JPH11236420A - Polymerizable and curable composition for optical lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition for providing a cured body having excellent physical properties of lens, by making the composition include a polymerizable monomer prepared by combining specific three kinds of polymerizable monomers in a prescribed ratio, a photopolymerization initiator and a thermal polymerization initiator. SOLUTION: This composition comprises (A) 100 pts.wt. of polymerizable monomers composed of 100 pts.wt. of a bifunctional (meth)acrylate-based polymerizable monomer of formula I (R<1> and R<2> are each H or methyl; (a) and (b) are each an integer of 1 to 2 and a+b=2-3), 50-200 pts.wt. of a bifunctional (meth)acrylate-based polymerizable monomer of formula II (R<3> and R<4> are each H or methyl; (c) and (d) are each an integer of 1-11 and c+d=6-12) and 5-100 pts.wt. of a monofunctional (meth)acrylate-based polymerizable monomer of formula III (R<5> is H or methyl), (B) 0.005-1 pt.wt. of a photopolymerization initiator (preferably a photopolymerization initiator such as preferably an acylphosphine oxide-based photopolymerization initiator or the like) and (C) 0.01-5 pts.wt. of a thermal polymerization initiator (one having preferably a decomposition temperature) of 70-90 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerizable composition suitable as a raw material for producing an optical lens such as an eyeglass lens. More specifically, the present invention relates to a polymerizable curable composition for an optical lens which cures in a short time, has a high refractive index, has a small optical distortion, and gives a cured product excellent in transparency, surface accuracy, impact resistance and dyeability.

[0002]

2. Description of the Related Art In recent years, glasses have been changed from glass to plastic from the viewpoint of lightness, impact resistance and dyeability.

In general, when a plastic lens is molded, it is usual that a polymerizable monomer is injected between two glass molds having different radii of curvature and is molded only by a method of thermal polymerization. However, the method using only thermal polymerization generally requires several hours of polymerization time, and is not satisfactory in terms of production of molded articles.

A method of irradiating a radical polymerizable monomer with an active energy ray to form a plastic lens in a short time is reported in Japanese Patent Application Laid-Open No. Sho 60-166305.

However, when a plastic lens is molded in a short time by irradiating with an active energy ray, internal stress is generated due to polymerization shrinkage, deformation occurs at the center of the lens after annealing, and the surface of the mold used is reduced. There was a drawback that it was not transferred accurately.

Therefore, in order to improve these problems,
JP-A-4-180911 and Japanese Patent Application No. 7-249938 report a method of molding by performing polymerization by irradiation with active energy rays and then performing polymerization by heating.

[0007] On the other hand, spectacle lenses are required to have impact resistance, but when a plastic spectacle lens is molded by performing prepolymerization by photopolymerization as described above, a photopolymerization which gives a cured product having excellent impact resistance is provided. Japanese Patent Application Laid-Open No. 4-420
No. 9 reports the following composition. However, the specific gravity of each of the cured products obtained by curing the composition is 1.20 or more, which is not satisfactory in terms of weight reduction, which is one of the features of plastic spectacle lenses. In addition, the gazette includes the following general formula (4)

[0008]

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(Wherein R ⁶ is a hydrogen atom or a methyl group, and 0 ≦ e + f ≦ 4).
An acrylate compound and the general formula (5)

[0010]

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(Wherein R ⁷ is a hydrogen atom or a methyl group and 7 ≦ g + h ≦ 12). The impact resistance can be improved by using different monomers of the di (meth) acrylate compound represented by the following formula: It is disclosed to improve.

According to the findings of the present inventors, when a crosslinked resin as described in JP-A-4-4209 is used, the heat distortion temperature can be increased by increasing the molecular weight between crosslink points. And the impact resistance improves if the heat distortion temperature is lowered. However, when the heat resistance is lowered to improve the impact resistance, a high temperature (generally, 1 hour) is applied to impart a hard coat or an antireflection film to the obtained spectacle lens.
(00 ° C. to 130 ° C.) In the surface treatment including the treatment step, problems such as deformation of the lens occur. Thus, as a polymer curable composition that can be prepolymerized by photopolymerization for an optical lens such as a plastic spectacle lens, the impact resistance and the heat resistance are balanced, the refractive index is low, the specific gravity is low,
Further, a polymer curable composition for an optical lens which gives a cured body having excellent surface accuracy and excellent lens properties such as transparency and dyeability has not been known so far.

[0013]

Means for Solving the Problems The present inventors have made intensive studies to develop a polymerizable curable composition for an optical lens having the above-mentioned excellent characteristics. A bifunctional (meth) acrylate polymerizable monomer having an oxide chain or a propylene oxide chain, a bifunctional (meth) acrylate polymerizable monomer having a relatively long ethylene oxide chain or a propylene oxide chain in the molecule, By pre-polymerizing a polymerizable monomer obtained by combining a monofunctional (meth) acrylate compound having a bulky alicyclic structure in the molecule at a specific ratio by photopolymerization, and then curing by thermal polymerization, The inventors have found that a cured product having excellent physical properties as described above can be obtained, and have completed the present invention.

That is, the present invention provides the following general formula (1)

[0015]

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(Wherein R ¹ and R ² are a hydrogen atom or a methyl group, a and b are each an integer of 1-2,
a + b is 2-3. ) With respect to 100 parts by weight of the bifunctional (meth) acrylate-based polymerizable monomer represented by the following general formula (2):

[0017]

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(Wherein R ³ and R ⁴ are hydrogen atoms or methyl groups, c and d are each an integer of 1 to 11, and c + d is 6 to 12). ) 50-200 parts by weight of an acrylate polymerizable monomer, and the following general formula (3)

[0019]

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(Wherein R ⁵ is a hydrogen atom or a methyl group.) A polymerizable monomer comprising a monofunctional (meth) acrylate-based polymerizable monomer represented by the formula: A polymerization curable composition for an optical lens, comprising 100 parts by weight of a polymer, 0.005 to 1 part by weight of a photopolymerization initiator, and 0.01 to 5 parts by weight of a thermal polymerization initiator.

Further, another invention is that the above-mentioned polymerizable curable composition for an optical lens is irradiated with an active energy ray to perform prepolymerization, and then the obtained prepolymer is heated and polymerized and cured. This is a method for producing a polymerized cured product for an optical lens.

In the polymerizable curable composition for an optical lens of the present invention, a lens having good impact resistance can be obtained by using monomers having different molecular weights between crosslinking points. It is thought that a cured product having a low specific gravity can be obtained without lowering the heat resistance and impact resistance by mixing the monomers represented by

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable curable composition for an optical lens of the present invention comprises a bifunctional (meth) acrylate polymerizable monomer represented by the above formula (1) as a polymerizable monomer (hereinafter referred to as a polymerizable monomer). , Simply referred to as a monomer A), a bifunctional (meth) acrylate-based polymerizable monomer represented by the general formula (2) (hereinafter, also simply referred to as a monomer B), and represented by the general formula (3). (Hereinafter, also simply referred to as monomer C).

The monomer A used in the present invention has a structure represented by the above general formula (1). From the viewpoint of polymerizability, R ¹ in the formula is a hydrogen atom or a methyl group. R ² in the formula is a hydrogen atom or a methyl group from the viewpoint of the viscosity of the polymer and the refractive index of the cured product obtained by polymerization.
From the viewpoint of the heat resistance of the cured product obtained by polymerization, a and b in the formula are 1 or 2, and a + b is 2-3. It is considered that the monomer A functions to increase the refractive index of the cured product obtained by polymerization and further increase the heat resistance.

Specific examples of the monomer A that can be preferably used in the present invention include 2,2-bis (4-methacryloyloxyethoxyphenyl) propane and 2- (4-methacryloyloxyethoxyphenyl) -2- (4- Methacryloylethoxyethoxyphenyl) propane, 2,2-bis (4-acryloyloxyethoxyphenyl) propane and the like can be mentioned.

The monomer B used in the present invention has a structure represented by the general formula (2). In the formula, R ³ is a hydrogen atom or a methyl group from the viewpoint of polymerizability. R ⁴ in the formula is a hydrogen atom or a methyl group from the viewpoint of the viscosity of the polymer and the refractive index of the cured product obtained by polymerization.
From the viewpoint of the heat resistance of the cured product obtained by polymerization, c and d in the formula are integers of 1 to 11 and c + d is 6 to 12. The monomer B is used as a monomer that imparts impact resistance to a cured product obtained by polymerization.

Specific examples of the monomer B which can be suitably used in the present invention include 2,2-bis (4-methacryloyloxytri (ethoxy) phenyl) propane and 2,2-bis (4-methacryloyloxytetra (ethoxy) ) Phenyl) propane, 2,2-bis (4-methacryloyloxypenta (ethoxy) phenyl) propane, 2,2-bis (4-methacryloyloxyhexa (ethoxy) phenyl) propane, 2- (4-methacryloyloxytetra (Ethoxy) phenyl) -2- (4-methacryloylethoxyhexa (ethoxy) phenyl) propane,
2,2-bis (4-acryloyloxypenta (ethoxy) phenyl) propane and the like can be mentioned.

The monomer C used in the present invention has a structure represented by the general formula (3), wherein R ⁵ is a hydrogen atom or a methyl group. The monomer C
Has a bulky isobornyl group in the molecule,
The cured product has a high glass transition temperature and a low specific gravity due to having an alicyclic structure. The monomer C is used as a monomer that imparts low specific gravity without lowering heat resistance and impact resistance of a cured product obtained by polymerization. Specific examples of the monomer C suitably used in the present invention include isobornyl methacrylate and isobornyl acrylate.

In the polymerizable monomers used in the polymerizable curable composition for an optical lens of the present invention, the mixing ratio of the monomers A, B and C is as follows.
The amount of monomer B is 50 to 200 parts by weight, preferably 75 to 150 parts by weight, and monomer C5 to 0 part by weight.
100 parts by weight, preferably in the range of 8 to 80 parts by weight.

When the amount of the monomer B is less than 50 parts by weight per 100 parts by weight of the monomer A, the resulting cured product is inferior in impact resistance and surface accuracy, and when the amount exceeds 200 parts by weight, it is insufficient. A cured product having a high degree of curing cannot be obtained. In addition, monomer C per 100 parts by weight of monomer A
When the amount is less than 5 parts by weight, not only does the heat resistance of the cured product decrease, but also the viscosity of the composition increases and the operability deteriorates. When the amount exceeds 100 parts by weight, the impact resistance of the cured product is poor.

As the polymerizable monomer used in the polymerizable curable composition for an optical lens of the present invention, a mixture containing the monomers A to C in the above mixing ratio may be used as it is, but it is finally obtained. In order to further improve the physical properties of the optical lens, other ethylenically unsaturated monomers copolymerizable with these monomers (hereinafter, also referred to as monomer D) may be further blended. Examples of the monomer D used here include di (meth) acrylate compounds such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, butanediol dimethacrylate, and hexamethylene dimethacrylate. Examples of the (meth) acrylate compound having a group include glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, and β-methylglycidyl methacrylate. These monomers D may be used alone or in combination of two or more.

The amount of the monomer D to be compounded may be appropriately determined in consideration of the physical properties of the finally obtained optical lens. In general, the total amount of the monomers A, B and C is 100%. It is 1 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to parts by weight.

The polymerization curable composition for an optical lens of the present invention contains both a photopolymerization initiator and a thermal polymerization initiator as a polymerization catalyst. By containing the above two polymerization catalysts, the polymerizable curable composition for an optical lens of the present invention can be subjected to two-stage polymerization in which preliminary polymerization is first performed by irradiating light, and then polymerization and curing is performed by thermal polymerization. I can do it. By performing such two-stage polymerization, an optical lens having excellent surface accuracy and internal uniformity can be easily obtained in a short time.

The photopolymerization initiator suitably used in the present invention is a photopolymerization initiator having a bleaching effect. Here, the bleaching effect means that the photopolymerization initiator is cleaved by the active energy ray, and as a result, absorption in a long wavelength region in the ultraviolet or visible region before cleavage disappears, and the absorption is shortened,
It means that active energy rays required for cleavage were absorbed in a region near the surface before cleavage, but could be transmitted to the inside without being absorbed by cleavage. As an example of such a photopolymerization initiator that can be suitably used in the present invention, the following general formula (6)

[0035]

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(In the formula, R ⁸ is independently a methyl group, a methoxy group or a chlorine atom, i is an integer of 2 or 3, and R ⁹ is a phenyl group or a methoxy group.) Fin oxide-based photopolymerization initiator,
And the following general formula (7)

[0037]

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(In the formula, R ¹⁰ is independently a methyl group, a methoxy group or a chlorine atom, j is an integer of 2 or 3, and R ¹¹ is a phenyl group or a 2,4,4-trimethylpentyl group. )), A diacylphosphine oxide-based photopolymerization initiator.

Specific examples of the acylphosphine oxide represented by the general formula (6) and the diacylphosphine oxide represented by the general formula (7) that can be suitably used in the present invention are 2,6-dimethylbenzoyl. Diphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4 -Trimethylpentylphosphine oxide, bis (2,6-dimethylbenzoyl) -2,
4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethoxybenzoyl) -2,4
4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like. These photopolymerization initiators can be used in combination of two or more.

The amount of the photopolymerization initiator is in the range of 0.005 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the polymerizable monomer. When the compounding amount exceeds 1 part by weight, the progress of polymerization becomes too fast to obtain a cured product having high internal uniformity of the obtained polymer, and when the compounding amount is less than 0.005 part by weight, Sufficient prepolymerization does not proceed.

The thermal polymerization initiator used in the present invention is not particularly limited, and known ones can be used, but those having a decomposition temperature defined by a 10-hour half-life temperature of 70 to 90 ° C. can be suitably used. When a thermal polymerization initiator having a decomposition temperature of less than 70 ° C. is used, the heat generated by the first-stage photopolymerization may cause the thermal polymerization initiator to be cleaved and the thermal polymerization may proceed to cause internal strain. is there. Further, when a thermal polymerization initiator having a decomposition temperature exceeding 90 ° C. is used, since the thermal polymerization needs to be performed at a high temperature, the lens may be colored. Specific examples of the thermal polymerization initiator that can be suitably used in the present invention include diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, t-butylperoxyisobutyrate, 1,1,3,3-tetramethyl And peroxyesters such as butylperoxy-2-ethylhexanoate. In addition, these thermal polymerization initiators can be used in combination of two or more.

The amount of the thermal polymerization initiator in the polymerization curable composition for an optical lens of the present invention is preferably 0.01 to 100 parts by weight of the polymerizable monomer from the viewpoint of uniformity of curing and hardness of the cured product. To 5 parts by weight, preferably 0.05 to 3 parts by weight.

The polymerizable curable composition for an optical lens of the present invention may contain a releasing agent, as long as the effects of the present invention are not impaired.
Various stabilizers and additives such as an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, a coloring inhibitor, an antistatic agent, a fluorescent dye, a dye, a pigment and a fragrance can be added.

As described above, the polymerizable curable composition for an optical lens of the present invention is first subjected to a prepolymerization by irradiating an active energy ray, and then the obtained prepolymer is polymerized and cured by heating. As a result, a lens having excellent surface accuracy and internal uniformity can be easily obtained in a short time.

In the above polymerization method, the active energy ray used in the prepolymerization means an energy ray having a wavelength in the range of 200 to 500 nm, and is an energy ray capable of cleaving the photopolymerization initiator. As a light source of such an active energy ray, those emitting ultraviolet rays and visible rays are preferable, for example, a metal halide lamp,
Low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp,
A germicidal lamp, a xenon lamp or the like is preferably used.

The method of the preliminary polymerization and the subsequent thermal polymerization are not particularly limited, and a known casting polymerization method can be suitably employed. For example, after injecting the polymerizable curable composition for an optical lens of the present invention between glass molds (molds) held by an elastomer gasket or a spacer and irradiating with an active energy ray to perform prepolymerization,
Further heating can be suitably performed by performing thermal polymerization and curing. When performing photopolymerization, at least the surface of the mold to be irradiated with light needs to be transparent, and glass or the like is generally used for this portion. In particular, a material that easily transmits ultraviolet light, such as quartz glass, is preferable, but the material is not particularly limited as long as it is transparent. At this time, polymerization may be performed while applying pressure from the outside.

In the above polymerization method, it is important from the viewpoint of surface accuracy that the polymerization is not completely terminated by the preliminary polymerization. When the polymerization is completely terminated by the prepolymerization, the surface accuracy is extremely poor. The degree of polymerization in the prepolymerization suitable for obtaining a lens with excellent surface accuracy and internal uniformity is generally defined because it varies depending on the wavelength of the light source used, the intensity, the type and composition of the monomer, and the mold shape and material. Although it is not possible, the shrinkage of the cured product (preliminary polymer) obtained by the preliminary polymerization is a final cured product. Here, the final cured product is polymerized and cured in two steps using a thermal polymerization initiator. Sometimes, a cured body whose hardness (Rockwell L scale) changes by 1 / hour or less when the cured body is cooled to room temperature. It is preferable to carry out the process so that the shrinkage ratio of｝ is 20 to 70%, preferably 30 to 50%. If the shrinkage of the prepolymer exceeds 70% of the shrinkage of the final cured product,
The surface accuracy of the final cured product tends to deteriorate, and the shrinkage ratio is 2
If it is less than 0%, it will peel off from the mold during thermal polymerization,
Internal uniformity tends to be poor.

Here, the shrinkage ratio is a value represented by the following equation.

Shrinkage (%) = {1− (specific gravity of monomer / specific gravity of cured product)} × 100 Since the degree of the prepolymerization is affected by many factors as described above, a preliminary experiment was conducted. It is preferable to preliminarily determine pre-polymerization conditions that give a suitable pre-polymer. In general, the higher the amount of the photoinitiator, the higher the intensity of the light source, and the thinner the shape of the polymer, the more quickly the prepolymerization can be completed. In addition, when using the same type of polymerization curable composition, using the same mold, and performing polymerization using the same light source, the shrinkage ratio is determined by the irradiation time of the active energy ray light to be irradiated. . In such a case, the relationship between the irradiation time and the shrinkage ratio of the prepolymer may be checked in advance for each polymerization system.

The thermal polymerization performed subsequent to the prepolymerization is performed by heating the prepolymer. The heating conditions at that time may be appropriately determined depending on the type of the thermal polymerization initiator used and the like. In the case of casting polymerization as described above,
After the prepolymerization, the mold can be directly heated in an air oven or a hot water bath at 60 to 140 ° C. for 10 to 120 minutes. At this time, the temperature may be raised in multiple stages.

The optical lens thus obtained can be subjected to the following processing depending on its use.
That is, dyeing using a disperse dye or the like, a silane coupling agent, a hard coat agent mainly containing a sol component such as silicon, zirconium, antimony, aluminum, tin, or tungsten, or a metal such as SiO ₂ , TiO ₂ , or ZrO ₂ Processing such as antireflection treatment and antistatic treatment by vapor deposition of an oxide thin film or application of a thin film of an organic polymer, and secondary treatment can also be performed.

[0052]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

The abbreviations of the reagents used in each Example and Comparative Example are shown below.

[Monomer A] BPE-2: 2,2-bis (4-methacryloyloxyethoxyphenyl) propane and 4- (4-methacryloyloxyethoxyphenyl) -2- (4-methacryloylethoxyethoxyphenyl) propane BPE-8: In the general formula (2), R ³ is a methyl group, R ⁴ is a hydrogen atom, and the sum of c + d is 6 to
A mixture of bifunctional (meth) acrylate-based polymerizable monomers, which is 10, and a mixture in which the average of c + d is 8. BPP-8: In the general formula (2), R ³ and R ⁴ are both methyl groups And a mixture of bifunctional (meth) acrylate-based polymerizable monomers having a total of c + d of 6 to 10, and a mixture having an average of c + d of 8 BPE-10: In the general formula (2), R ³ is a methyl group, R ⁴ is a hydrogen atom, and the sum of c + d is 6 to
A mixture of bifunctional (meth) acrylate-based polymerizable monomers having an average of c + d of 10 [monomer C] IBM: isobornyl methacrylate IBA: isobornyl acrylate [monomer D GMA: glycidyl methacrylate HEMA: 2-hydroxyethyl methacrylate 4GDM: tetraethylene glycol dimethacrylate [Reference monomer] CR-39: diethylene glycol bisallyl carbonate [photopolymerization initiator] BAPO1: bis (2,6-dimethoxybenzoyl) −
2,4,4-trimethylpentylphosphine oxide BAPO2: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide [Thermal polymerization initiator] TI1 : Perbutyl IB (trade name: Nippon Oil & Fats): t-
Butylperoxy-2-ethylhexanate TI2: Perocta O (trade name: Nippon Yushi): 1,
1,3,3-tetramethylbutylperoxy-2-ethylhexanate TI3: Perbutyl ND (trade name: Nippon Yushi): t-
Butyl peroxy neodecanoate TI4: Parloyl IPP (trade name: Nippon Oil & Fat): diisopropyl peroxydicarbonate Example 1 BPE-2 (45 parts by weight), BPE-10 (45 parts by weight), IBM (10 parts by weight) Part), BA as photopolymerization initiator
PO1 (0.02 parts by weight), TI1 as a thermal polymerization initiator
(0.5 parts by weight), mixed well, and then degassed under reduced pressure. This liquid was used for two glass molds having an outer diameter of 80 mm, using a gasket made of an ethylene-vinyl acetate copolymer, a flat plate having a center thickness of 2.0 mm, and a glass having an outer diameter of 80 mm and radii of curvature of 210 mm and 75 mm. Using a gasket made of an ethylene-vinyl acetate copolymer, the mold is injected into a mold combined so that a concave lens having a center thickness of 1.5 mm can be molded, and a 1.5 kw metal halide lamp (with a heat ray cut filter) is used. For use, active energy rays were irradiated from both sides for 1 minute from a distance of 25 cm, photopolymerized, and prepolymerized. At this time, the shrinkage after the pre-polymerization was 40% of the shrinkage of the final cured product. The UV intensity of the mold surface was 15 mW / wavelength at 365 nm.
cm ² . Then in an air oven at 110 ° C for 1
Upon heating for an hour, it was completely cured.

After releasing the cured plastic lens, 1
Annealing was performed by heating at 10 ° C. for 2 hours, and the refractive index, specific gravity, optical strain, surface accuracy, impact resistance, heat resistance, and dyeability were evaluated as follows.

Refractive index: Measured at 20 ° C. using an Abbe refractometer manufactured by Atago.

Optical distortion: Observation was made by the orthogonal Nicols method in which the polarization planes of two polarizing plates were orthogonal to each other, and polymerization distortion was evaluated. The evaluation criteria are as follows.

(○) No distortion (X) Distortion Surface accuracy: The concave surface of the lens was visually observed, and the surface accuracy was evaluated. The evaluation criteria are as follows.

(○) Non-curved (△) Slightly curved (×) Curved Impact resistance: 5 to 10 test plates each having a thickness of 2 mm and a diameter of 65 mm From the height of 127cm to 16g, 32g,
48g, 64g, 80g, 96g, 112g, 131
g, 151 g of steel balls were allowed to fall naturally, and the average of the weights of the heaviest steel balls that did not damage the test plate was evaluated.

Heat resistance: After leaving in an air oven at 120 ° C. for 3 hours, the lens was taken out, allowed to cool to room temperature, and the surface distortion was visually observed.

(○) Good (△) Slightly distorted (×) Distorted Stainability: Using a liquid in which BPI black was dispersed in water,
Staining was performed at 90 ° C. for 3 minutes, and evaluated visually.

(◎) Very good dyeing (○) Good dyeing (×) Hard to dyeing The evaluation results are shown in Table 1.

[0063]

[Table 1]

Example 2 Using the polymerizable composition shown in Table 1, molding was performed in the same manner as in Example 1. After releasing the obtained plastic lens, it was annealed and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 3 Using the polymerizable composition shown in Table 1, molding was carried out in the same manner as in Example 1 except that the irradiation time was changed to 3 minutes. At this time, the shrinkage rate after the pre-polymerization was 8 times the shrinkage rate of the final cured product.
It was 0%. Then, after releasing each plastic lens, annealing was performed in the same manner as in Example 1, and the evaluation was performed.
Table 1 shows the results.

Examples 4 to 7 Using the respective polymerizable compositions shown in Table 1, molding was carried out in the same manner as in Example 1. After releasing the obtained plastic lens, it was annealed and evaluated in the same manner as in Example 1.
Table 1 shows the results.

Comparative Example 1 Diethylene glycol bisallyl carbonate (CR-
39) IPP (3 parts by weight) was added to (100 parts by weight), mixed well, and then degassed under reduced pressure. This liquid was prepared by using two glass molds having an outer diameter of 80 mm using a gasket made of an ethylene-vinyl acetate copolymer, and having a center thickness of 2.0 mm.
Flat plate, the radius of curvature of the outer diameter 80mm is 210mm and 75mm
Was molded into a combined mold using a gasket made of an ethylene-vinyl acetate copolymer so that a concave lens having a center thickness of 1.5 mm could be molded. Thereafter, thermal polymerization was performed at 45 ° C. for 8 hours, at 60 ° C. for 3 hours, at 80 ° C. for 3 hours, and at 95 ° C. for 4 hours. Example 1 after release
Annealing was performed in the same manner as described above, and evaluation was performed. Table 2 shows the results.

[0068]

[Table 2]

Comparative Examples 2 to 9 Using the polymerizable compositions shown in Table 2, molding was carried out in the same manner as in Example 1. After releasing each plastic lens, annealing was performed in the same manner as in Example 1, and the evaluation was performed. Table 2 shows the results.

From the above results, the polymerizable curable composition for an optical lens of the present invention is prepolymerized by irradiating active energy rays and then thermally polymerized to obtain a high refractive index and a low specific gravity.
It can be seen that a lens having good impact resistance and surface accuracy can be molded in a short time. Further, Comparative Examples 2 to 4 are cases in which the amount of the polymerization initiator is different from that of the polymerization curable composition for an optical lens of the present invention. In this case, optical distortion and only a lens with poor surface accuracy can be obtained. Was. Comparative Examples 5 to 9 are cases in which the proportions of the monomers A, B, and C are different from those of the polymerizable curable composition for an optical lens of the present invention. In this case, the surface accuracy and impact resistance of the obtained lens are It can be seen that the physical properties, heat resistance and dyeing properties are inferior.

[0071]

The polymer obtained by polymerizing the polymerizable curable composition for an optical lens of the present invention has a high refractive index, a low specific gravity, excellent impact resistance, surface accuracy, transparency, and dyeability, and has excellent spectacles. It has excellent physical properties as an optical lens such as a lens.

Claims (3)

[Claims] [Claim 1] The following general formula (1) (Wherein R ¹ and R ² are a hydrogen atom or a methyl group,
a and b are each an integer of 1-2, and a + b is 2-
3. )) And 100 parts by weight of the bifunctional (meth) acrylate polymerizable monomer represented by the formula (2): (Wherein R ³ and R ⁴ are a hydrogen atom or a methyl group,
c and d are each an integer of 1 to 11, and c + d is 6
~ 12. ), 50 to 200 parts by weight of the polymerizable monomer represented by the following formula (3): (Wherein R ⁵ is a hydrogen atom or a methyl group).
100 parts by weight of polymerizable monomer 100
A polymerizable curable composition for an optical lens, comprising: parts by weight, 0.005 to 1 part by weight of a photopolymerization initiator, and 0.01 to 5 parts by weight of a thermal polymerization initiator. 2. The photopolymerization initiator is an acylphosphine oxide-based or diacylphosphine oxide-based photopolymerization initiator, and the thermal polymerization initiator has a decomposition temperature of 70-9.
The polymerization curable composition for an optical lens according to claim 1, which is a thermal polymerization initiator at 0 ° C. 3. The polymerizable curable composition for an optical lens according to claim 1 or 2 is irradiated with an active energy ray to perform a prepolymerization, and then the obtained prepolymer is heated and polymerized and cured. A method for producing a polymer cured product for an optical lens, comprising: