JP2001302755A - Monomer composition for optical material, production method for synthetic resin lens, and lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a monomer composition for an optical material which gives a synthetic resin lens having high refractive index Abbe number, low specific gravity, and excellent heat resistance, dyeability, impact resistance, or the like a simple and convenient method for producing a homogeneous-quality synthetic resin lens which has good mold release characteristics and hardly exhibits strain; and to provide a synthetic resin lens. SOLUTION: The composition contains 5-50 wt.% specific di(meth)acylate, 5-40 wt.% polyfunctional methacrylate having at least three polymerizable groups; 10-50 wt.% 3-isopropenyl-α,α-dimethylbenzyl isocyanate, and 10-40 wt.% polythiol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin lens, and more particularly, to a lens having excellent optical characteristics, a high refractive index, a high Abbe number, and various physical properties such as low specific gravity, dyeability, heat resistance and impact resistance. The present invention relates to a monomer composition for an optical material for obtaining a synthetic resin lens having excellent characteristics, a production method capable of obtaining a homogeneous synthetic resin lens, and a synthetic resin lens.

[0002]

2. Description of the Related Art In recent years, light weight, safety, fashionability, and the like have also been emphasized for optical lenses, and synthetic resin materials have been widely used in place of conventional inorganic glass.
As typical examples, polydiethylene glycol bisallyl carbonate (PADC), polymethyl methacrylate (PMMA), polycarbonate (PC) and the like are well known.

However, PADC and PMMA have low specific gravity,
Although it has properties superior to inorganic glass in terms of impact resistance, dyeing properties, etc., it has a refractive index of about 1.49, which is lower than 1.52 of general inorganic glass. There was a disadvantage that the edge thickness had to be increased. Further, PC has a high refractive index of about 1.58, but has a low Abbe number of 29, and has a problem of optical anisotropy and coloring because the molding method is melt molding.

Recently, in order to improve such disadvantages,
Plastic lenses with higher refraction and higher Abbe number have been proposed. For example, JP-A-55-13747 discloses a copolymer of dimethacrylate of a bisphenol A derivative and styrene, and JP-A-55-69543 discloses a polymer of a dimethacrylate of a halogenated bisphenol A derivative. . Also, Japanese Patent Application Laid-Open No. 62-267
No. 316 discloses a thiourethane resin comprising a polyisocyanate and a polythiol. However, in the copolymer disclosed in JP-A-55-13747, the refractive index is not sufficiently satisfactory at about 1.55, and in the polymer disclosed in JP-A-55-69543, Although the refractive index is as high as about 1.60, there are disadvantages such as a high specific gravity and a decrease in weather resistance due to halogenation, and also a problem that it is difficult to control polymerization of a methacrylate monomer. Further, in the resin disclosed in Japanese Patent Application Laid-Open No. 62-267316, in addition to the drawback that the specific gravity is high and the heat resistance is inferior, complicated water management and control of the curing temperature are required because of curing by the thiourethane reaction. There were problems such as becoming indispensable.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned drawbacks of the prior art by providing a high refractive index, an Abbe number, a low specific gravity, heat resistance, dyeability, impact resistance and the like. To provide a monomer composition for an optical material for obtaining a synthetic resin lens having excellent characteristics, a simple manufacturing method capable of obtaining a homogeneous synthetic resin lens with good mold release and little distortion, and a synthetic resin lens. It is in.

[0006]

The present invention provides the following monomer composition for an optical material, a method for producing a synthetic resin lens, and a synthetic resin lens. (1) 5 to 50% by weight of a di (meth) acrylate represented by the following formula (1) as the component A;

[0007]

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(Wherein, R ₁ represents a hydrogen atom or a methyl group, x and z represent the same or different integers from 1 to 5, and y represents 0 or 1.) As the B component, three or more polymerizations 5 to 40% by weight of a polyfunctional methacrylate having a group, 3-isopropenyl-α, α-dimethylbenzyl isocyanate as a C component
0% by weight, and polythiol 10 to 40 as the D component
% Of a monomer composition for an optical material. (2) Production of a synthetic resin lens, wherein a radical polymerization initiator and an amine catalyst or an organometallic catalyst as a curing agent are added to the monomer composition for an optical material of (1), and then the composition is cured. Method. (3) A synthetic resin lens having a refractive index of 1.55 to 1.65 and an Abbe number of 30 to 42 obtained by the invention of (2).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The component A used in the synthetic resin lens of the present invention is a specific di (meth) acrylate represented by the above formula, wherein R ₁ represents a hydrogen atom or a methyl group, and x , Z are the same or different integers from 1 to 5,
When 6 or more di (meth) acrylates are used, the refractive index and heat resistance of the produced resin are significantly reduced.

As the di (meth) acrylate, for example, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis [4- (2-methacryloxyethoxy) ethoxy] propane, 2,2 -Bis [4-
(2-methacryloxyethoxy) diethoxy] propane, 2,2-bis [4- (2-methacryloxyethoxy) triethoxyphenyl] propane, 2,2-bis [4- (2-methacryloxyethoxy) tetraethoxyphenyl ] Propane, 2,2-bis [4- (2-methacryloxyethoxycarbonyloxy) phenyl] propane, 2,2-bis {4-[(2-methacryloxyethoxy) ethoxycarbonyloxy] phenyl} propane Examples thereof include methacrylate and diacrylate having the structural formula, and they can be used alone or as a mixture of two or more. Such di (meth) acrylates have high Abbe number, impact resistance,
It can impart dyeing properties and is used in the range of 5 to 50% by weight.
If the content is more than 10% by weight, the refractive index is significantly reduced.

As the B component used in the synthetic resin lens of the present invention, a polyfunctional methacrylate having three or more polymer groups is used in a range of 5 to 40% by weight. Examples of the polyfunctional methacrylate, for example, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate,
Examples thereof include ditrimethylolpropane tetramethacrylate and the like, and one kind or a mixture of two or more kinds can be used. The polyfunctional methacrylate can give the heat resistance of the synthetic resin lens, but is 5% by weight.
If it is less than 40%, the effect of use is small. The charge weight ratio of the component A and the component B is generally in the range of 0.5 to 3, and preferably in the range of 0.8 to 1.4.

As the C component used in the synthetic resin lens of the present invention, 3-isopropenyl-α, α-dimethylbenzyl isocyanate is used in a range of 10 to 50% by weight. The 3-isopropenyl-α, α-dimethylbenzyl isocyanate can improve the refractive index of a lens made of synthetic resin, and is also effective in controlling a rapid polymerization reaction by causing radical chain transfer. As shown, when the content is less than 10% by weight, the effect of use is small, and when it exceeds 50% by weight, poor curing tends to occur.

The D component used in the synthetic resin lens of the present invention contains 10 to 40% by weight of polythiol. Examples of the polythiol include ethanedithiol, diethylenethioglycol, triethylenethioglycol, pentaerythritol tetrakis (mercaptopropionate), and pentaerythritol tetrakis (thioglycolate). Can be used in mixtures. Such a polythiol is a component that reacts with the component C of the present invention to form a thiourethane bond, can improve the refractive index of a synthetic resin lens, and is used in an amount of 10 to 40% by weight. If it is less than 10% by weight, the effect of the addition is small, and if it exceeds 40% by weight, poor curing and weather resistance tend to be remarkably reduced.
The charged molar ratio of the C component and the D component is generally 0.5 to
It is in the range of 1.5, preferably in the range of 1.0 to 1.4.

The synthetic resin lens of the present invention is characterized in that
A mixture containing the components B, C and D as essential components is cured, but other vinyl monomers copolymerizable as the component E can also be used. Examples of other copolymerizable vinyl monomers include styrene, halogen nucleus-substituted styrene, methyl nucleus-substituted styrene, vinylnaphthalene, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and ethylene. Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, various urethane poly (meth) acrylates, various urethane poly (meth) acrylates, diallyl phthalate, glyceroyl (meth) acrylate, (meth) One or two kinds of mixed monomers such as acrylic acid, (meth) acrylic amide, N, N-dimethylacrylamide and the like can be mentioned, and they can be selected and used according to a required refractive index. The use amount of the component E is generally in the range of 0 to 40% by weight, preferably in the range of 0 to 20% by weight based on the whole.

The total amount of the component A, the component B, and the component E relating to the radical polymerization resin, and the amount of the C relating to the thiourethane resin
The charged weight ratio of the total amount of the component and the D component is generally from 0.3 to 2, preferably from 0.5 to 1.7.

The synthetic resin lens of the present invention is characterized in that:
It is obtained by curing a raw material mixture containing components B, C and D using a radical polymerization initiator and an amine-based catalyst or an organometallic catalyst as a curing agent.

The radical polymerization initiator in this case is used for curing vinyl monomers, and includes, for example, benzoyl peroxide, lauroyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, One or more of t-butyl peroxy neodecanoate, t-butyl peroxy pivalate, t-butyl peroxy diisobutyrate, azobisisobutyronitrile, azobisdimethylvaleronitrile and the like may be used in combination. it can. The amount of the radical polymerization initiator to be used is 0.1 wt.
The amount is from 0.01 to 10 parts by weight, more preferably from 0.1 to 5 parts by weight.

The amine catalyst and the organometallic catalyst are preferably
-Used as a catalyst for the addition polymerization of isopropenyl-α, α-dimethylbenzyl isocyanate and polythiol. Examples of the amine catalyst include triethylenediamine, triethyleneamine, pyridine, 1,8-diazabicyclo (5,4,0) undecene-7, and examples of the organometallic catalyst include dibutyltin dilaurate. The amount used is 1-1000p for the whole
pm range.

The synthetic resin lens of the present invention may further comprise an ultraviolet absorber, an antioxidant,
Additives such as colorants, release agents, surfactants, and antimicrobial agents can also be used. For example, a benzotriazole-based ultraviolet absorber can be used in the range of 0.05 to 2% by weight based on the whole.

In order to obtain the synthetic resin lens of the present invention, a raw material mixture containing a curing agent is injected into a metal, glass, plastic, or other metal mold having a desired lens shape, followed by heat curing. As the curing conditions, the polymerization temperature is in the range of 10 to 110 ° C., and the temperature is controlled in multiple stages to control. Usually, the polymerization time is about 5 to 72 hours, and the obtained cured product is a colorless and transparent crosslinked resin insoluble in a solvent. Further, it is preferable that the cured lens is subjected to an annealing treatment at a temperature of 80 to 120 ° C. for 1 to 5 hours in a nitrogen or air atmosphere after the mold release. As another method, it can be obtained by directly cutting a cured product into a desired lens shape.

The refractive index of the synthetic resin lens of the present invention is
It is in the range of 1.55 to 1.65, preferably 1.
The range is from 58 to 1.63. When the refractive index is low, the edge thickness of the lens increases, and when the refractive index is high, the edge thickness can be reduced. The Abbe number of the synthetic resin lens of the present invention is in the range of 30 to 42, and preferably in the range of 34 to 42. If the Abbe number is low, the field of view seen by the lens becomes unclear, and if it is high, the field of view becomes clear.

As the synthetic resin lens of the present invention, usually, the lens obtained by the above-mentioned preparation method can be used as it is, but if necessary, a hard coat treatment for improving the surface hardness and a fashion property are imparted. Can be colored by a disperse dye or a photochromic dye.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail by reference examples and examples.

Examples 1 to 6 Raw material mixture 2 of each component blended in the proportions shown in Table 1
In 0 g, 1,8-diazabicyclo (5,
4,0) 100 ppm of undecene-7 and 0.2 g of t-butylperoxyneodecanoate are further added and mixed with stirring. The composition is poured into a mold consisting of two glass disks of 7 cm diameter and a gasket of ethylene-propylene rubber of 2 mm thickness. Curing is performed at 30 ° C to 100 ° C in a hot air oven with a programmed temperature controller.
The temperature was raised to 80 ° C. over 18 hours, kept at 100 ° C. for 2 hours, and then cooled to 40 ° C. over 2 hours. The disc-shaped resin removed from the mold after curing was subjected to an annealing treatment at 120 ° C. for another 2 hours. The obtained resin plate was subjected to each test as described below, and the results are shown in Table 1. (1) Light transmittance JIS K using a transmittance photometer manufactured by Nippon Denshoku Industries Co., Ltd.
The light transmittance was measured according to 7105. (2) Refractive Index and Abbe Number A 1 cm × 1.5 cm test piece was cut out from a cured resin plate at 25 ° C. using an Atago Abbe refractometer and measured. (3) Specific gravity According to JIS K 7112, the test piece was measured at 25 ° C by a water displacement method. (4) Impact resistance A steel ball having a weight of 16 g is naturally dropped on a resin plate from a height of 127 cm, and those that are not damaged are marked with a circle.
Damaged ones were marked as x. (5) Heat resistance A 1 cm × 4 cm plate was cut out from a resin plate, and dynamic viscoelasticity was measured using a Leo vibron manufactured by Toyo Baldwin Co., Ltd. did. (6) Dyeing property The test piece was immersed in a brown dyeing bath at 92 ° C. for 10 minutes, and the light transmittance after dyeing was measured by the transmittance meter used in (1).

Examples 7 to 10 Raw material mixture 2 of each component blended in the proportions shown in Table 1
0 g of dibutyltin dilaurate 200 as a curing agent.
ppm, t-butyl peroxy neodecanoate in 0.1%.
Curing was carried out in exactly the same manner as in Examples 1 to 6 except that 4 g was used, and the physical properties were evaluated using test pieces. Table 2 shows the results. Add, stir and mix.

Comparative Examples 1 to 3 A test piece was cut out from a commercially available 2 mm plate made of PADC, PMMA, or PC, and the physical property test was performed in the same manner as in Examples 1 to 10. Further, 0.6 g of diisopropyl peroxydicarbonate was added as a curing agent to a mixture of 14 g of diallyl diphenate as a raw material and 6 g of diallyl isophthalate, and cured under the same conditions as in Examples 1 to 10. went. Table 2 shows the results.

[0027]

[Table 1]

(Note) BPE-2E; 2,2-bis (4-methacryloxyethoxyphenyl) propane, BPE-4E; 2,2-bis [4- (2-methacryloxyethoxy) ethoxy] propane, BPE- 6E; 2,2-bis [4- (2-methacryloxyethoxy) diethoxy] propane, A-BPE
-4; 2,2-bis [4- (2-acryloxyethoxy) ethoxy] propane, HE-BP; 2,2-bis [4- (2-methacryloxyethoxycarbonyloxy) phenyl] propane, TMP; Methylolpropane trimethacrylate, GMT; ditrimethylolpropane tetramethacrylate, TMI; 3-isopropenyl-α, α-dimethylbenzyl isocyanate, ED
T; ethanedithiol, ETT; diethylenethioglycol, ETRT; triethylenethioglycol, ST;
Styrene, BzMA; benzyl methacrylate.

[0029]

[Table 2]

Each of the synthetic resin lenses manufactured in Examples 1 to 10 has high transmittance, refractive index, Abbe number and low specific gravity, impact resistance, heat resistance, and various dyeing properties. Are better. On the other hand, the lenses of Comparative Examples 1 and 2 have a low refractive index, the lens of Comparative Example 3 has a low Abbe number, and the dyeability is not sufficient, and the lens of Comparative Example 4 has insufficient impact resistance. It cannot be used as a synthetic resin lens for this purpose.

[0031]

According to the present invention, a unit for an optical material for obtaining a lens made of a synthetic resin having a high refractive index, an Abbe number, and excellent in various properties such as low specific gravity, heat resistance, dyeability and impact resistance. It is possible to provide a simple production method and a synthetic resin lens which can obtain a homogenous composition, a homogeneous synthetic resin lens with good mold release and little distortion. The synthetic resin lens of the present invention has a refractive index of 1.55 to 1.65 and an Abbe number of 3
0 to 42, having high optical properties, low specific gravity of 1.3 or less, and excellent in various physical properties such as dyeability, heat resistance and impact resistance required for lenses. It is a lens made. For this reason, the lens thickness is thinner,
A lighter lens having optical homogeneity can be obtained.

Claims (3)

[Claims] 1. A di (meth) acrylate represented by the following formula (1): 5 to 50% by weight, (In the formula, R ₁ represents a hydrogen atom or a methyl group, x and z represent the same or different integers from 1 to 5, and y represents 0 or 1.) Polyfunctional methacrylate having three or more polymer groups 5-4
A monomer composition for an optical material containing 0% by weight, 10 to 50% by weight of 3-isopropenyl-α, α-dimethylbenzyl isocyanate, and 10 to 40% by weight of polythiol. 2. A monomer composition for an optical material according to claim 1, wherein a radical polymerization initiator and an amine catalyst or an organometallic catalyst as a curing agent are added, and then the monomer composition is cured. A method for producing a synthetic resin lens. 3. A synthetic resin lens having a refractive index of 1.55 to 1.65 and an Abbe number of 30 to 42 obtained by the method of claim 2.