JP2002014201A - Synthetic resin lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic resin lens which is excellent in optical properties, has a high refractive index and a high Abbe number, and is also excellent in various physical properties such as low specific gravity, dyeability, heat resistance and impact resistance. SOLUTION: A specific trithiol is 30 to 90% by weight, divinylbenzene and / or divinylbiphenyl is 5 to 40% by weight, and 3-isopropenyl-α, α-dimethylbenzyl isocyanate is 5 to 50% by weight. A synthetic resin lens obtained by curing a mixture containing 0 to 60% by weight of a vinyl monomer (excluding divinylbenzene and divinylbiphenyl) as an essential component.

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 lens made of a synthetic resin which is also excellent.

[0002]

2. Description of the Related Art In recent years, light weight, safety, fashionability and the like have been emphasized for optical lenses, and synthetic resin materials have been widely used instead of conventional inorganic glass. Typical examples are polydiethylene glycol bisallyl carbonate (PADC), polymethyl methacrylate (PMMA), polycarbonate (PC)
Etc. are well known. However, PADC and PMMA have properties superior to inorganic glass in terms of low specific gravity, impact resistance, dyeing properties, etc., but have a refractive index of about 1.49, which is about 1.49 of general inorganic glass. If it is lower than 52 and the power is high, there is a disadvantage that the edge thickness of the lens must 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, in JP-A-55-13747, a copolymer of dimethacrylate of bisphenol A derivative and styrene is disclosed, and in JP-A-55-69543, a polymer of dimethacrylate of halogenated bisphenol A derivative is exemplified. The former has a refractive index of about 1.55, which is not satisfactory, and the latter has a refractive index of 1.6.
Although it was as high as about 0, there were drawbacks such as a high specific gravity and a decrease in weather resistance due to halogenation. Further, as proposals for further increasing the refractive index, JP-A-63-23908 discloses a polymer of diallyl diphenate, and JP-A-62-267316 discloses a polyisocyanate and pentaerythritol tetrakis (mercaptopropionate) and pentane. A thiourethane resin composed of polythiol such as erythritol tetrakis (thioglycolate) has been released, but the former has a low Abbe number of about 29 and has a low impact resistance, and the latter has a high specific gravity and a high heat resistance. Was inferior.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to have high optical characteristics with a refractive index of 1.55 or more, an Abbe number of 30 or more, and a low specific gravity of 1.3 or less. An object of the present invention is to provide a synthetic resin lens which is excellent in various physical properties such as dyeability, heat resistance and impact resistance required for the lens. For this reason, it is possible to provide a lens having a smaller thickness and a lighter optical homogeneity.

[0005]

SUMMARY OF THE INVENTION The present invention provides the following synthetic resin lens. (1) Trithiol represented by the following general formula (1) as A component,

Embedded image (Wherein, R ¹ and R ² are the same or different groups and each represent a hydrogen atom,
Represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, j,
h and m represent the same or different integers of 1 to 3, and k represents 0 or 1. ), And 30 to 90% by weight of divinylbenzene or / and divinylbiphenyl as the B component.
%, 3-isopropenyl-α, α-dimethylbenzyl isocyanate as an essential component is 5 to 50% by weight as a C component, and a vinyl monomer (provided as a component D)
Excluding divinylbenzene and divinylbiphenyl. ) To 0
A synthetic resin lens obtained by curing a mixture containing 〜60% by weight. (2) A synthetic resin lens obtained by curing the mixture according to (1) using a radical polymerization initiator and an amine catalyst or an organometallic catalyst as a curing agent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The synthetic resin lens of the present invention
Trithiol as a component, divinylbenzene or / and divinylbiphenyl as a B component, and 3-isopropenyl-α, α-dimethylbenzyl isocyanate as a C component.
And a mixture containing a vinyl monomer (excluding divinylbenzene and divinylbiphenyl) as a D component. In the trithiol compound represented by the general formula (1) of the present invention, R ¹ and R ² in the formula are the same or different groups, and are hydrogen atoms,
It represents an alkyl group or a phenyl group having 1 to 3 carbon atoms. When the number of carbon atoms of the alkyl group is 4 or more, the synthesis yield decreases. j, h, and m are the same or different integers of 1 to 3, and when the number is 4 or more, synthesis of dithiol as a raw material becomes difficult. k represents 0 or 1.

Specific examples of the trithiol compound
Include the following compounds. HSCH_TwoCH_TwoS-CH_Two-CH_Two-CH- (SCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoS-CH (CH
_Three) -CH- (SCH_TwoCH_Two-SH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH_Two-CH_Two-CH-
(SCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH (CH_Three) -CH-
(SCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH_Two-C
H_Two-CH- (SCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoS
CH_TwoCH_TwoS-CH (CH_Three) -CH- (SCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH _TwoSH)_Two, HSC
H_TwoCH_TwoS-CH_Two-CH_Two-C (CH_Three)-(SCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoS-CH (C
H_Three) -C (CH_Three)-(SCH_TwoCH_Two-SH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH_Two-CH_Two
-C (CH_Three)-(SCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH (C
H_Three) -C (CH_Three)-(SCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoSCH
_TwoCH_TwoS-CH_Two-CH_Two-C (CH_Three)-(SCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, H
SCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH (CH _Three) -C (CH_Three)-(SCH_TwoCH_TwoSCH_Two
CH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoS-CH (CH_Three) -CH_Two-CH- (SCH_TwoCH_Two
SH)_Two, HSCH_TwoCH_TwoS-CH (CH_TwoCH_Three) -CH- (SCH_TwoCH_TwoSH)_Two, HSCH_TwoC
H_TwoSCH_TwoCH_TwoS-CH (CH_Three) -CH_Two-CH- (SCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, HSC
H_TwoCH_TwoSCH_TwoCH_TwoS-CH (CH_TwoCH_Three) -CH- (SCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, H
SCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH (CH_Three) -CH_Two-CH- (SCH_TwoCH_TwoSCH_Two
CH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH (CH_TwoCH_Three)
-CH- (SCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoS-CH (C₆H_Five)
-CH_Two-CH- (SCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoS-CH (CH_TwoC₆H_Five) -CH- (SC
H_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH (C₆H_Five) -CH_Two-CH- (SCH_TwoC
H_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH (CH_TwoC₆H_Five) -CH- (SC
H_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH (C₆H_Five)
-CH _Two-CH- (SCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, HSCH_TwoCH_TwoSCH_TwoCH
_TwoSCH_TwoCH_TwoS-CH (CH_TwoC₆H_Five) -CH- (SCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoSH)
_Two.

[0008] Such a trithiol forms an addition reaction to a vinyl group with the B and C components of the present invention and a thiourethane bond with an isocyanate group by the thiol group, thereby improving the refractive index of a synthetic resin lens. Can be
It is used in the range of 30 to 90% by weight. When the content of the polythiol is less than 30% by weight, the refractive index is not sufficiently improved. When the content is more than 90% by weight, curing failure and weather resistance are remarkably reduced, so that the composition cannot be used.

The trithiol compound represented by the general formula (1) of the present invention is, for example, an unsaturated aldehyde or an unsaturated ketone such as acrolein, crotonaldehyde, cinnamaldehyde, methyl vinyl ketone and ethanedithiol.
By using a dithiol such as 2,2'-thiodiethanethiol or dimercaptotriethylene disulfide as a raw material, using an acid catalyst or a base catalyst without a catalyst or as a catalyst, and further adding a radical initiator as needed, the thiol is obtained. The compound can be synthesized by an addition reaction of a group to an unsaturated group and a thioketalization reaction of a carbonyl group. If necessary, the desired trithiol compound can be obtained by purifying the compound.

As the B component used in the synthetic resin lens of the present invention, divinylbenzene and / or divinylbiphenyl is used in a range of 5 to 40% by weight. The divinyl monomer improves the refractive index of the synthetic resin lens,
Heat resistance can be imparted, but if it is less than 5% by weight, the effect of use cannot be obtained, and if it exceeds 40% by weight, the impact resistance is remarkably reduced and it is not suitable for use.

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 5 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 effective in controlling a rapid polymerization reaction. The effect of use cannot be obtained, and if it exceeds 50% by weight, poor curing occurs, and it is not suitable for use.

The B component and the C component used in the synthetic resin lens of the present invention react with trithiol as the A component, and the composition ratio of the B component and the C component is 1: 0.8 to 0.8.
A range of 1: 2 is preferred. The C component is 0.
If the amount is less than 8 times, the impact resistance is reduced. If the amount is more than 2 times, curing failure occurs, and the material is not suitable for use.

The synthetic resin lens of the present invention is characterized in that:
A mixture comprising the components B and C as constituent components is cured, but another vinyl monomer other than the copolymerizable component B may be used as the component D. 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 diene. (Meth) acrylate, diethylene glycol di (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 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 Methacrylate and diacrylate having the structural formula, various urethane poly (meth) acrylates, (meth)
One or two kinds of mixed monomers such as acrylic acid, (meth) acrylic amide, N, N-dimethylacrylamide, etc. may be mentioned, and may be selected and used according to various physical properties such as refractive index, heat resistance and impact resistance. Can be.

As the D component used in the synthetic resin lens of the present invention, a copolymerizable vinyl monomer other than the B component, ie, divinylbenzene or divinylbiphenyl, is 0 to 60.
It is used in the range of weight%. The other copolymerizable vinyl monomer can improve the heat resistance of the lens made of synthetic resin and is also effective in improving the impact resistance. However, when the content exceeds 60% by weight, the refractive index decreases. And become unsuitable for use.

The synthetic resin lens of the present invention is characterized in that
It is obtained by curing a raw material mixture composed of B and C or a raw material mixture composed of A, B, C and D using a radical polymerization initiator and an amine catalyst or an organometallic catalyst as a curing agent. The radical polymerization initiator in this case is used for curing vinyl monomers, and for example, benzoyl peroxide, lauroyl peroxide, diisopropyl dicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy One or more of pivalate, t-butylperoxydiisobutyrate, azobisisobutyronitrile, azobisdimethylvaleronitrile, etc.
A mixture of more than one species can be used. The amount of the polymerization initiator used is 0.0
It is 1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

The amine catalyst and the organometallic catalyst are preferably
Used for 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-7,1,1,8-diazabicyclo (5,4,0) undecene-7 salt and the like. Examples of the organometallic catalyst include dibutyltin dilaurate and the like.
It is used in the range of 000 ppm.

In order to obtain the synthetic resin lens of the present invention, a raw material mixture containing a curing agent is injected into a casting made of a metal, glass, plastic or the like having a desired lens shape, followed by heat curing. As the curing conditions, the polymerization temperature was raised in the range of 30 to 100 ° C, and the polymerization time was 5 to 5.
After about 72 hours, the obtained cured product becomes a colorless and transparent crosslinked resin insoluble in a solvent. In addition, cured lenses
After demolding, it is desirable to perform an annealing treatment at a temperature of 80 to 120 ° C. for 1 to 5 hours in a nitrogen or air atmosphere. 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 1.
The refractive index is preferably 55 or more. If the refractive index is less than 1.55, there is a disadvantage that the edge thickness of the lens increases as the power increases. The Abbe number of the synthetic resin lens of the present invention is preferably 30 or more. If the Abbe number is less than 30, chromatic aberration is likely to occur and the field of view becomes unclear. The specific gravity of the synthetic resin lens of the present invention is preferably 1.30 or less, and if it is higher than 1.30, the feature of a lightweight lens is lost.

The synthetic resin lens of the present invention uses additives such as an ultraviolet absorber, an antioxidant, a coloring agent, a release agent, a surfactant, and an antibacterial agent in addition to the raw material and the curing agent. You can also. The synthetic resin lens of the present invention is usually
The product obtained by the above preparation method can be used as it is, but if necessary, a hard coat treatment for improving the surface hardness, a coloring treatment with a disperse dye or a photochromic dye for imparting fashionability can also be performed. .

[0020]

EXAMPLES Hereinafter, the present invention will be described in detail by reference examples and examples, but the present invention is not limited to these examples.

Examples 1 to 20 20 g of a raw material mixture containing each component in the proportions shown in Table 1
And 0.4 g of t-butylperoxyneodecanoate as a curing agent and 1,8-diazabicyclo (5,4,0)
100 ppm of undecene-7 is added and mixed with stirring. The composition was mixed with two glass disks with a diameter of 7 cm and a thickness of 2
into a glass casting made of a gasket made of 1 mm ethylene-propylene rubber. For curing, the temperature was raised from 50 ° C. to 100 ° C. over 18 hours in a hot air thermostat equipped with a program temperature controller, kept at 100 ° C. for 2 hours, and then cooled down to 40 ° C. over 2 hours. The disc-shaped resin demolded after curing was further subjected to an annealing treatment at 100 ° C. for 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 Using a transmittance photometer manufactured by Nippon Denshoku Industries Co., Ltd., JISK
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 was spontaneously dropped onto a resin plate from a height of 127 cm. (5) Heat resistance A 1 cm × 4 cm plate was cut out from a resin plate, dynamic viscoelasticity was measured with a Leo vibron manufactured by Toyo Baldwin Co., and the temperature at which the maximum of tan δ was reached was taken as the glass transition temperature (Tg). did. (6) Dyeability After immersing the test piece in a brown dyeing bath at 92 ° C. for 10 minutes, the light transmittance after dyeing was measured by a transmittance meter in the same manner as in (1) above.

Comparative Examples 1 to 4 Test pieces were cut out from commercially available 2 mm plates made of ADC, PMMA, and PC, and subjected to the physical property tests in the same manner as in Examples 1 to 7 (Comparative Examples 1 to 3). In addition, a mixture of 14 g of diallyl diphenate as a raw material and 6 g of diallyl isophthalate was added to a mixture of 0.1 g of diisopropyl peroxycarbonate as a curing agent.
6 g was added, cured under the same conditions as in Examples 1 to 6, and physical properties were evaluated (Comparative Example 4). The results are shown in Table 2.

[0023]

[Table 1]

(Note) DET; HSCH_TwoCH_TwoS-CH_Two-CH_Two-CH- (SCH_TwoCH_TwoSH)_Two, TET; HSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH_Two-CH_Two-CH- (SCH_TwoCH_TwoSCH_TwoCH
_TwoSH)_Two,  TETT; HSCH_TwoCH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH_Two-CH_Two-CH- (SCH_Two
CH_TwoSCH_TwoCH_TwoSCH_TwoCH_TwoSH)_Two, TETC; HSCH_TwoCH_TwoSCH_TwoCH_TwoS-CH (C₆H_Five) -CH_Two-CH- (SCH_TwoCH
_TwoSCH_TwoCH_TwoSH)_Two, DVB; divinylbenzene, DVBP; divinylbiphenyl, TMI; 3-isopropenyl-α, α-dimethylbenzyl
Luisocyanate, BPE-2E; 2,2-bis (4-methacryloxy
(Xylphenyl) propane, ST; styrene.

[0025]

[Table 2]

(Note) PADC; Polydiethylene glycol bisallyl carbonate PMMA; Polymethyl methacrylate PC; Polycarbonate

The cured products of Examples 1 to 6 have a high refractive index of 1.60 or more and a high Abbe number of 30 or more as compared with the conventional optical materials shown in Comparative Examples. At the same time, a material having a specific gravity as low as 1.3 or less and having various physical properties such as dyeability, heat resistance and impact resistance required for other lenses has been obtained.

[0028]

According to the synthetic resin lens of the present invention, it has a high optical characteristic with a refractive index of 1.55 or more, an Abbe number of 30 or more, and a low specific gravity of 1.3 or less. ,
Further, there is provided a synthetic resin lens excellent in various physical properties required for the lens, such as dyeability, heat resistance and impact resistance. For this reason, it is possible to obtain a thinner lens and a lighter lens having optical homogeneity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) // C07C 321/14 C07C 321/14 321/20 321/20 F term (reference) 4H006 AA03 AB48 TA04 TB75 4J034 CA32. FA03 JA33

Claims (2)

[Claims] 1. A trithiol represented by the following general formula (1): (Wherein, R ¹ and R ² are the same or different groups and each represent a hydrogen atom,
Represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, j,
h and m represent the same or different integers of 1 to 3, and k represents 0 or 1. ) Of 30 to 90% by weight, divinylbenzene and / or divinylbiphenyl of 5 to 40% by weight, 3-
A mixture containing 5 to 50% by weight of isopropenyl-α, α-dimethylbenzyl isocyanate as an essential component and 0 to 60% by weight of a vinyl monomer (excluding divinylbenzene and divinylbiphenyl) is cured. Synthetic resin lens. 2. A synthetic resin lens obtained by curing the mixture according to claim 1 using a radical polymerization initiator and an amine catalyst or an organometallic catalyst as a curing agent.