JP3028009B2 - Composition for high refractive index optical material and manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Background of the Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for a plastic lens, and more particularly to a resin for a lens having a high refractive index and excellent impact resistance.

[0002]

2. Description of the Related Art Diethylene glycol bisaryl carbonate resins have been widely used as resins for plastic lenses. This resin has advantages such as excellent impact resistance, transparency, and good light dispersion characteristics, but has a low refractive index of 1.50, and requires a lens to obtain refraction equivalent to glass. However, there was a disadvantage that the thickness became thick.

On the other hand, it is known that various diacrylates or dimethacrylates easily undergo radical polymerization to give a lens having excellent transparency. For example, di (meth) acrylates having a bromine-containing bisphenol A skeleton (JP-A-59-184210, JP-A-59-19)
3915) and di (meth) acrylates having a sulfur-containing aromatic skeleton (JP-A-60-26010 and JP-A-62-195357) have a high refractive index. In addition, it is known to exhibit excellent optical characteristics with a high balance of a high Abebe number.

[0004] However, these compounds form a highly crosslinked structure by radical polymerization, exhibiting excellent heat resistance and polishing properties, but tend to make the cured product brittle. As a method for improving these disadvantages, a method of converting a bromine-containing bisphenol A derivative into urethane (meth) acrylate is disclosed in Japanese Patent Application Laid-Open No. 60-51706. However, since a bromine atom is contained, the specific gravity increases. Inevitably, the weather resistance deteriorates.

[0005] On the other hand, the present inventors have solved the above problem by converting the mercapto compound represented by the general formula [II], which is an object of the present invention, into a specific bis (meta) compound also represented by the general formula (I). ) It has been found that an improved high refractive index optical material is obtained by specifically reacting with an acrylate compound (all of which will be described later) to give a good cured product.
No. 05 was proposed. However, it has been found that, although the high refractive index optical material comprising these compounds is excellent in impact resistance, when the content of the mercapto compound exceeds a certain level, the elastic modulus at room temperature tends to decrease.

Further, a material obtained by curing a composition comprising a bis (meth) acrylate compound represented by the general formula [I] and a polyfunctional isocyanate, which is the subject of the present invention, is disclosed in
As disclosed by the present inventors, as far as the present inventors are aware, in this composition, polymerization is not uniform, and striae are liable to occur, and it takes a long time to cure uniformly.

[Summary of the Invention]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems and to provide a resin for a lens which is lightweight, has high refraction, and is excellent in transparency and impact resistance.

<Summary>

According to the present invention, there is provided a high refractive index optical material comprising a composition comprising the following components A, B, and C, wherein the composition comprises heat and / or active energy rays and / or ethylenically unsaturated. It is characterized by comprising a resin which is polymerized and cured by being subjected to the action of a radical generator and / or a urethanation reaction catalyst for bonding. Component (A): Sulfur-containing (meth) acrylic monomer represented by the following formula [I]

[0009]

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[In each formula, R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ each have 1 to 12 carbon atoms.
X represents a halogen atom excluding fluorine, and n represents 0 or an integer of 1 to 4. A plurality of groups may be the same or different. Component (B): a mercapto compound selected from the group consisting of compounds represented by the following formulas [II], [III] and [IV] [Wherein, R ⁴ represents —CH ₂ — or —CH ₂ CH ₂ —, and R ⁵ has 2 to 15 carbon atoms that may contain ether oxygen.
And a represents an integer of 2 to 6. A plurality of groups may be the same or different. ]

[0011]

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[0012] _c- (where b and c each represent an integer of 1 to 8, d represents an integer of 0 to 2. A plurality of groups may be the same or different.)

[0013]

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[Wherein, Z is a halogen atom except fluorine,
e, f, e 'and f' each represent an integer of 1 to 3, and g and g 'each represent an integer of 0 to 2. A plurality of groups may be the same or different. However, the weight ratio of component (B) / component (A) is from 5/95 to 50/50.
It is. Component (C): an isocyanate compound having a plurality of -NCO groups. However, the ratio of the -NCO group of the component (C) to the total of -SH groups of the compounds of the components (A) and (B) is -SH / -NC
O is 1/3 to 3/1.

The method for producing a high-refractive-index optical material according to the present invention comprises the steps of: preparing a composition comprising the following components (A), (B) and (C) by using a radical polymerization initiator and a urethanization reaction catalyst. The method is characterized in that radical polymerization or radical polymerization and urethanation reaction are simultaneously performed by irradiation with ultraviolet rays, and then the polymerization is completed by heating. Component (A): Sulfur-containing (meth) acrylic monomer represented by the following formula [I]

[0016]

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[In each formula, R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are each a carbon atom having 1 to 12 carbon atoms.
X represents a halogen atom excluding fluorine, and n represents 0 or an integer of 1 to 4. A plurality of groups may be the same or different. Component (B): a mercapto compound selected from the group consisting of compounds represented by the following formulas [II], [III] and [IV] [Wherein, R ⁴ represents —CH ₂ — or —CH ₂ CH ₂ —, and R ⁵ has 2 to 15 carbon atoms that may contain ether oxygen.
And a represents an integer of 2 to 6. A plurality of groups may be the same or different. ]

[0018]

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[0019] _c- (where b and c each represent an integer of 1 to 8, d represents an integer of 0 to 2. A plurality of groups may be the same or different.)

[0020]

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[Wherein, Z is a halogen atom except fluorine,
e, f, e 'and f' each represent an integer of 1 to 3, and g and g 'each represent an integer of 0 to 2. A plurality of groups may be the same or different. However, the weight ratio of component (B) / component (A) is from 5/95 to 50/50.
It is. Component (C): an isocyanate compound having a plurality of -NCO groups. However, the ratio of the -NCO group of the component (C) to the total of -SH groups of the compounds of the components (A) and (B) is -SH / -NC
O is 1/3 to 3/1.

<Effect> A resin for a lens which is lightweight, has a high refractive index, and is excellent in transparency and impact resistance can be obtained.

[Specific Description of the Invention] [High Refractive Index Optical Material] The high refractive index optical material according to the present invention is obtained by polymerizing and curing a composition containing the components (A), (B) and (C). It is. Here, "comprising" includes a small amount of auxiliary components (details described later) in addition to the listed components, that is, components (A) to (C), as long as the gist of the present invention is not impaired. It means that it is OK.

<Component (A): Sulfur-Containing (Meth) acrylic Monomer> The component (A) is a sulfur-containing bis (meth) acrylate represented by the formula [I].

[0025]

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[In each formula, R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are each a carbon atom having 1 to 12 carbon atoms.
X represents a halogen atom excluding fluorine, and n represents 0 or an integer of 1 to 4. A plurality of groups may be the same or different. Note that “(meth) acryl” and “(meth) acrylate” are generic terms for acryl or methacryl and acrylate or methacrylate.

The sulfur-containing (meth) -containing compound represented by the formula (I)
Specific examples of the acrylate compound include, for example, p-
Bis (β-methacryloyloxyethylthio) xylylene, p-bis (β-acryloyloxyethylthio) xylylene, m-bis (β-methacryloyloxyethylthio) xylylene, m-bis (β-acryloyloxyethylthio) xylylene, p-bis (β-methacryloyloxyethylthio) tetrabromoxylylene and the like.

These compounds are described, for example, in
195357 can be synthesized.

<Component (B): Mercapto Compound> The mercapto compound of the component (B) is a compound represented by each of the following formulas [II] to [IV]. The mercapto compound as the component (B) can be used in each group and / or between each group. [Wherein, R ⁴ represents —CH ₂ — or —CH ₂ CH ₂ —, and R ⁵ has 2 to 15 carbon atoms that may contain ether oxygen.
And a represents an integer of 2 to 6. A plurality of groups may be the same or different. ]

[0030]

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[0031] _c- (where b and c each represent an integer of 1 to 8, d represents an integer of 0 to 2. A plurality of groups may be the same or different.)

[0032]

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[Wherein, Z is a halogen atom except fluorine,
e, f, e 'and f' each represent an integer of 1 to 3, and g and g 'each represent an integer of 0 to 2. A plurality of groups may be the same or different. The mercapto compound represented by the formula [II] is a di- to hexavalent thioglycolic acid or thiopropionate.

Specific examples of the compound of the formula [II] include, for example, pentaerythritol tetrakis (β-thiopropionate), pentaerythritol tetrakis (thioglycolate), trimethylolpropane tris (β-thioglycolate).
Thiopropionate), trimethylolpropane tris (thioglycolate), diethylene glycol bis (β
-Thiopropionate), diethylene glycol bis (thioglycolate), triethylene glycol bis (β-thiopropionate), triethylene glycol bis (thioglycolate), dipentaerythritol hexakis (β-thiopropionate) ), Dipentaerythritol hexakis (thioglycolate) and the like.

The compound of the formula [III] is a ω-SH group-containing triisocyanurate. Specific examples of the compound of the formula [II] include, for example, tris [2- (β-thiopropionyloxy) ethyl] triisocyanurate, tris (2-thioglyconyloxyethyl) isocyanurate, tris [2- (β -Thiopropionyloxyethoxy) ethyl] triisocyanurate, tris (2-thioglyconyloxyethoxyethyl) triisocyanurate, tris [3- (β-thiopropionyloxy) propyl] triisocyanurate, tris (3-thioglycol Nyloxypropyl) triisocyanurate and the like.

The compound represented by the formula [IV] is α, ω-SH
It is a group-containing ether. Specific examples of the compound of the formula [IV] include, for example, 2,2-bis [4- (β-hydroxyethoxy) phenyl] propane = di-β-thiopropionate, 2,2-bis [4- (Β-hydroxyethoxy) phenyl] propane = di-β-thioglycolate,
2,2-bis [4- (β-hydroxyethoxyethoxy) phenyl] propane = di-β-thiopropionate, 2,2-bis [4- (β-hydroxyethoxyethoxy) phenyl] propane = di-β -Thioglycolate, 2,2-bis [3,5-dibromo-4- (β-hydroxyethoxy) phenyl] = propane-di-β-thiopropionate, 2,2-bis [3,5-dibromo -4
-(Β-hydroxyethoxy) phenyl] propane = di-β-thioglycolate.

<Component (C)> Polyfunctional isocyanates for urethanizing the above compounds, ie, isocyanates having a plurality of —NCO groups, include o-xylylene diisocyanate, m-xylylene diisocyanate, p-type
-Xylylene diisocyanate, isophorone diisocyanate, triisocyanurate, tolylene diisocyanate and its nuclear hydrogenated product, hexamethylene diisocyanate, and the like. Particularly preferred among these isocyanate compounds are m-xylylene diisocyanate.

<Composition> The ratio of component (A) to component (B) is as follows. B / A = 5 parts by weight / 95 parts by weight / 50 parts by weight / 50 parts by weight, preferably 15 parts by weight / 85 parts by weight / 40 parts by weight / 60 parts by weight

Component (B) is 5 parts by weight relative to component (A).
If it is less than / 95, there is almost no effect of improving the physical properties such as the impact resistance of the cured product, and if it is more than 1/1, the heat resistance of the cured product is lowered. On the other hand, the amount of the polyfunctional isocyanate (component (C)) added when the mixture of the above components (A) and (B) is urethanized depends on the number of -SH groups in the mixture and -NCO in the polyfunctional isocyanate. The ratio of the number of groups is as follows. -NCO / -SH = 1/3 to 3/1, preferably 1/2 to 2/1

The number of -NCO groups is 3 by weight with respect to -SH.
If it is excessive, the heat resistance decreases, and if it is less than 1/3, the bending properties deteriorate. If the heat resistance decreases, cracks tend to occur in the coating film applied to the lens, and if the bending characteristics deteriorate, the center thickness of the lens cannot be reduced, which is not preferable.

<Auxiliary Components> The high refractive index optical material according to the present invention is obtained by polymerizing and curing a composition containing components (A) to (C), and this composition contains a small amount of auxiliary components. However, it is as described above. Therefore, the resin for a lens of the present invention can be produced by mixing a relatively small amount of another monomer capable of radical polymerization with the composition before curing and copolymerizing the mixture. Other monomers used at that time, for example, styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene,
Core and / or side chain substituted and unsubstituted styrene such as divinylbenzene and α-methylstyrene, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and halogen-substituted halogens other than fluorine, trimethylolpropane Tri (meth) acrylate, 2,2-bis [4 (β-methacryloyloxyethoxy) phenyl] propane, 2,2-bis [4 (β
-Acryloyloxyethoxy) phenyl] propane,
(Meth) acrylate compounds such as triethylene glycol di (meth) acrylate are exemplified. Of these other monomers, styrene, chlorostyrene, dibromostyrene, divinylbenzene, 4,4'-bis (methacryloyloxyethoxy) diphenylpropane, and mixtures thereof are particularly preferred. As auxiliary ingredients,
Other examples include antioxidants, ultraviolet absorbers, dyes and pigments, and fillers.

<Polymerization and Curing> The high refractive index optical material according to the present invention provides a composition containing the components A, B and C by generating radicals for heat and / or active energy rays and / or ethylenically unsaturated bonds. And / or a resin which is polymerized and cured by the action of a urethanization reaction catalyst.

The type and strength of these excitation means to be applied are arbitrary as long as a predetermined polymerized cured product can be obtained, but from the viewpoint of improving operability and productivity of the resulting cured product, component (A) The composition comprising (C) to (C) is irradiated with ultraviolet light in the presence of a radical polymerization initiator and a urethanization reaction catalyst to perform radical polymerization or urethanation reaction with the radical polymerization, and then heat to complete the polymerization. Is preferred.

The amount of the ultraviolet light to be irradiated is arbitrary as long as the photopolymerization initiator generates radicals. If the amount is extremely small, the effect of photopolymerization cannot be obtained. Cause degradation of the polymer by light,
Total energy of ultraviolet light of 0.01 nm to 390 nm is 0.01
It is preferable to appropriately select an ultraviolet ray in the range of J to 300 J, preferably 0.1 J to 200 J, according to the composition of the monomer and the type of additive such as the type of photopolymerization initiator. Specific examples of the lamp to be used include a metal halide lamp and a high-pressure mercury lamp.

The temperature and time of the heat polymerization after the irradiation of the ultraviolet rays vary depending on the type and amount of the thermal polymerization initiator and the urethanization reaction catalyst to be added, and are selected in accordance with the desired physical properties of the lens. In general, excessive heating usually causes the lens to easily turn yellow, and a catalyst that is too active at low temperatures makes the composition unstable during handling.
At a temperature of 0.05 to 10 hours. The term “heat polymerization” as used herein includes post-treatment steps of a lens molded product, for example, polymerization by heat applied during coating.

By using this method, the polymerization time can be greatly reduced as compared with the case of heating polymerization alone, and
The problem of thickening or separation in some cases when a compound which has been urethanized beforehand is mixed with the compound of the formula [I] is solved, and productivity and operability are improved. In general, when copolymerizing with urethane acrylate in order to improve physical properties, it is inevitable to increase the viscosity during mixing. Particularly, when a liquid is injected like a lens, it is desirable to use the above method.

The photopolymerization initiator used here is 2,2.
6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, ,
Acylphosphine oxides and acylphosphinic esters such as 6-dimethoxybenzoyldiphenylphosphine oxide, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4-diphenoxy Dichloroacetophenone, diethoxyacetophenone, 1- (4
Acetophenone compounds such as -isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzophenone, methyl benzoylbenzoate,
Phenylbenzophenone, hydroxybenzophenone,
Benzophenone compounds such as 3,3'-dimethyl-4-methoxybenzophenone and diphenoxybenzophenone.

Preferred photopolymerization initiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Trimethylbenzoylphenylphosphinic acid methyl ester, 1-hydroxycyclohexylphenylketone, benzophenone and diphenoxybenzophenone.

The ratio of these photopolymerization initiators is from 0.01 to 0.1 based on 100 parts by weight of the diethylenically unsaturated monomer.
It is about 3 parts by weight, preferably about 0.02 to 0.2 parts by weight. If the mixing ratio of the photopolymerization initiator is too large, not only is the internal homogeneity of the cured resin inferior, but also the hue is deteriorated.If the photopolymerization initiator is too small, the composition can be sufficiently cured. Disappears. The thermal polymerization initiator is not always essential, but it is desirable to add it in order to complete the polymerization better. The amount used is the composition 100
It is preferably 5 parts by weight or less based on parts by weight. Excessive use is not preferred because it has adverse effects such as deterioration of the hue of the cured product. Specific examples of the thermal polymerization initiator include benzoyl peroxide, diisopropyl peroxycarbonate, ralloyl peroxide, t-butylperoxy (2-ethylhexanoate), azobisisobutyronitrile,
And the like. In general, any of those used for thermal polymerization of (meth) acrylates can be used. These generally belong to the category of radical generators for ethylenically unsaturated bonds.

On the other hand, as the catalyst for the urethanation reaction, a known catalyst can be used. Specific examples include metal compounds such as dibutyltin dilaurate and aluminum triisopropoxide, and Lewis bases such as tertiary amines and tertiary phosphines. The amount used should be the component (A)
10 to 10,000 ppm based on the composition consisting of (C)
Level, preferably about 100 to 1000 ppm.
When the amount of the urethanization reaction catalyst exceeds 10,000 ppm, the composition of the components (A) to (C) is thickened by the urethanization reaction, so that injection becomes difficult. Conversely, if it is less than 10 ppm, it is difficult to complete the polymerization, and various physical properties are reduced.

In the present invention, as described above, the composition before curing can be cured by adding an antioxidant, an ultraviolet absorber, a coloring agent, and the like as auxiliary components. The cured resin molded into a shape can be subjected to a surface treatment such as a hard coat and an anti-reflection coat.

[0052]

The following examples serve to explain the present invention more specifically. In addition, the part in an example shows a weight part. Various properties of the cured product described in the examples were measured by the following test methods. (1) Appearance Visual observation (2) Refractive index Measured at 25 ° C. using an Abbe refractometer (manufactured by Atago). (3) Optical distortion The cured product obtained using the lens mold was inspected with a distortion inspection machine (manufactured by Toshiba Glass Co., Ltd.). (4) Impact resistance A hard ball (weight: 16.3 g, diameter: 15.9 mm) is 127 on a flat plate having a thickness of 2 mm based on the FDA standard.
The sample was dropped from a height of cm, and no damage was generated. Measurement temperature 25 ° C (5) Flexural modulus For a 1cm wide and 2mm thick plate
It measured with the autograph at the distance between fulcrums of 3 cm. Measurement temperature 25 ° C

Example 1 87.4 parts of p-bis (β-methacryloyloxyethylthio) xylylene (TEMA) as the component (A) and pentaerythritol tetrakis (β-thiopropionate) (PETP) as the component (B) 7.1 parts, component (C)
As m-xylylene diisocyanate (m-XD
I) 5.5 parts, and as a polymerization initiator and a polymerization catalyst, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Lucirin T.L.
P. O ") 0.05 parts, t-butylperoxy-2-ethylhexanoate (" Perbutyl O "manufactured by NOF Corporation)
After uniformly stirring and mixing 0.3 part and 0.05 part of dibutyltin dilaurate, the composition was defoamed to obtain a composition.

This composition was poured into a mirror-finished glass plate and a gasket made of ethylene-vinyl acetate copolymer having a depth of 2 mm, and a distance of 40 cm from the glass surface.
Then, ultraviolet rays were irradiated for 10 minutes while being put on a conveyor between metal halide lamps having an output of 80 W / cm above and below. Further, after that, the mixture is placed in an oven at 80 ° C. for 2 hours,
After heat polymerization at 00 ° C. for 2 hours, the product was demolded to obtain a colorless and transparent cured product. The measurement results of physical properties of the cured product were as shown in Table 1.

The defoamed composition was similarly poured into a minus lens lens mold having a diameter of 80 mm and a center thickness of 1.3 mm composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. After irradiating with ultraviolet rays in the same manner as above, heat polymerization was carried out, and the mold was removed to obtain a colorless and transparent lens. The optical distortion of this lens was as shown in Table 1.

Example 2 56.8 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A), 24.4 parts of pentaerythritol tetrakis (β-thiopropionate) as the component (B) and the component A cured product was obtained in exactly the same manner as in Example 1 except that 18.8 parts of m-xylylene diisocyanate was used as (C). The measurement results of physical properties and the optical distortion of the lens were as shown in Table 1.

Example 3 76.2 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A), 13.5 parts of pentaerythritol tetrakis (β-thiopropionate) as the component (B) and the component A cured product was obtained in exactly the same manner as in Example 1 except that 10.3 parts of m-xylylene diisocyanate was used as (C). The measurement results of physical properties and the optical distortion of the lens were as shown in Table 1.

Example 4 62.3 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A), 11.0 parts of pentaerythritol tetrakis (β-thiopropionate) as the component (B), As (C), 8.4 parts of m-xylylene diisocyanate and 18.3 parts of styrene as an auxiliary component (component (D)) were used to emit ultraviolet light.
A cured part was obtained in exactly the same manner as in Example 1 except that irradiation was performed for 0 minutes. The measurement results of physical properties and the optical distortion of the lens were as shown in Table 1.

Example 5 69.1 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A), 12.2 parts of pentaerythritol tetrakis (β-thiopropionate) as the component (B) and the component A cured product was obtained in exactly the same manner as in Example 1 except that 18.7 parts of m-xylylene diisocyanate was used as (C). The measurement results of physical properties and the optical distortion of the lens were as shown in Table 1.

Comparative Example 1 100 parts of p-bis (β-methacryloyloxyethylthioxyrylene) Using 0.05 part of “Lucillin TPO” and 0.3 part of “Perbutyl O”) as a polymerization initiator A cured product was obtained in the same manner as in Example 1. The measurement results of physical properties and the optical distortion of the lens were as shown in Table 1.

Comparative Example 2 The procedure was carried out except that 60 parts of p-bis (β-methacryloyloxyethylthio) xylylene was used as the component (A) and 40 parts of pentaerythritol tetrakis (β-thiopropionate) were used as the component (B). A cured product was obtained in exactly the same manner as in Example 1. The cured product was very soft and could not be used as a lens material.

Example 6 As a component (A), 88.9 parts of p-bis (β-methacryloyloxyethylthio) xylylene (TEMA), and as a component (B), tris [2- (β-thiopropionyloxy) ethyl] triethyl Isocyanurate (THEIC) 7.
2 parts, 3.9 parts of m-xylylene diisocyanate (m-XDI) as the component (C), and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF) as a polymerization initiator and a polymerization catalyst 0.05 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation) and 0.05 parts of dibutyltin dilaurate. After stirring and mixing, defoaming was performed to obtain a composition.

This composition was poured into a 2 mm deep mold composed of a mirror-finished glass plate and a gasket made of ethylene-vinyl acetate copolymer, and was placed at a distance of 40 mm from the glass surface.
Ultraviolet rays were irradiated for 10 minutes while being put on a conveyor between metal halide lamps having an output of 80 W / cm, which were vertically arranged at a height of cm. Furthermore, after this, in an oven at 80 ° C. for 2 hours,
After heat polymerization at 100 ° C. for 2 hours, the product was demolded to obtain a colorless and transparent cured product. The measurement results of physical properties of the cured product were as shown in Table-2.

The defoamed composition was similarly injected into a minus lens lens mold having a diameter of 80 mm and a center thickness of 1.3 mm constituted by a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. After irradiating with ultraviolet rays in the same manner as above, heat polymerization was carried out, and the mold was removed to obtain a colorless and transparent lens. The optical distortion of this lens was as shown in Table-2.

Example 7 78.6 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A) and tris [2- (β-thiopropionyloxy) ethyl] as the component (B)
A cured product was obtained in exactly the same manner as in Example 6 except that 13.9 parts of triisocyanurate and 7.5 parts of m-xylylene diisocyanate were used as the component (C). The measurement results of physical properties and the optical distortion of the lens were as shown in Table-2.

Example 8 60.3 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A) and tris [2- (β-thiopropionyloxy) ethyl] as the component (B)
25.8 parts of triisocyanurate, as component (C),
A cured product was obtained in exactly the same manner as in Example 6, except that 13.9 parts of m-xylylene diisocyanate was used. The measurement results of physical properties and the optical distortion of the lens were as shown in Table-2.

Example 9 73.1 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A) and tris [2- (β-thiopropionyloxy) ethyl] as the component (B)
A cured product was obtained in exactly the same manner as in Example 6, except that 12.9 parts of triisocyanurate and 14 parts of m-xylylene diisocyanate were used as the component (C). The measurement results of physical properties and the optical distortion of the lens were as shown in Table-2.

Example 10 62.9 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A) and tris [2- (β-thiopropionyloxy) ethyl] as the component (B)
11.1 parts of triisocyanurate, as component (C),
A cured product was obtained in exactly the same manner as in Example 6, except that ultraviolet rays were irradiated for 30 minutes using 6 parts of m-xylylene diisocyanate and 20 parts of styrene as an auxiliary component (component (D)). Table 1 shows the physical property measurement results and the optical distortion of the lens.
As shown in FIG.

Example 11 90.0 parts of p-bis (β-methacryloyloxyethylthio) xylylene (TEMA) as the component (A) and 2,2-bis [4- (β-hydroxyethoxy) as the component (B) Phenyl] propanedi-β-thiopropionate (BDESH) (7.2 parts), m-xylylene diisocyanate (m-XDI) (2.8 parts) as component (C), and 2,2 4,6-Trimethylbenzoyldiphenylphosphine oxide (“Lucillin TPO” manufactured by BASF) 0.05
Parts, 0.3 part of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation) and 0.05 part of dibutyltin dilaurate were uniformly stirred and mixed, and then defoamed to obtain a composition. I got something.

This composition was poured into a 2 mm deep mold composed of a mirror-finished glass plate and a gasket made of ethylene-vinyl acetate copolymer, and was placed at a distance of 40 mm from the glass surface.
Ultraviolet rays were irradiated for 10 minutes while being put on a conveyor between metal halide lamps having an output of 80 W / cm, which were vertically arranged at a height of cm. Furthermore, after this, in an oven at 80 ° C. for 2 hours,
After heat polymerization at 100 ° C. for 2 hours, the product was demolded to obtain a colorless and transparent cured product. The measurement results of physical properties of the cured product were as shown in Table-3.

The defoamed composition was similarly poured into a lens mold for a minus lens having a diameter of 80 mm and a center thickness of 1.3 mm composed of a glass mold and a gasket made of an ethylene-vinyl acetate copolymer. After irradiating with ultraviolet rays in the same manner as above, heat polymerization was carried out, and the mold was removed to obtain a colorless and transparent lens. The optical distortion of this lens was as shown in Table-3.

Example 12 80.4 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A) and 2,2-bis [4- (β-hydroxyethoxy) phenyl] propanedi as the component (B) A cured product was obtained in exactly the same manner as in Example 11 except that 14.2 parts of -β-thiopropionate and 5.4 parts of m-xylylene diisocyanate were used as the component (C). Physical property measurement result and optical distortion of lens
As shown in Table-3.

Example 13 62.8 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A) and 2,2-bis [4- (β-hydroxyethoxy) phenyl] propanedi as the component (B) A cured product was obtained in exactly the same manner as in Example 11 except that 26.9 parts of -β-thiopropionate and 10.3 parts of m-xylylene diisocyanate were used as the component (C). The measurement results of physical properties and the optical distortion of the lens were as shown in Table-3.

Example 14 76.3 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A) and 2,2-bis [4- (β-hydroxyethoxy) phenyl] propanedi as the component (B) A cured product was obtained in exactly the same manner as in Example 11 except that 13.5 parts of -β-thiopropionate and 10.2 parts of m-xylylene diisocyanate were used as the component (C). The measurement results of physical properties and the optical distortion of the lens were as shown in Table-3.

Example 15 64.3 parts of p-bis (β-methacryloyloxyethylthio) xylylene as the component (A) and 2,2-bis [4- (β-hydroxyethoxy) phenyl] propanedi as the component (B) 11.4 parts of -β-thiopropionate,
4.3 parts of m-xylylene diisocyanate as component (C) and styrene 20 as auxiliary component (component (D))
A cured product was obtained in exactly the same manner as in Example 11 except that UV light was irradiated for 30 minutes using the part. The measurement results of physical properties and the optical distortion of the lens were as shown in Table-3.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

According to the present invention, it is possible to obtain a resin for a lens which is lightweight, has a high refractive index, and is excellent in transparency and impact resistance.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-1-96208 (JP, A) JP-A-3-79614 (JP, A) JP-A-1-163702 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08G 18/38 C08F 20/38 C08G 75 / 02,75 / 04

Claims (2)

(57) [Claims] 1. A composition for a high refractive index optical material, comprising the following components A, B and C: Component (A): a sulfur-containing (meth) acrylic monomer represented by the following formula [I]: [In each formula, R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ each represent a hydrocarbon group having 1 to 12 carbon atoms; X represents a halogen atom excluding fluorine;
Or an integer of 1 to 4. A plurality of groups may be the same or different. Component (B): a mercapto compound O‖ (HSR ⁴ C—O—) a-R ⁵ [II] selected from the group consisting of compounds represented by the following formulas [II], [III] and [IV] [Wherein, R ⁴ represents —CH ₂ — or —CH ₂ CH ₂ —, and R ⁵ has 2 to 15 carbon atoms that may contain ether oxygen.
And a represents an integer of 2 to 6. A plurality of groups may be the same or different. [Chemical formula 2] O ‖ wherein X is HS- (CH _2- ) _b -C- (CH ₂ CH ₂ O-) _d- (CH ₂ ) _c- (where b and c are each an integer of 1 to 8 And d represents an integer of 0 to 2. A plurality of groups may be the same or different.] [Wherein, Z is a halogen atom excluding fluorine, e, f, e '
And f 'each represent an integer of 1 to 3, and g and g' each represent an integer of 0 to 2. A plurality of groups may be the same or different. However, the weight ratio of component (B) / component (A) is 5/95 to 50/50. Component (C): an isocyanate compound having a plurality of -NCO groups. However, the ratio of the -NCO group of the component (C) to the total of -SH groups of the compounds of the components (A) and (B)-
SH / -NCO is 1/3 to 3/1. 2. A composition comprising the following components (A), (B) and (C), which is subjected to ultraviolet irradiation in the presence of a radical polymerization initiator and a urethanation reaction catalyst to perform radical polymerization or A method for producing a high-refractive-index optical material, wherein a radical polymerization and a urethanization reaction are simultaneously performed, followed by heating to complete the polymerization. Component (A): a sulfur-containing (meth) acrylic monomer represented by the following formula [I]: [In each formula, R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ each represent a hydrocarbon group having 1 to 12 carbon atoms; X represents a halogen atom excluding fluorine;
Or an integer of 1 to 4. A plurality of groups may be the same or different. Component (B): a mercapto compound O‖ (HSR ⁴ C—O—) a-R ⁵ [II] selected from the group consisting of compounds represented by the following formulas [II], [III] and [IV] [Wherein, R ⁴ represents —CH ₂ — or —CH ₂ CH ₂ —, and R ⁵ has 2 to 15 carbon atoms that may contain ether oxygen.
And a represents an integer of 2 to 6. A plurality of groups may be the same or different. [Chemical formula 5] O ‖ wherein X is HS- (CH _2- ) _b -C- (CH ₂ CH ₂ O-) _d- (CH ₂ ) _c- (where b and c are each an integer of 1 to 8 And d represents an integer of 0 to 2. A plurality of groups may be the same or different.] [Wherein, Z is a halogen atom excluding fluorine, e, f, e '
And f 'each represent an integer of 1 to 3, and g and g' each represent an integer of 0 to 2. A plurality of groups may be the same or different. However, the weight ratio of component (B) / component (A) is 5/95 to 50/50. Component (C): an isocyanate compound having a plurality of -NCO groups. However, the ratio of the -NCO group of the component (C) to the total of -SH groups of the compounds of the components (A) and (B)-
SH / -NCO is 1/3 to 3/1.