JPH11183703A - Synthetic resin lens and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic resin lens having high refractive index and low dispersion of light and to provide a producing method of a synthetic resin lens by which a desired lens can be easily formed. SOLUTION: This synthetic resin lens is obtd. by forming a monomer mixture containing divinylbenzene and a thiourethane compd. having a thiol group by radical polymn. In the producing method. a thiourethane compd. having thiol group is obtd. by the reaction of polythiol (a<1> ) and polyisocyanate (a<2> ). Then a monomer mixture containing the thiourethane compd. having thiol groups above described and divinylbenzene is prepared, and the monomer mixture is injected into a mold and formed by radical polymn.

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 spectacle lens having a high refractive index (for example, 1.58 or more) and low light dispersion (for example, an Abbe number of 30 or more). And a synthetic resin lens having excellent characteristics.

[0002]

2. Description of the Related Art Recently, synthetic resin lenses have been widely used as spectacle lenses. Important characteristics required for such a synthetic resin lens include a high refractive index,
Light dispersibility is low. According to the synthetic resin having a high refractive index, it is possible to reduce the thickness of the peripheral portion of the lens for correcting myopia and the thickness of the central portion of the lens for correcting hyperopia and the lens for presbyopia. The appearance can be improved. Further, according to the synthetic resin having low light dispersibility, a lens having small chromatic aberration can be obtained.

On the other hand, polydiethylene glycol bisallyl carbonate (CR-39), which is frequently used as a constituent material of spectacle lenses, has a refractive index as low as about 1.50, and sufficiently reduces the thickness of the lens. Cannot be performed, and the appearance is not preferable. Under such circumstances, development of a synthetic resin lens having a high refractive index and a low dispersibility has been desired.

As a means for responding to such demands, attempts have been made to introduce a sulfur atom into a synthetic resin (Japanese Patent Application Laid-Open Nos. 2-27059 and 5-2089).
No. 50). In this case, as the content ratio of the sulfur atom increases, the refractive index of the obtained lens increases, and the light dispersibility decreases.

The following methods (1) to (3) are known as methods for introducing a sulfur atom into a synthetic resin. (1) A method of synthesizing a radically polymerizable monomer containing a sulfur atom and polymerizing the monomer (JP-A-63-18)
8660, JP-A-2-261808). (2) A method of reacting a thiol compound with an isocyanate compound to obtain a thiourethane polymer (JP-A-60-1)
No. 199016, JP-A-3-236386). (3) A method of adding a thiol compound to a double bond portion of a radical polymerizable monomer (JP-A-62-270627)
JP-A-63-235332, JP-A-63-309
509, JP-A-1-197528).

However, in the above method (1), the operation of synthesizing and purifying a monomer containing a sulfur atom is complicated, and for example, a reaction between a (meth) acrylic acid derivative and a thiol compound is carried out to prepare a monomer. When the thiol compound is obtained, the thiol compound is added to the double bond of the (meth) acrylic acid derivative, and the yield of the target monomer is significantly reduced.

In the above method (2), when a lens is molded by a casting polymerization method, a sealing material (for example, a gasket tape for sealing a joint portion between a male mold and a female mold).
However, there is a problem that it is eluted in the monomer composition, and the design for preventing this is complicated. The above (2)
In the method described above, there is also a problem that the glass constituting the mold reacts with the isocyanate compound, and the releasability is impaired. In this case, it is conceivable to add a release agent to the monomer composition, but the release agent may remain in the polymer (lens material) and adversely affect the processability of the lens material. is there.

[0008] Also in the above method (3), there is a problem that the sealing material is eluted into the monomer composition when the lens is molded by the casting polymerization method. Here, in order to prevent elution and breakage of the sealing material, it is also possible to control the viscosity of the system by performing pre-polymerization of the monomer composition (JP-A-63-309509, JP-A No. 2-309509). -289
622, JP-A-2-283731).
However, it is difficult to control the viscosity in a suitable range by pre-polymerization, and a reproducible pre-polymer (monomer composition) cannot be obtained.
Furthermore, when performing thermal polymerization or photopolymerization as this preliminary polymerization, the stability of the preliminary polymer (monomer composition) is impaired by the residual polymerization initiator.

[0009]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances. A first object of the present invention is to provide a synthetic resin lens having a high refractive index and low light dispersion. A second object of the present invention is to
An object of the present invention is to provide a synthetic resin lens having low specific gravity and excellent transparency. A third object of the present invention is to provide moldability (moldability).
The object of the present invention is to provide a good synthetic resin lens. A fourth object of the present invention is to provide a synthetic lens capable of easily molding (molding) a desired lens without dissolution or breakage of a sealing material when molded by a casting polymerization method. An object of the present invention is to provide a method for manufacturing a resin lens.

[0010]

The synthetic resin lens of the present invention comprises [A] a thiourethane compound having a thiol group,
[B] It is obtained by subjecting a monomer mixture containing divinylbenzene to radical polymerization and molding. Further, the synthetic resin lens of the present invention,
[A] a thiourethane compound having a thiol group,
[B] It is characterized by being obtained by radical polymerization of a monomer mixture containing divinylbenzene and [C] an aromatic compound having two or more (meth) acryl groups, followed by molding.

[0011] manufacturing process of the synthetic resin lens of the present invention, the polythiol (a ^1), a polyisocyanate (a ^2), the polythiol (a ¹ to the number of moles of isocyanate groups of the said polyisocyanate (a ²⁾ ) Has the molar ratio of thiol groups ([SH] / [NC
O]) by reaction at a ratio of 1 or more,
(A) a thiourethane compound having a thiol group is obtained, and (A) a thiourethane compound having a thiol group;
[B] It is characterized in that a monomer mixture containing divinylbenzene is prepared, and the monomer mixture is injected into a mold and subjected to radical polymerization to mold. Further, the method of manufacturing a synthetic resin lens of the present invention, the polythiol (a ¹⁾ and, a polyisocyanate (a ^2), the polythiol (a ¹⁾ to the number of moles of isocyanate groups of the said polyisocyanate (a ²⁾ ([SH] / [NC)
O]) by reaction at a ratio of 1 or more,
(A) a thiourethane compound having a thiol group is obtained, and (A) a thiourethane compound having a thiol group;
[B] A monomer mixture containing divinylbenzene and [C] an aromatic compound having two or more (meth) acryl groups is prepared, and the monomer mixture is injected into a mold to form a radical mixture. It is characterized by being formed by polymerization. In the above-mentioned production method, it is preferable that the monomer mixture is preliminarily polymerized to increase the viscosity, and then injected into a mold.

According to the production method of the present invention, a monomer mixture containing a polythiol (a ¹ ), a polyisocyanate (a ² ) and [B] divinylbenzene is prepared, and this monomer mixture is prepared. It is characterized in that it is injected into a mold, and is formed by thiourethanation reaction and radical polymerization. In addition, the production method of the present invention comprises a polythiol (a ¹ ), a polyisocyanate (a ² ),
[B] A monomer mixture containing divinylbenzene and [C] an aromatic compound having two or more (meth) acryl groups is prepared, and the monomer mixture is injected into a mold, It is characterized by molding by urethanization reaction and radical polymerization.

[0013]

(1) As an essential component of the monomer mixture, [A]
By containing a thiourethane compound having a thiol group, a thiourethane bond is introduced into a copolymer (lens material) obtained by polymerizing the thiourethane compound. And
A lens made of a copolymer having a thiourethane bond has excellent toughness and is hard to crack. In addition, since the lens has a hydrophilic property, cutting powder and the like adhering to the surface can be easily removed by a non-organic solvent-based cleaning liquid, and further, a complicated hydrophilic treatment (for example, Excellent adhesion to the hard coat layer can be exhibited without performing plasma treatment and hydrophilic treatment by corona discharge treatment.

(2) [A] The viscosity of the monomer mixture containing a thiourethane compound having a thiol group is 40.
２００200 cp (25 ° C.), relatively high, and polythiol or polyisocyanate becomes an oligomer to lower the solubility in the sealing material. Therefore, when casting polymerization of the monomer mixture is performed, the sealing material is eluted. , And can be easily formed (molded). In addition, since the viscosity of the monomer mixture can be adjusted to a suitable range by the thiourethane compound, the monomer mixture has a higher storage stability than a composition obtained by performing preliminary polymerization by radical polymerization. It will be excellent.

(3) [B] A thiourethane compound having a thiol group is added to the unsaturated double bond of divinylbenzene. Then, the copolymer (lens material) into which the sulfur atom has been introduced in this way has both high refractive index and low dispersion.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The monomer mixture used to obtain the synthetic resin lens of the present invention contains [A] a thiourethane compound having a thiol group and [B] divinylbenzene as essential components, and comprises (meth) acrylic An aromatic compound having two or more groups may be contained.

The thiourethane compound (A) having a thiol group (hereinafter, also referred to as "component (A)") constituting the monomer mixture is a polythiol (a ¹ ) having two or more thiol groups in the molecule. And two isocyanate groups in the molecule
One or more and a polyisocyanate (a ^2), the ratio of moles of thiol groups of the relative number of moles of isocyanate groups of the said polyisocyanate (a ²⁾ a polythiol ^{(a 1) ([SH]} / [NCO] ) Is 1 or more (thiourethanation reaction).

The polythiol (a ¹ ) used to obtain the component (A) includes 1,4-bismercaptomethylbenzene, ethanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene Glycol dithioglycolate, 1,2-propanedithiol,
2-mercaptoethyl ether, bismercaptoethylsulfide, bis (mercaptoethylthio) ethane, trimethylolpropane tris (thioglycolate), trimethylolpropane tris (thiopropionate),
Examples thereof include pentaerythritol tetrakis (thioglycolate) and pentaerythritol tetrakis (thiopropionate). These can be used alone or in combination of two or more.
Among them, aliphatic dithiols such as 1,4-butanedithiol, 1,6-hexanedithiol, 2-mercaptoethylether, bismercaptoethylsulfide, bis (mercaptoethylthio) ethane, and 1,4-bis Aromatic dithiols such as mercaptomethylbenzene are preferred.

The polyisocyanate (a ² ) used to obtain the component (A) includes hexamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 4,4- Dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, tolylene diisocyanate, bis (isocyanatomethyl) cyclohexane, 4,4-diphenylmethane diisocyanate, naphthalene diisocyanate, 3,
3-dimethyl-4,4-bisphenylene diisocyanate, metaxylylene diisocyanate, a buret reaction product of hexamethylene diisocyanate, a compound having a trimer structure or an adduct reaction product with trimethylolpropane, and 3 derived from isophorone diisocyanate Functional or tetrafunctional polyisocyanate compounds,
Examples thereof include 2-isocyanatoethyl-2,6-diisocyanatoethylhexanoate, and these can be used alone or in combination of two or more. Among these, 4,4-dicyclohexylmethane diisocyanate, tolylene diisocyanate,
Bis (isocyanatomethyl) cyclohexane, 3,3
-Dimethyl-4,4-bisphenylene diisocyanate and meta-xylylene diisocyanate are preferred from the viewpoint that the finally obtained lens has a high refractive index.

The ratio of the polythiol (a ¹ ) and the polyisocyanate (a ² ) used in the thiourethane-forming reaction is represented by [SH], the number of moles of the thiol group contained in the polythiol (a ¹ ), Polyisocyanate (a
^{When the} number of moles of isocyanate groups contained in ² ) is [NCO], the molar ratio ([SH] / [NCO]) must be 1 or more (that is, no isocyanate groups remain after the reaction). And the molar ratio is 3 to 1
00 is preferred. If the value of [SH] / [NCO] is less than 3, the specific gravity of the finally obtained lens may increase, or the lens may become cloudy. On the other hand, when the value of [SH] / [NCO] exceeds 100, a sufficient amount of thiourethane bond cannot be generated to exhibit the effect of improving moldability and toughness.

The catalyst used for the thiourethanation reaction includes triethylamine, diethylaniline, N, N-
Examples thereof include amine catalysts such as dimethylaminocyclohexane, metal salt catalysts such as stannous chloride, and organometallic catalysts such as dibutyltin dilaurate.

[B] divinylbenzene constituting the monomer mixture is a compound having an unsaturated double bond to which the component [A] is added. [B] divinylbenzene to be subjected to the addition reaction preferably does not contain impurities such as non-polymerizable alkylbenzene and monofunctional alkylstyrene. It is preferable to use those having less than 5% by mass of the alkylbenzene.

The aromatic compound having two or more [C] (meth) acrylic groups constituting the monomer mixture as an optional component (hereinafter also referred to as “[C] component”) is 2,
Bisphenol A derivatives such as 2-bis (4-methacryloxyethoxyphenyl) propane; 2,2-bis (3,5-dichloro-4-methacryloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo) -4
A derivative of a halogen-substituted bisphenol A such as -methacryloxyethoxyphenyl) propane; a diphenylfluorene derivative such as 9,9-bis (4-methacryloxyethoxyphenyl) fluorene. Since the component [C] is contained in the monomer mixture, the moldability (moldability) of the lens can be improved, and the heat resistance and the dyeability of the finally obtained lens are improved. It can also be done. When the component [C] is contained in the monomer mixture, it is preferable to add the component [C] to the system after the preliminary polymerization reaction described later.

Component (A) in the monomer mixture,
The content ratio of [B] divinylbenzene and the component [C] is preferably a ratio satisfying the following formula (i), and more preferably a ratio satisfying the following formula (ii).

[0025]

(I) 1.5 ≦ (b + c) /a≦5.0 (ii) 1.5 ≦ (b + c) /a≦3.0 where a: the thiol group of the component [A] Number of moles b: [B] Number of moles of vinyl group of divinylbenzene c: Number of moles of (meth) acryl group of component [C]

When the value of (b + c) / a is less than 1.5, the finally obtained lens does not have sufficient hardness, elasticity and heat resistance, and when used as a spectacle lens, When the hard coat layer is removed or a hard coat layer is formed, fine cracks are generated in the hard coat layer. On the other hand, when the value of (b + c) / a exceeds 5.0, the finally obtained lens becomes brittle, and the lens into which a sufficient amount of sulfur atoms has not been introduced has a high refractive index and a low refractive index. It does not have dispersibility. Further, the content ratio of the component [A] in the monomer mixture becomes too small, and it becomes difficult to control the viscosity of the monomer mixture in a suitable range [40 to 200 cp (25 ° C.)]. (Moldability) cannot be sufficiently improved.

Various additives may be contained in the monomer mixture in order to improve the weather resistance and the thermal characteristics of the synthetic resin lens of the present invention. Examples of such additives include salicylate UV absorbers such as p-tert-butylphenyl salicylate, benzophenone UV absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone,
(2'hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
Benzotriazole-based ultraviolet absorbers such as (2'-hydroxy-5'-octylphenyl) benzotriazole, cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate; bis (1, 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, di (1,2,2,6)
6-pentamethyl-4-piperidyl) -butyl (3 ′,
5'-ditert-butyl-4-hydroxybenzyl)
Malonate, 1- (2- (3- (3,5-ditert-
Butyl-4-hydroxyphenyl) propionyloxy) ethyl) -4- (3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy)-
2,2,6,6-tetramethylpiperidine, poly ((6
-{(1,1,3,3-tetramethylbutyl) amino}
-1,3,5-triazine-2,4-diyl) (1,6
-{2,2,6,6-tetramethyl-4-piperidinyl {aminohexamethylene)}, poly {6- (morpholino) -S-triazine-2,4-diyl} 1,6
-(2,2,6,6-tetramethyl-4-piperidyl)
Amino {hexamethylene}, 4-hydroxy-2,2,
Hindered amine-based light stabilizers such as dimethyl succinate polymer with 6,6-tetramethyl-1-piperidinethanol; hindered phenol-based antioxidants, trialkylphosphine-based antioxidants, and sulfur-based oxidation Polymerization inhibitor such as 2,4-diphenyl-4-methyl-1-pentene; polymerization inhibitor such as methoxyphenol (storage stabilizer for monomer mixture); coloring agent for adjusting the color tone of the lens Can be mentioned.

The viscosity of the monomer mixture subjected to the casting polymerization needs to be high to some extent from the viewpoint of facilitating the molding (molding) operation.
It is preferably 0 cp (25 ° C.), and more preferably 35 to 200 cp (25 ° C.). If the viscosity of the monomer mixture is too low, it becomes difficult to ensure the sealing property when performing the casting polymerization. On the other hand, if the viscosity is too high, it becomes difficult to perform a filtering operation and a deaeration (defoaming) process before pouring into a mold. Then, since the monomer mixture containing the component (A) at a certain ratio has a viscosity in the above preferable range, the desired lens is obtained by performing cast polymerization of the monomer mixture. It can be easily formed (molded).

The method for preparing the monomer mixture is not particularly limited, but the component [A] is obtained by reacting the polythiol (a ¹ ) with the polyisocyanate (a ² ). [B] A method in which divinylbenzene is added, and if necessary, the component [C] and various additives are added. Here, as a specific example of a preferable preparation method, the component [A] is obtained by subjecting a polythiol (a ¹ ) and a polyisocyanate (a ² ) to a thiourethanation reaction in the presence of a reaction catalyst. [B] divinylbenzene (part or all), a radical polymerization initiator or a photopolymerization initiator, and a polymerization regulator (for example, 2,4-diphenyl-4-methyl-1-pentene). A prepolymer was obtained by heating and mixing the system to obtain a prepolymer. The prepolymer was added to a polymerization inhibitor (for example, methoxyphenol), [B] divinylbenzene (remainder), and an ultraviolet absorber. And a method of adding and mixing the component [C] if necessary.

In the above step, the reaction temperature of the thiourethane reaction is usually 20 to 120 ° C., preferably 30 to 80 ° C. In the above steps, it is not necessary that all of the polythiol (a ¹ ) and the polyisocyanate (a ² ) react,
It may be contained in the monomer mixture together with the component (A).

The above-mentioned step (preliminary polymerization) is an optional thickening step carried out to obtain a monomer mixture having a viscosity in a preferable range (for example, 40 to 200 cp), and the viscosity can be imparted. When the component [A] and [B] divinylbenzene are mixed and the mixture has a viscosity within a suitable range, this step need not be performed.
In addition, this preliminary polymerization can also be performed only by heating the system without using a polymerization initiator.

The synthetic resin lens of the present invention comprises a radical polymerization initiator added to the above monomer mixture comprising the components [A] and [B] divinylbenzene as essential components and the component [C] and various additives as optional components. To obtain a monomer composition,
The monomer composition can be produced by performing a polymerization treatment by a cast polymerization method. Here, in the casting polymerization method, a monomer composition is poured into a mold or a mold (mold) made of glass, plastic, or metal designed to obtain a lens having a desired shape and power. This is a method of polymerizing by raising the temperature.

Since the viscosity of the monomer mixture containing the component (A) is relatively high at 40 to 200 cp (25 ° C.), a monomer mixture obtained by adding a radical polymerization initiator to this monomer mixture is used. By subjecting the body composition to cast polymerization, the desired lens can be easily molded (molded).

Here, examples of the radical polymerization initiator include ordinary organic peroxide-based polymerization initiators.
Specifically, tert-butyl peroxy neodecanoate, tert-butyl peroxypivalate, ter
peroxyesters such as t-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxylaurate, tert-butylperoxy-3,5,5-trimethylhexanoate; Lauroyl peroxide, 3,5
Preferred examples include diacyl peroxides such as 5-trimethylhexanoyl peroxide and peroxyketals such as 1,1-bis (tert-butylperoxy) -3,5,5-trimethylcyclohexane. Also, azo radicals such as 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and 1,1′-azobis (cyclohexane-2-carbonitrile) Polymerization initiators are also preferred.

The synthetic resin lens obtained as described above can be used as it is, but may be subjected to grinding, polishing, dyeing, forming a hard coat layer, forming an anti-reflection layer, or the like. It is possible. The synthetic resin lens of the present invention has a high refractive index (for example, 1.58 or more,
Light dispersibility is low (for example, Abbe number is 30 or more, especially 31 or more). Further, the synthetic resin lens of the present invention has a low specific gravity (for example, 1.30 or less) and is excellent in transparency.

[0036]

The present invention will now be described by way of examples, which should not be construed as limiting the invention. In the following, “parts” means “parts by mass”.

Example 1 (1) Thiourethane-forming reaction: 62.8 parts of bismercaptoethyl sulfide [polythiol (a ¹ )] and 4,4-dicyclohexylmethane diisocyanate [poly Isocyanate (a ² )]
0.7 parts were charged into a reaction vessel, and this was mixed well at room temperature. After adding 0.05 parts of triethylamine (thiourethanation reaction catalyst) to this system, a thiourethanation reaction (reaction for producing the component [A]) was performed at 60 ° C. for 4 hours. Here, when the number of moles of thiol groups in bismercaptoethyl sulfide is [SH] and the number of moles of isocyanate groups in 4,4-dicyclohexylmethane diisocyanate is [NCO], the molar ratio ([S
H] / [NCO]) is 85.

(2) Prepolymerization reaction: 37.4 parts of divinylbenzene and 2,4-diphenyl-4-
0.2 parts of methyl-1-pentene (polymerization regulator) and 2,
2'-azobis (2,4-dimethylvaleronitrile)
(Radical polymerization initiator) was added, and the system was stirred and mixed at 55 ° C. for 2 hours to perform a preliminary polymerization reaction.

(3) Preparation of monomer mixture: After the completion of the prepolymerization reaction, 0.08 parts of methoxyphenol (polymerization inhibitor), 10.0 parts of divinylbenzene, and 2- (2'-hydroxy-5 ') -Tert-octylphenyl) benztriazole (ultraviolet absorber) (0.25 parts) was added thereto, followed by stirring and mixing to prepare a monomer mixture having a viscosity of 70 cp (25 ° C). In the obtained monomer mixture, when the number of moles of the thiol group of the component (A) is a and the number of moles of the vinyl group of divinylbenzene is b,
The value of (b / a) was 2.06.

(4) Production of lens: 0.6 part of tert-butyl peroxybenzoate (radical polymerization initiator) was added to this monomer mixture, and the mixture was stirred and mixed to prepare a monomer composition. . The joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold. And inject
After maintaining at 50 ° C. for 8 hours, the temperature was raised to 95 ° C. over 4 hours, and further raised to 130 ° C. over 2 hours. 1
After maintaining at 30 ° C. for 1 hour, the glass mold was cooled to 70 ° C. and divided to obtain a colorless and transparent lens (the synthetic resin lens of the present invention). The refractive index of this lens was as high as 1.641, the Abbe number was 32, and the light dispersion was low. The specific gravity was 1.18, which was light.
The above results are shown in Table 2 below.

Example 2 (1) Thiourethane-forming reaction: According to the formulation shown in Table 1 below, 47.4 parts of bismercaptoethyl sulfide [polythiol (a ¹ )] and isophorone diisocyanate [polyisocyanate (a ² )] 15.0 parts was charged into a reaction vessel, and the mixture was thoroughly stirred and mixed at room temperature. After adding 0.05 part of N, N-dimethylaminocyclohexane (thiourethanation reaction catalyst) to this system, the thiourethanation reaction (formation reaction of component [A]) is performed at 70 ° C. for 4 hours.
Was done. Here, the number of moles of the thiol group of bismercaptoethyl sulfide is [SH], and the number of moles of the isocyanate group of isophorone diisocyanate is [N].
CO], the value of the molar ratio ([SH] / [NCO]) is 3.6.

(2) Prepolymerization reaction: 47.4 parts of divinylbenzene and 2,4-diphenyl-4-
0.2 parts of methyl-1-pentene (polymerization regulator),
1-bis (tert-butylperoxy) -3,5,5
-Trimethylcyclohexane (radical polymerization initiator)
0.01 part was added, and this system was stirred and mixed at 55 ° C. for 13 hours to perform a prepolymerization reaction.

(3) Preparation of monomer mixture: After completion of the prepolymerization reaction, 0.05 parts of methoxyphenol (polymerization inhibitor) and 2- (2'-hydroxy-5'-tert-octylphenyl) benztriazole ( UV absorber) 0.2
5 parts were added and mixed with stirring to prepare a monomer mixture having a viscosity of 95 cp (25 ° C.). In the obtained monomer mixture, when the number of moles of the thiol group of the component [A] is a and the number of moles of the vinyl group of divinylbenzene is b, the value of (b / a) is 2.06. Was.

(4) Production of lens: 0.6 part of 2,2'-azobis (isobutyronitrile) (radical polymerization initiator) is added to this monomer mixture, and the mixture is stirred and mixed to obtain a single monomer. A body composition was prepared. The joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold. Was maintained at 50 ° C. for 8 hours, then heated to 95 ° C. over 4 hours, and further heated to 130 ° C. over 2 hours. After holding at 130 ° C. for 1 hour, the glass mold was cooled to 70 ° C. and divided to obtain a colorless and transparent lens (the synthetic resin lens of the present invention). The refractive index of this lens is 1.6
It was as high as 28, and the Abbe number was 34, indicating low light dispersion. The specific gravity was 1.19, which was light. The above results are shown in Table 2 below.

Example 3 (1) Thiourethane reaction: 39.1 parts of bismercaptoethyl sulfide [polythiol (a ¹ )] and bis (isocyanatomethyl) cyclohexane [polyisocyanate, according to the formulation shown in Table 1 below (A ² )]
3.9 parts were charged into a reaction vessel, which was well stirred and mixed at room temperature. After adding 0.05 part of N, N-dimethylaminocyclohexane (thiourethanation reaction catalyst) to this system, a thiourethanation reaction (a reaction for producing the component (A)) was performed at 70 ° C. for 4 hours. Here: When the number of moles of thiol groups in bismercaptoethyl sulfide is [SH] and the number of moles of isocyanate groups in bis (isocyanatomethyl) cyclohexane is [NCO], the molar ratio ([SH] / [NCO] ) Is 12.
6.

(2) Prepolymerization reaction: 47.0 parts of divinylbenzene, 2,4-diphenyl-4-
0.2 parts of methyl-1-pentene (polymerization regulator),
1-bis (tert-butylperoxy) -3,5,5
-Trimethylcyclohexane (radical polymerization initiator)
0.01 part was added, and the system was stirred and mixed at 55 ° C. for 15 hours to perform a prepolymerization reaction.

(3) Preparation of monomer mixture: After completion of the prepolymerization reaction, 0.05 parts of methoxyphenol (polymerization inhibitor), 10.0 parts of divinylbenzene, and 2- (2'-hydroxy-5 ') -Tert-octylphenyl) benztriazole (ultraviolet absorber) 0.25 parts, and 1- (2-
(3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -4- (3-
0.23 parts of (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy) -2,2,6,6-tetramethylpiperidine are added, and the mixture is stirred and mixed to obtain a viscosity of 130 cp ( (25 ° C.). In the obtained monomer mixture, [A]
When the number of moles of the thiol group of the component is a and the number of moles of the vinyl group of divinylbenzene is b, (b / a)
Was 1.88.

(4) Production of lens: 0.5 part of tert-butyl peroxybenzoate (radical polymerization initiator) was added to this monomer mixture, and this was stirred and mixed to prepare a monomer composition. . The joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold. And inject
After maintaining at 50 ° C. for 8 hours, the temperature was raised to 95 ° C. over 4 hours, and further raised to 130 ° C. over 2 hours. 1
After maintaining at 30 ° C. for 1 hour, the glass mold was cooled to 70 ° C. and divided to obtain a colorless and transparent lens (the synthetic resin lens of the present invention). The refractive index of this lens was as high as 1.640, the Abbe number was 33, and the light dispersion was low. The specific gravity was 1.19, which was light.
The above results are shown in Table 2 below.

Example 4 (1) Thiourethane Formation Reaction: According to the formulation shown in Table 1 below, p- (7-mercapto-2,5-dithiaheptyl)
57.5 parts of benzene [polythiol (a ¹ )] and 5.7 parts of bis (isocyanatomethyl) cyclohexane [polyisocyanate (a ² )] were charged into a reaction vessel,
This was well stirred and mixed at room temperature. After 0.1 part of triethylamine (thiourethanation reaction catalyst) was added to this system, the thiourethanation reaction ([A]) was carried out at 55 ° C. for 6 hours.
Component formation reaction). Here, when the number of moles of the thiol group of p- (7-mercapto-2,5-dithiaheptyl) benzene is [SH] and the number of moles of the isocyanate group of bis (isocyanatomethyl) cyclohexane is [NCO], Molar ratio ([SH] / [NC
O]) is 4.7.

(2) Preliminary polymerization reaction: 36.8 parts of divinylbenzene and 2,4-diphenyl-4-
0.2 parts of methyl-1-pentene (polymerization regulator) and 2,
2'-azobis (2,4-dimethylvaleronitrile)
(Radical polymerization initiator) was added, and the system was stirred and mixed at 54 ° C. for 2 hours to perform a preliminary polymerization reaction.

(3) Preparation of monomer mixture: After completion of the prepolymerization reaction, 0.08 parts of methoxyphenol (polymerization inhibitor) and 2- (2'-hydroxy-5'-tert-octylphenyl) benztriazole ( UV absorber) 0.2
5 parts and 1- (2- (3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -4- (3- (3,5-ditert-butyl-4)
-Hydroxyphenyl) propionyloxy) -2,
0.26 parts of 2,6,6-tetramethylpiperidine was added, and the mixture was stirred and mixed to give a viscosity of 60 cp (2
(5 ° C.). In the obtained monomer mixture, when the number of moles of the thiol group of the component [A] is a and the number of moles of the vinyl group of divinylbenzene is b, the value of (b / a) is 2.56. Was.

(4) Production of lens: 0.5 part of tert-butyl peroxybenzoate (radical polymerization initiator) was added to this monomer mixture, and the mixture was stirred and mixed to prepare a monomer composition. . The joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold. And inject
After maintaining at 50 ° C. for 8 hours, the temperature was raised to 95 ° C. over 4 hours, and further raised to 130 ° C. over 2 hours. 1
After maintaining at 30 ° C. for 1 hour, the glass mold was cooled to 70 ° C. and divided to obtain a colorless and transparent lens (the synthetic resin lens of the present invention). This lens had a high refractive index of 1.650, an Abbe number of 31, and a low light dispersion. The specific gravity was as light as 1.22.
The above results are shown in Table 2 below.

Example 5 (1) Thiourethane-forming reaction: According to the formulation shown in Table 1 below, 45.5 parts of bis (mercaptoethylthio) ethane [polythiol (a ¹ )] and isophorone diisocyanate [polyisocyanate ( a ² )] was placed in a reaction vessel, and the mixture was well stirred and mixed at room temperature. After adding 0.05 part of N, N-dimethylaminocyclohexane (thiourethanation reaction catalyst) to this system, the thiourethanation reaction (formation reaction of component [A]) is performed at 70 ° C. for 4 hours.
Was done. Here, when the number of moles of the thiol group of bis (mercaptoethylthio) ethane is [SH] and the number of moles of the isocyanate group of isophorone diisocyanate is [NCO], the molar ratio ([SH] / [NC
O]) is 10.

(2) Preliminary polymerization reaction: 50.0 parts of divinylbenzene and 2,4-diphenyl-4-
0.2 parts of methyl-1-pentene (polymerization regulator) and 2,
2'-azobis (2,4-dimethylvaleronitrile)
(Radical polymerization initiator) was added, and the system was stirred and mixed at 54 ° C. for 2 hours to perform a preliminary polymerization reaction.

(3) Preparation of monomer mixture: After completion of the prepolymerization reaction, 0.08 parts of methoxyphenol (polymerization inhibitor) and 2- (2'-hydroxy-5'-tert-octylphenyl) benztriazole ( UV absorber) 0.2
5 parts were added and mixed with stirring to prepare a monomer mixture having a viscosity of 80 cp (25 ° C.). In the obtained monomer mixture, when the number of moles of the thiol group of the component [A] is a and the number of moles of the vinyl group of divinylbenzene is b, the value of (b / a) is 2.0. Was.

(4) Production of lens: 0.6 part of 2,2'-azobis (isobutyronitrile) (radical polymerization initiator) was added to this monomer mixture, and the mixture was stirred and mixed to obtain a single monomer. A body composition was prepared. The joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold. Was maintained at 50 ° C. for 8 hours, then heated to 95 ° C. over 4 hours, and further heated to 130 ° C. over 2 hours. After holding at 130 ° C. for 1 hour, the glass mold was cooled to 70 ° C. and divided to obtain a colorless and transparent lens (the synthetic resin lens of the present invention). The refractive index of this lens is 1.6
It was as high as 41, and the Abbe number was 33 with low light dispersion. The specific gravity was 1.19, which was light. The above results are shown in Table 2 below.

<Example 6> (1) Thiourethane reaction: 31.2 parts of pentaerythritol tetrakis (thiopropionate) [polythiol (a ¹ )] and m-xylylene diisocyanate were prepared according to the formulation shown in Table 1 below. [Polyisocyanate (a ² )] 6.0 parts, divinylbenzene 20.0 parts, and 2,4-diphenyl-4-methyl-1-pentene (polymerization regulator) 0.2 part in a reaction vessel. It was charged and mixed well at room temperature. After adding 0.03 part of triethylamine (thiourethanation reaction catalyst) to this system,
The thiourethanation reaction (reaction for producing the component (A)) was performed at room temperature for 30 minutes and further at 60 ° C. for 3 hours. Here, when the number of moles of the thiol group of bis (mercaptoethylthio) ethane is [SH] and the number of moles of the isocyanate group of isophorone diisocyanate is [NCO], the molar ratio ([SH] / [NCO]) Is 4.

(2) Preliminary polymerization reaction: After cooling this production system to room temperature, 27.8 parts of divinylbenzene was added to 2,2
2'-azobis (2,4-dimethylvaleronitrile)
(Radical polymerization initiator) was added, and the system was stirred and mixed at 54 ° C. for 2 hours to perform a preliminary polymerization reaction.

(3) Preparation of monomer mixture: After completion of the prepolymerization reaction, 0.08 parts of methoxyphenol (polymerization inhibitor) and 2,2-bis (4-methacryloxyethoxyphenyl) propane ([C] Component) 15.0 parts and 2- (2 ′
-Hydroxy-5'-tert-octylphenyl) benztriazole (ultraviolet absorber) (0.25 parts), and the mixture was stirred and mixed to give a viscosity of 120 cp.
(25 ° C.) to prepare a monomer mixture. In the obtained monomer mixture, a represents the number of moles of the thiol group of the component [A], b represents the number of moles of the vinyl group of the divinylbenzene, and c represents the number of moles of the (meth) acryl group of the component [C]. , The value of (b / a) is 3.83, [(b +
c) / a] was 4.17.

(4) Production of lens: To this monomer mixture was added 1.0 part of tert-butylperoxy-2-ethylhexanoate (radical polymerization initiator), and the mixture was stirred and mixed to obtain a monomer. A body composition was prepared. The joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold. Was maintained at 45 ° C. for 8 hours, then heated to 80 ° C. over 4 hours, and further heated to 120 ° C. over 2 hours. After holding at 120 ° C. for 1 hour, the glass mold was cooled to 70 ° C. and divided to obtain a colorless and transparent lens (the synthetic resin lens of the present invention). The refractive index of this lens was as high as 1.595, the Abbe number was 32, and the light dispersion was low. The specific gravity was 1.19, which was light. The above results are shown in Table 2 below.

<Example 7> (1) Thiourethane reaction: 42.6 parts of pentaerythritol tetrakis (thiopropionate) [polythiol (a ¹ )] and meta-xylylene diisocyanate were prepared according to the formulation shown in Table 1 below. [Polyisocyanate (a ² )] 8.2 parts, divinylbenzene 28.4 parts, and 2,4-diphenyl-4-methyl-1-pentene (polymerization regulator) 0.2 part are charged in a reaction vessel. This was well stirred and mixed at room temperature. After adding 0.03 part of triethylamine (thiourethanation reaction catalyst) to this system,
The thiourethanation reaction (reaction for producing the component (A)) was performed at room temperature for 30 minutes and further at 60 ° C. for 3 hours. Here, when the number of moles of the thiol group of bis (mercaptoethylthio) ethane is [SH] and the number of moles of the isocyanate group of isophorone diisocyanate is [NCO], the molar ratio ([SH] / [NCO]) Is 4.

(2) Preparation of monomer mixture: After cooling this production system to room temperature, 2,2-bis (4-methacryloxyethoxyphenyl) propane ([C] component) 20.8
Part and 2- (2'-hydroxy-5'-tert-octylphenyl) benztriazole (ultraviolet absorber).
Then, 25 parts were added, and the mixture was stirred and mixed to prepare a monomer mixture having a viscosity of 90 cp (25 ° C.). In the obtained monomer mixture, a represents the number of moles of the thiol group of the component [A], b represents the number of moles of the vinyl group of the divinylbenzene, and c represents the number of moles of the (meth) acryl group of the component [C]. Then, the value of (b / a) is 1.67,
The value of [(b + c) / a] was 2.02.

(3) Production of lens: 1.0 part of tert-butylperoxy-2-ethylhexanoate (radical polymerization initiator) was added to the monomer mixture, and the mixture was stirred and mixed to obtain a monomer. A body composition was prepared. The joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and the monomer composition obtained as described above is placed in the cavity of the glass mold. Was maintained at 45 ° C. for 8 hours, then heated to 80 ° C. over 4 hours, and further heated to 120 ° C. over 2 hours. After holding at 120 ° C. for 1 hour, the glass mold was cooled to 70 ° C. and divided to obtain a colorless and transparent lens (the synthetic resin lens of the present invention). The refractive index of this lens was as high as 1.588, the Abbe number was 34, and the light dispersion was low. Further, the specific gravity was 1.21 and was light. The above results are shown in Table 2 below.

<Comparative Example 1> This is a comparative example in which no polyisocyanate (a ² ) is used and no preliminary polymerization is performed. According to the formulation shown in Table 1 below, divinylbenzene 5
2 parts, 48 parts of pentaerythritol tetrakis (thiopropionate), and 2- (2′-hydroxy-5′-
0.2 part of tert-octylphenyl) benztriazole (ultraviolet absorber) was charged into a reaction vessel, and this was mixed well by stirring to prepare a monomer mixture having a viscosity of 15 cp (25 ° C.). In the obtained monomer mixture, when the number of moles of the thiol group of pentaerythritol tetrakis (thiopropionate) is a and the number of moles of the vinyl group of divinylbenzene is b, (b /
The value of a) was 2.0.

To this monomer mixture was added 0.8 part of tert-butylperoxy-2-ethylhexanoate (radical polymerization initiator), and the mixture was stirred and mixed to prepare a monomer composition. . The joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and in the cavity of the glass mold,
The monomer composition obtained as described above was injected, and 45
After holding at 8 ° C. for 8 hours, the temperature was raised to 80 ° C. over 4 hours, and further raised to 120 ° C. over 2 hours.
The seal with the adhesive tape was broken, and the monomer composition leaked out of the glass mold. When the same operation was repeated 10 times in total, the monomer composition leaked out 7 times before the polymerization reaction was completed. In addition, for three of the ten times, the temperature was raised to 120 ° C.
, And cooled to 70 ° C. to divide the glass mold to obtain a lens. Observation of the obtained lenses revealed that each peripheral portion was clouded.

Comparative Example 2 This is a comparative example in which no polyisocyanate (a ² ) is used. According to the formulation shown in Table 1 below, 52 parts of divinylbenzene, 48 parts of pentaerythritol tetrakis (thiopropionate), and 2- (2′-hydroxy-5′-tert-octylphenyl) benztriazole (ultraviolet absorber) 0 .2
Were charged into a reaction vessel, and the mixture was well stirred and mixed.
After cooling the system, 2,2′-azobis (2,4-dimethylvaleronitrile) (radical polymerization initiator) 0.1
The mixture was stirred and mixed at 54 ° C. for 2 hours to carry out a prepolymerization reaction, thereby preparing a monomer mixture having a viscosity of 65 cp (25 ° C.). In the obtained monomer mixture, when the number of moles of the thiol group of pentaerythritol tetrakis (thiopropionate) is a and the number of moles of the vinyl group of divinylbenzene is b, (b /
The value of a) was 2.0.

To this monomer mixture was added 0.8 part of tert-butylperoxy-2-ethylhexanoate (radical polymerization initiator), and the mixture was stirred and mixed to prepare a monomer composition. . The joint between the male mold and the female mold constituting the glass mold is sealed with an adhesive tape having an acrylic resin-based adhesive layer, and in the cavity of the glass mold,
The monomer composition obtained as described above was injected, and 45
After holding at 8 ° C. for 8 hours, the temperature was raised to 80 ° C. over 4 hours, and further raised to 120 ° C. over 2 hours. 120
After holding at 1 ° C. for 1 hour, it was cooled to 70 ° C. and the glass mold was divided to obtain a lens. Such operations are performed in total 1
By performing 0 times, ten lenses were obtained. Four of these lenses had poor surface quality because a part of the intermediate molded product was peeled off from the surface of the glass mold during the polymerization reaction (a wrinkle-like pattern was formed on the surface of the part peeled off during the polymerization). There has occurred. In addition, three of the ten lenses have a part thereof (a part corresponding to an inlet of the monomer composition).
Was cloudy.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

The lens of the present invention has a high refractive index and low light dispersion. Further, the lens of the present invention has a low specific gravity and is excellent in transparency. Further, the lens of the present invention can be easily molded (molded).
ADVANTAGE OF THE INVENTION According to the manufacturing method of this invention, when shape | molding by casting polymerization method, a sealing material does not elute or break, and as a result, an expected lens is easily molded (molded). Can be.

Claims (7)

[Claims] 1. A synthetic resin obtained by subjecting a monomer mixture comprising [A] a thiourethane compound having a thiol group and [B] divinylbenzene to radical polymerization and molding. lens. 2. [A] a thiourethane compound having a thiol group, [B] divinylbenzene, and [C] (meth)
A synthetic resin lens obtained by subjecting a monomer mixture containing an aromatic compound having two or more acrylic groups to radical polymerization and molding. 3. A method for converting a polythiol (a ¹ ) and a polyisocyanate (a ² ) into a polyisocyanate (a ² )
Of the number of moles of thiol groups of the polythiol (a ¹ ) to the number of moles of isocyanate groups of
[H] / [NCO]) are reacted at a ratio of 1 or more to obtain [A] a thiourethane compound having a thiol group, and [A] a thiourethane compound having a thiol group;
[B] A method for producing a synthetic resin lens, comprising preparing a monomer mixture containing divinylbenzene and injecting the monomer mixture into a mold and subjecting the mixture to radical polymerization to mold. 4. A method for converting a polythiol (a ¹ ) and a polyisocyanate (a ² ) into a polyisocyanate (a ² )
Of the number of moles of thiol groups of the polythiol (a ¹ ) to the number of moles of isocyanate groups of
[H] / [NCO]) are reacted at a ratio of 1 or more to obtain [A] a thiourethane compound having a thiol group, and [A] a thiourethane compound having a thiol group;
[B] A monomer mixture containing divinylbenzene and [C] an aromatic compound having two or more (meth) acryl groups is prepared, and the monomer mixture is injected into a mold to form a radical mixture. A method for producing a synthetic resin lens, characterized by forming by polymerization. 5. The method for producing a synthetic resin lens according to claim 3, wherein a prepolymerization of the monomer mixture is performed to increase the viscosity, and then the mixture is injected into a mold. 6. A monomer mixture containing polythiol (a ¹ ), polyisocyanate (a ² ) and [B] divinylbenzene is prepared, and the monomer mixture is injected into a mold. Molding by thiourethanation reaction and radical polymerization. 7. A polythiol (a ¹ ), a polyisocyanate (a ² ), [B] divinylbenzene, and [C]
A monomer mixture containing an aromatic compound having two or more (meth) acryl groups is prepared, and this monomer mixture is injected into a mold, and molded by thiourethane reaction and radical polymerization. A method of manufacturing a synthetic resin lens.