerizing an acrylic monomer shown by formula III with a monomer to derive a unit A such as unit shown by formula IV.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a polyalicyclic polyacrylic acid ester derivative, and this polymer resin composition can be used for optical lenses,
It is particularly useful as a resin for optical materials used in digital audio discs, optical memory discs, etc.

[Prior Art] Acrylic resins such as polymethyl methacrylate have traditionally been used for optical lenses, digital audio discs, optical memory discs, etc. due to their properties such as transparency and strength.
It is applied to optical fibers, etc. (Japanese Patent Laid-Open No. 57-74
701.63-180906, etc.). However, it has been pointed out that conventional acrylic resins have drawbacks such as a low glass transition temperature and a high water absorption rate.

Various methods have been proposed to date to solve these problems. For example, as a method aiming at improving heat resistance and decreasing hygroscopicity, JP-A-62-151413.63
-72708, Special Publication No. 46-28419, etc.
These still have many problems such as moldability, and have not been put to practical use.

In contrast to the acrylic resins mentioned above, epoxy resins have traditionally been known as resins with high heat resistance.
Epoxy resins, like acrylic resins, have excellent optical properties such as transparency and optical anisotropy, but they have problems with molding time, etc., and they have high molecular weight in bulk reactions by photocuring using ultraviolet rays. Problems have been pointed out, such as difficulty in proceeding with three-dimensional crosslinking and three-dimensional crosslinking.

[Problems to be Solved by the Invention] In view of the above-mentioned condition 61, the present inventors have created a resin that maintains the properties of conventional methacrylic resins in terms of transparency and strength, while achieving a high glass transition temperature and low water absorption. The present invention aims to provide a polymer resin composition and an optical material molded article formed from the polymer resin composition.

Ta.

That is, the present invention solves the above problem by formula (1). In order to make a decision, we conducted a thorough investigation. As a result, a derivative whose basic constituent is a polyalicyclic acrylic ester derivative represented by the following structural formula (2) exhibits excellent physical properties such as optical homogeneity, mechanical strength, heat resistance, and water absorption. In the formula, R and R' each independently represent a hydrogen atom or a methyl group, and R1 represents C1 ~C4 represents a straight chain or branched alkyl group, A represents a structural unit derived from a random copolymerizable with acrylic acid esters, and 11m and n are respectively 0.04 to 1.0 to 0 in this order.
．． 96 and O to 0.5, the sum of which is 1, and when m is 0.2 or less, n is a number that is 0.01 or less), and the molecular weight is 5.000 to 1.00.
This product contains 1,000 polyalicyclic polyacrylic acid ester derivatives.

As the acrylic ester derivative leading to structural unit A,
In particular, a polymer in which m is not 0 and n is 0 in formula (1),
That is, a monomer represented by formula (4) can be exemplified.

The polymer represented by formula (3) (in the formula, R represents a hydrogen atom or a methyl group) in which both mSn is 0 in formula (1) has extremely high heat resistance, and its glass transition temperature is 200°C or higher. It is. Although this is preferable, it also increases the melting temperature, so when molding a resin composition containing this polymer, a considerably higher temperature is required compared to other acrylic resins.

(In the formula, R and R' each independently represent a hydrogen atom or a methyl group, and R3 represents a straight chain or branched alkyl group of Cl""' Ca) and a polymer where neither m nor n is 0. , especially equations (5), (6) or (7
) (in each formula, R and R- each independently represent a hydrogen atom or a methyl group, and R represents a C1 to C4 linear or branched alkyl group) have different thermal properties. It has the following characteristics. For example, the copolymer of formula (4) can adjust the glass transition temperature of the polymer of formula (3) by adjusting the copolymerization ratio, and the copolymer of formula (5) can adjust the fluidity when melted. It is particularly rich in the formula (
The polymers represented by 6) and (7) are particularly excellent in heat decomposition resistance.

The compound represented by formula (2) that can be used in the production of the polyalicyclic polyacrylic ester derivative of the present invention is 3.
4-Epoxyhydroxytricyclo(5,2,1,0”
) Decane is reacted with acryloyl chloride or methacryloyl chloride in the presence of a base in an inert gas at a temperature of -50 to 100°C, preferably 0 to 50°C, and a reaction time of 0.5 to 30 hr, preferably 1 to 10 hr. Obtained by carrying out a reaction. A solvent may be added to the reaction if necessary.

Solvents used here include n-hexane, n-pentane, cyclohexane, benzene, toluene, xylene, trichloroethylene, tetrachloroethylene, chloroform, diethyl ether, tetrahydrofuran, diisopropyl ether, and the salt U is sodium hydroxide. , alkali metal hydroxides such as potassium hydroxide,
Alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, or pyridine, triethylamine, dimethylaminopyridine, etc. amines can be used.

The monomer (2) synthesized as described above can be used alone or according to the formula (8) (wherein R' represents a hydrogen atom or a methyl group, and R1 represents a C
1-C4 linear or branched alkyl group) and a group copolymerizable with acrylic acid esters, such as formula (9), to obtain the desired regular polymer. However, the blending ratio of these monomers is expressed as the respective molar fraction (2
), (8), and (9) in the order of 0.04 to 1.0 to 0.96 and 0 to 0.5, the sum of which is 1, and the fraction of formula (8) is 0.2. Formula (9) when:
The fraction is a number that is 0.01 or less.

As the polymerization method, ordinary radical polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, etc. can be used. Examples of polymerization initiators used in this case include organic peroxides such as benzoyl peroxide, diisopropyl peroxide, tert-butyl peroxypivalate, and lauroyl peroxide, azo compounds such as azoisobisbutyronitrile, and photopolymerization As the initiator, photosensitizers such as benzophenone, benzoynethyl ether, dibenzyl, acetophenone, and anthraquinone, and sulfur compounds such as diphenyl sulfide and thiocarbamate can be used. The amount of polymerization initiator used is 0.001 parts by weight based on 100 parts by weight of total monomers.
-10 parts by weight, preferably 0.01-10 parts by weight.

The polymerization temperature varies depending on the type of polymerization initiator, but it ranges from 0 to
The temperature is preferably 200°C, preferably in the range of 50 to 120°C.

Through the above process, the copolymer of the repeating unit (6) of the present invention can be produced. The molecular weight of this polymer is about 5,000 to 1,000,000, preferably about 30,000 to about 500,000.

In the present invention, the thus obtained polymer is molded by a general molding method for polymer resin compositions, such as injection molding, to form an optical material molded body.

In addition, during such molding, antioxidants,
An antistatic agent or the like may be added.

Although this molded body sufficiently exhibits the desired physical properties and can be put to practical use as it is, it is necessary to further increase the heat resistance and mechanical strength of the molded body after molding (3). It is possible to add a crosslinking agent to the polymers shown in , (4), (5), (6), and (7) and form a three-dimensional crosslinked product by the action of light and/or heat. .

This process is carried out by adding an epoxy curing catalyst, a curing agent, a curing accelerator, etc. to the polycyclic acrylic ester derivative obtained as described above.

Examples of photocuring catalysts include onium salt compounds of Lewis acid anions, and complexes of photocleavable silanol derivatives and aluminum chelates. Examples of onium salts in onium salts of Lewis acid anions include aromatic halonium salts such as diaryliodonium salts and diarylbromonium salts, aromatic chalconium salts such as triarylsulfonium salts and triarylselenium salts, and diazonium salts that are efficiently photocleaved. things are used. Lewis acids that form salts with onium ions, such as ClO4-, BF
4-PF6-, ASF'6SbF6-, etc.

In the photocleavable silanol derivative-aluminum chelate complex compound, 0-nitrobenzylsilyl ether, trialkylmethanesilyl peroxide, which is obtained by derivatizing silanol with 0-nitrobenzyl alcohol, trialkylmethane hydroperoxide, etc., is used as the photocleavable silanol derivative. Oxide etc. are used. Examples of aluminum chelates include aluminum tris-acetoacetate chelates such as aluminum tris-ethyl acetoacetate;
Aluminum tris-0-carbonylphenol chelate such as aluminum tris salicylaldehydate, aluminum tris acetylacetone chelate, etc. are used.

The amount of the photocuring catalyst used is 0.01 to 5 parts by weight per 100 parts by weight of the polycyclic acrylic ester derivative polymer of the present invention.
Part by weight, preferably 0.01 to 1 part by weight. Also,
Additives such as photosensitizers and stabilizers may be used as necessary. Although the light used during curing varies depending on the curing catalyst used, it is usually 180 to 700 nm, and ultraviolet light is particularly effective. Examples of light sources include low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, metal halide lamps, hydrogen discharge tubes, tungsten lamps, halogen lamps, sodium discharge tubes, neon discharge tubes, and He-
Examples include Ne laser and Ar laser shade. The irradiation time is preferably about 1 second to 15 minutes.

Curing agents used during thermal curing include amines such as aliphatic polyamines, aromatic polyamines, secondary and tertiary amines,
Polyamide resins such as fatty acids, condensates of fatty acids such as dimer acid and trimer acid with aliphatic polyamines, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride Acid, chlorendic anhydride, dodecylsuccinic anhydride, methyltetrahydrophthalic anhydride,
Examples include acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride, and complexes of boron trifluoride with monoethylamine, piperidine, aniline, butylamine, triethanolamine, and the like. Hardener is epoxy prepolymer 10
5 to 200 parts by weight is added to 0 parts by weight.

As curing accelerators, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylethanolamine, dimethylaminoethanol, tri(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2- Imidazoles such as phenyl-4-methylimidazole and 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, diphenylphosphine,
Examples include organic phosphines such as triphenylphosphine and phenylphosphine, and tetraphenylboron salts such as tetraphenolphosphonium tetraphenylborate and 2-ethyl-4-methylimidazole tetraphenylboreto.

The curing accelerator is a total of 100ff of the polymer and curing agent used.
0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight, based on part f.
05 to 5 parts by weight are used.

Thermal curing is usually from 0 to 200°C, preferably from 20 to 130°C.
Performed at °C.

When crosslinking and curing the resin of the present invention, an antioxidant, an antistatic agent, an ultraviolet absorber, a mold release agent, etc. may be added as necessary.

It should be noted that the above synthesis methods and polymerization methods are merely examples.
It is not necessarily limited to nature.

Furthermore, the following method is also possible as a method for producing a three-dimensional crosslinked product. That is, it is a method in which a polymerization initiator is added to the monomer represented by formula (2), and the polymerization reaction and crosslinking reaction are simultaneously proceeded by the action of light and/or heat, and the resin obtained by this method is also transparent. It was found that the material has excellent properties such as hardness, heat resistance, moisture resistance, mechanical strength, and optical homogeneity. In this method, a photocuring initiator, a thermosetting initiator, a curing agent, and a curing accelerator are added to the compound represented by formula (2) as necessary, and a photocuring reaction, a thermosetting reaction, or both curing reactions occur. The desired three-dimensionally crosslinked resin molded article is manufactured by using the above in combination.

The photocuring initiator is a compound of formula (3), (4), (5), (6), (7) that acts on the epoxy μ of the compound of formula (2).
) The same onium salt compound of a Lewis acid anion as used in crosslinking and curing the polymer, a composite of a photocleavable silanol derivative and an aluminum chelate, etc. can be used. The amount of the photocuring initiator used is 0.01 to 5 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the monomer.
1 part by weight is good.

In addition, as a photocuring initiator that acts on the vinyl bond in the acrylic ester in formula (2), benzophenone, benzoin ethyl ether, dibenzyl, acetophenone,
Photosensitizers such as anthraquinone, diphenyl sulfide,
Sulfur compounds such as thiocarbamates can be used. The use of this initiator is 0.001 to 10 parts by weight, preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the compound represented by formula (2).
A range of 0.01 to 5 parts by weight is preferable.

The light used during curing is expressed by formulas (3), (4), (5), and (6).
), the same light source used when crosslinking and curing the polymer in (7) can be used. Irradiation time is 1
A good time is between seconds and 15 minutes.

As the epoxy curing agent used during thermal curing, formula (3)
, (4), (5), (6), the same aliphatic polyamine as that used when crosslinking and curing the polymers of (7),
Aromatic polyamines, amines such as secondary and tertiary amines, polyamide resins such as condensates of fatty acids and aliphatic polyamines such as fatty acids, dimer acids and trimer acids, phthalic anhydride,
Acids such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, chlorendic anhydride, dodecyl succinic anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc. Examples include anhydrides, complexes of boron trifluoride with monoethylamine, piperidine, aniline, butylamine, triethanolamine, etc. The curing agent is compound 1 represented by formula (2)
5 to 200 parts by weight per 00 parts by weight.

Examples of the thermal polymerization initiator that acts on the vinyl bond in the acrylic ester in formula (2) include organic peroxides such as benzoyl peroxide, diisopropyl peroxide, tert-butyl peroxyvivalate, and lauroyl peroxide; Examples include azo compounds such as isobisbutyronitrile. The amount of the polymerization initiator used is 0.00 parts by weight per 100 parts by weight of the compound represented by formula (2).・01~10!
! f parts, preferably in the range of 0.61 to 5 parts by weight.

Curing accelerators also have formulas (3), (4), (5), (6), (7
) The same curing accelerator used when crosslinking and curing the polymer can be used.

The curing accelerator is a total of 100 monomers and epoxy curing initiator.
0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight.
05 to 5 parts by weight are used.

When curing the resin of the present invention, antioxidants, antistatic agents, ultraviolet absorbers, photosensitizers, stabilizers, mold release agents, etc. may be added as necessary.

In addition, for the purpose of adjusting transparency, mechanical strength, heat resistance, etc., monomers that can be radically copolymerized with the monomer shown in formula (2), such as methyl acrylate, methyl methacrylate, styrene, N-phenyl A cured composition may be formed by blending maleimide, N-cyclohexylmaleimide, etc. with the monomer (2).

Molding is carried out by casting under anaerobic conditions, but the curing temperature is 0 to 200°C when using only a photocuring reaction.
℃, and in the case of utilizing a thermosetting reaction, a range of 50 to 200℃ is preferable.

Through the above process, the three-dimensional crosslinked polyalicyclic acrylic ester of the present invention can be produced.

The three-dimensional crosslinked composition of the present invention consists of a polymer of repeating units (10) (in the formula, R represents a hydrogen atom or a methyl group).

Note that the above curing method is merely an example, and is not necessarily limited to washing with water.

The m-coalescence of polyalicyclic acrylic acid ester derivatives and the three-dimensional crosslinked compositions thereof of the present invention can be used as optical materials.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited only to these examples. In addition, various physical properties obtained in Example (1) were determined by the following test method.

(1) Light transmittance: Measure the light transmittance at 500 nm using a spectrophotometer. (2) Birefringence Nihon Kogaku Co., Ltd. Seibu Light microscope with a Senarmon convencator attached to an 80 mm diameter section of the molded body (3) Heat distortion temperature: Measured with a heat distortion tester according to ASTM-D-648 (4) Hardness: Measured with a pencil hardness tester according to JIS-6911 (5) Water absorption: A S T hl -D -57
According to 0 (SilN determination Example 1) Into a 3i flask equipped with a dropping funnel, 166 g of 3,4-epoxyhydroxytrinchlor[5,2,1°02.6] dehydrogen, 500 mj of ether, and 20 g of sodium hydroxide were added.
After stirring in an argon atmosphere, 250 m of methacryloyl chloride was added dropwise, and 15 m of methacryloyl chloride was added with stirring.
The reaction was carried out at ℃ for 3 hours. After the reaction was completed, the reaction mixture was washed five times with pure water, the organic layer was separated from the aqueous layer, and the solvent was distilled off from the organic layer under reduced pressure to concentrate.
Vacuum distillation was performed at 130°C to obtain the reaction products 3 and 4.
-Epoxymethacryloyloxytricyclo[5,2,
1,02.6] 195 g of delinton was obtained. An IR spectrum chart of the product is shown in FIG.

Example 2 195 g of 3,4-epoxymethacryloyloxytricyclo(5,2,1,026)decane obtained in Example 1
was made into a 18% by weight benzene solution, 25 mg of azoisobisbutynitrile was added as a polymerization initiator, and after degassing, polymerization was carried out at 75° C. for 5 hours.

After the reaction was completed, the product was poured into methanol to recover a polymer.

The obtained polymer was dissolved in tetrahydrofuran and poured into methanol again for purification. The yield was determined by API after drying the white solid thus obtained at 40° C. under vacuum, and the yield was 117 g.

When the obtained polymer was subjected to G P Crll determination, the weight average molecular weight was 11 in terms of polystyrene.
．． It was 8x10'. Further, an IR spectrum chart of the product is shown in FIG.

Further, the glass transition temperature of this polymer was measured by differential calorimetry and was found to be 213°C.

1 g of 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate was added to 100 g of this polymer, and the mixture was press-molded using a mold with a diameter of 120 mm and a thickness of 1.2 mm.
", distance 20 cm) for 30 seconds to perform three-dimensional crosslinking.

The light transmittance, birefringence, heat distortion temperature, hardness and water absorption of the obtained molded article were measured. The results are shown in Table 1.

Example 3 3,4-epoxymethacryloyloxytricyclo[5,2,1,02.6]decane was synthesized in the same manner as in Example 1. The reaction yield was 198g.

The obtained 3,4-epoxymethacryloyloxytricyclo[5,2,1,02.6]decane was made into a 15% by weight benzene solution, and 36 mg of azoisobisbutyronitrile was added as a polymerization initiator. , 75℃ after degassing,
Polymerization was carried out for 3.5 hours.

After the reaction was completed, the product was poured into methanol to recover the desired polymer.

The obtained polymer was dissolved in tetrahydrofuran and poured into methanol again for purification. After drying the white solid thus obtained at 40° C. under vacuum, the yield was determined to be 71111, and the yield was 138 g.

When the obtained polymer was subjected to GPC measurement,
Weight average molecular weight is 8.4X10 in terms of polystyrene.
'Met.

30 g of phthalic anhydride per 100 g of the obtained polymer
was added, and this composition was press-molded in the same manner as in Example 2, and then held at 100°C for 3 hours to perform three-dimensional crosslinking. Table 1 shows the physical properties of the obtained molded product.

Example 4 Monomer 3.4-epoxymethacryloyloxytricyclo[5°2.1.0”・obtained in the same manner as in Example 1
6] 300 g of dehydrogen and 700 g of methyl methacrylate were mixed to make 1000 g of benzene solution. 12 g of azoisobisbutyronitrile was added as a polymerization initiator to this benzene solution, and after degassing, radical copolymerization was carried out at 75° C. for 3 hours in an argon atmosphere. After the reaction was completed, the product was poured into methanol to recover the desired polymer. The weight average molecular weight of the obtained polymer was 75.000 in terms of polystyrene.

This polymer was injection molded at 240°C, with a diameter of 120 mm.
After forming a molded product with a thickness of 1.2 mm and a thickness of 1.2 mm, the light transmittance,
Birefringence, heat distortion temperature, hardness and water absorption were measured. The results are shown in Table 1.

Example 5 Monomer 3,4-epoxymethacryloyloxytricyclo[5゜2.1.0''・obtained in the same manner as in Example 1
6] 200 g of dehydrogen and 800 g of methyl methacrylate were mixed to prepare 1000 g of benzene solution. 12 g of azoisobisbutyronitrile was added as a polymerization initiator to this benzene solution, and radical copolymerization was carried out in the same manner as in Example 2.

After the reaction was completed, the product was poured into methanol to recover the desired polymer. The weight average molecular weight of the obtained polymer was 80.000 in terms of polystyrene.

This polymer was injection molded under the same conditions as in Example 4, and the light transmittance, birefringence, heat distortion temperature, hardness and water absorption were
It was fixed at 1. The results are shown in Table 1.

Example 6 Monomer 3.4-Eboxymethacryloyloxytricyclo[5°2.1.026 obtained in the same manner as in Example 1
] 702 g of dehydrogen, 600 g of methyl methacrylate and 104 g of styrene were mixed with 1400 g of benzene.

14 g of azoisobisbutyronitrile was added as a polymerization initiator to this benzene solution, and after degassing, radical copolymerization was carried out at 75° C. for 3 hours in an argon atmosphere. After the reaction is complete, the product is poured into methanol and Ll
The target polymer was recovered. The weight average molecular weight of the obtained polymer was 92.000 in terms of polystyrene.

This polymer was injection molded at 240°C, with a diameter of 129 mm.
After forming a molded product with a thickness of 1.2 mm and a thickness of 1.2 mm, the light transmittance,
Birefringence, heat distortion temperature, hardness and water absorption were measured. The results are shown in Table 1.

Example 7 Monomer 3.4-epoxymethacryloyloxytricyclo[5°2.1.026 obtained in the same manner as in Example 1
1,350 g of benzene, 700 g of methyl methacrylate, and 177 g of N-phenylmaleimide.
Dissolved in g. 12.7 g of azoisobisbutyronitrile was added as a polymerization initiator to this benzene solution, and radical copolymerization was carried out in the same manner as in Example 2 for 5 hours. After the reaction was completed, the product was poured into methanol to recover the desired polymer. The weight average molecular weight of the obtained polymer is
The polystyrene equivalent value was 89,000.

This polymer was injection molded at 245°C, with a diameter of 120 mm.
After forming a molded product with a thickness of 1.2 mm and a thickness of 1.2 mm, the light transmittance,
Birefringence, heat distortion temperature, hardness and water absorption were measured. The results are shown in Table 1.

Example 8 Monomer 3.4-epoxymethacryloyloxytricyclo[5゜2.1.02.
6] 468 g of dehydrogen, 700 g of methyl methacrylate and 182 g of N-cyclohexylmaleimide were dissolved in 1350 g of benzene.

13 g of azoisobisbutyronitrile was added as a polymerization initiator to this benzene solution, and radical copolymerization was carried out in the same manner as in Example 7. After the reaction was completed, the product was poured into methanol to recover the desired polymer. The weight average molecular weight of the obtained polymer was 87,000 in terms of polystyrene.

This polymer was injection molded at 245°C, with a diameter of 120 mm.
After forming a molded product with a thickness of 1.2 mm and a thickness of 1.2 mm, the light transmittance,
Birefringence, heat distortion temperature, hardness and water absorption were measured. The results are shown in Table 1.

Example 9 3,4-epoxymethacryloyloxytricyclo[5,2,1,02.6]deforcen 100 obtained in Example 1
0.5 g of benzophenone per g.

After adding 1 g of 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate and vacuum degassing, the composition was placed on a glass plate with a diameter of 120 mm and a thickness of 1.2 m.
It was injected into a mold consisting of a spacer of
cm), a cured molded product was obtained in 10 minutes.

The water absorption rate, light transmittance,
Pencil hardness, birefringence and heat distortion temperature were measured. The results are shown in Table 1.

Example 10 3,4-epoxymethacryloyloxytricyclo[5,2°1.02.6]decane 100 obtained in Example 1
0.5 g of azoisobisbutyronitrile and 30 g of phthalic anhydride were added to the composition, and after vacuum degassing, the composition was molded into a mold consisting of a glass plate with a diameter of 120 mm and a spacer with a thickness of 1.2 mm. When the mixture was injected into the inside and heat-cured at 100°C, a cured molded product was obtained in 3 hours.

The water absorption rate, light transmittance,
Pencil hardness, birefringence and heat distortion temperature were determined. The results are shown in Table 1.

Example 11 3,4-epoxymethacryloyloxytricyclo(5,2,1,02.6)deforcen 100 obtained in Example 1
0.5 g of benzophenone per g.

1 g of 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 0.5 g of azoisobisbutyronitrile, and 30 g of phthalic anhydride were added, and the composition was degassed under vacuum, then placed on a glass plate with a diameter of 120 mm and a thickness of 1.5 g. It was poured into a mold constructed with a 2 mm spacer, and while kept at 100 °C, it was exposed to ultraviolet light (80 W / cm, distance Ill 20 °C) using a metal halide lamp.
When irradiated with m), a cured molded product could be obtained in 1 minute.

Take out the cured acid body from the mold and check the water absorption rate, light transmittance,
Pencil hardness, birefringence and heat distortion temperature were determined as All+.

The results are shown in Table 1.

Table 1 [Effects of the Invention] The polyalicyclic acrylic ester derivative obtained by the production method of the present invention is a polymer with excellent transparency, strength, heat resistance, water absorption, and optical homogeneity such as birefringence. It is extremely useful as a resin for optical materials such as optical lenses, digital audio discs, and optical memory discs.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing an infrared absorption spectrum of the polyalicyclic acrylic acid ester derivative monomer of the present invention synthesized in Example 1. Moreover, FIG. 2 is a diagram showing an infrared absorption spectrum of the polyalicyclic acrylic acid ester derivative polymer of the present invention synthesized in Example 2.

Claims (1)

[Claims] (1) Repeating unit ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R and R' each independently represent a hydrogen atom or a methyl group, and R_1 is a direct link between C_1 and C_4. Represents a chain or branched alkyl group, A represents a structural unit derived from a group copolymerizable with acrylic esters, l, m and n are 0.04 to 1 and 0 to 0, respectively, in this order.
．． 96 and 0 to 0.5, the sum of which is 1, and when m is 0.2 or less, n is 0.01 or less), and the molecular weight is about 5,000 to about 1. ，
000,000 polyacrylic acid ester derivatives. (2) A claim consisting of a repeating unit represented by the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (in the formula, R represents a hydrogen atom or a methyl group) where l is 1 and m and n are 0. Polyacrylic acid ester derivative of Item 1. (3) l is a number from 0.05 to 0.8, and m is 0.
2 to 0.95, and n is 0. There are formulas, mathematical formulas, chemical formulas, tables, etc. (In the formula, R and R' each independently represent a hydrogen atom or a methyl group, and R_1 is C_1~ The polyacrylic acid ester derivative according to claim 1, comprising a repeating unit represented by C_4 (representing a straight chain or branched alkyl group). (4) l is a number from 0.04 to 0.8, and m is 0.
The polyacrylic acid ester derivative according to claim 1, wherein n is a number from 2 to 0.95, and n is a number from 0.01 to 0.5. (5) The polyester according to claim 2, characterized in that the monomer represented by formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R represents a hydrogen atom or a methyl group) is radically polymerized. A method for producing an acrylic acid ester derivative. (6) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R in the formula represents a hydrogen atom or methyl group) Monomers and formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R in the formula 'represents a hydrogen atom or a methyl group, and R_1 represents a straight chain or branched alkyl group of C_1 to C_4), as well as the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is (represents a hydrogen atom or a methyl group) and the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R' represents a hydrogen atom or a methyl group) 4. The method for producing a polyacrylic acid ester derivative according to claim 3, which comprises copolymerizing. 5. The method for producing a polyacrylic acid ester derivative according to claim 4, wherein the monomer represented by formula (7) is radically copolymerized. (8) The polyacrylic acid ester derivative according to any one of claims 1 to 4 is obtained by crosslinking and curing the polyacrylic acid ester derivative according to any one of claims 1 to 4 by the action of light and/or heat in the presence of an initiator that acts by light and/or heat. An insoluble, infusible three-dimensional polymer. (9) A three-dimensional polymer consisting of repeating units represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (10) The polyacrylic acid ester derivative according to any one of claims 1 to 4 is crosslinked and cured by the action of light and/or heat in the presence of an initiator that acts with light and/or heat. A method for producing a characteristic three-dimensional polymer. (11) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R represents a hydrogen atom or a methyl group in the formula). and/or a three-dimensional polymer obtained by crosslinking and curing by the action of heat. (12) Claim 11 obtained by polymerizing and curing with light and/or heat using either a radical initiator or a cationic initiator, or both, as a photo and/or heat curing reaction initiator. term polymer. (13) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R represents a hydrogen atom or a methyl group in the formula). 10. The method for producing a three-dimensional polymer according to claim 9, characterized in that polymerization and curing is carried out by and/or heat. (14) Claims 1 to 4, 8, 9,
A resin composition for optical materials comprising the polyacrylic acid ester derivative or polymer according to any one of Items 11 and 12. (15) An optical material molded article comprising the resin composition for optical materials according to claim 14. (16) An optical material molded article obtained by injection molding a resin composition comprising the acrylic ester derivative according to any one of claims 1 to 4. (17) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a hydrogen atom or a methyl group). and/or a method for producing an optical material molded article, characterized in that it is cured and molded by heat.