JPH10114825A - Composition for optical resin and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polymerizable compsn. for an optical resin which can be polymerized at a high rate and gives a resin having high refractive index and Abbe number and excellent in transparency and optical homogeneity. SOLUTION: This compsn. contains 10-50wt.% thiourethane compd. (A) obtd. by reacting a trifunctional or higher polythiol compd. having sulfide bonds in the molecule with a polyisocyanate compd. in a molar ratio of -SH/-NCO of 3.0-7.0, 35-70wt.% at least one difunctional or higher (meth)acrylate compd. (B), and 5-30wt.% compd. (C) free-radical-polymerizable with ingredients A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a high refractive index,
The present invention relates to a composition for an optical resin that gives a resin having a well-balanced transparency, optical strain, heat resistance, dyeability, impact resistance, and the like, an optical resin obtained by polymerizing and curing the composition, and an optical lens.

[0002]

2. Description of the Related Art At present, thermosetting optical resins and their monomers, which are practically used for eyeglass lenses, are roughly classified into two types. One is a polycondensation type represented by a thiourethane resin, and the other is a radical type represented by an acrylic or vinyl compound. Thiourethane resin has high refraction, excellent impact resistance,
It is widely used as an optical resin mainly for eyeglass lenses. However, in order to produce a resin by forming a urethane bond by a condensation reaction between a thiol and an isocyanate, and to carry out polymerization while maintaining optical uniformity, for example, a long time such as 24 hours or more is required. . Therefore, it is considered that the sulfur-containing urethane resin is excellent in performance as a resin, but still has room for improvement in productivity.

On the other hand, a (meth) acrylate resin is excellent in productivity because a monomer can be polymerized at a high speed by a radical reaction. However, from the viewpoint of the physical properties of the resin, it has a fatal disadvantage of inferior impact resistance, and can not significantly improve the refractive index except for the case where some thioacrylate is used. Absent. Similarly, a resin obtained by a polyene-polythiol reaction has one aspect of high productivity because a monomer can be polymerized at a high speed by a radical reaction. But,
It also has disadvantages such as a large volume shrinkage at the time of curing (during polymerization) and difficulty in precise casting polymerization. Also, in view of the physical properties of the resin, it is generally brittle, so that its use is naturally limited. In addition, in order to improve the refractive index of the resin, the content of thiol in the monomer must be increased, but as the content of the thiol compound is increased, the resin obtained by polymerization becomes more rubbery. It cannot be used for optical products.

That is, it can be said that a thiourethane resin excellent in physical properties has a problem in productivity, and a radical polymerization type resin having high productivity has problems in physical properties. Several techniques have been reported to combine urethane bonds and radical polymerization of polyene, (meth) acrylate or thiol in order to achieve both the productivity (high-speed polymerization) and physical properties of this resin. For example, Japanese Patent Publication No. 63-29692 discloses that to solve the problems of brittleness of a resin comprising only a polyene compound and volume shrinkage during polymerization, a prepolymer obtained from a polythiol compound and a polyisocyanate and a polyene compound are used. Contained polymerizable compositions have been proposed. However, this composition mainly provides a casting material for electronic applications, and there is no description about optical applications, and it is difficult to use as a high refractive index optical resin required to be optically uniform. . For example, if tolylene diisocyanate is used among the isocyanates exemplified in the publication, light resistance is insufficient, and if other aromatic isocyanates are used, the Abbe number is insufficient, and hexamethylene diisocyanate is used. The refractive index becomes low because of the above, and also when the mercapto carboxylic acid ester which is recommended and optimal in the publication is used for the thiol compound, the refractive index becomes low, and to realize a high refractive index optical resin. There's a problem.

[0005] Further, the equivalent ratio of SH group to NCO group is described only as 1.5 to 50, and no special consideration is found. However, this equivalence ratio is an important parameter that affects the properties of the prepolymer, and requires strict control. That is, if this ratio is too small, the resulting prepolymer will have an extremely high viscosity and cannot be mixed with other polyene compounds, and if it is too large, a sufficient prepolymer effect cannot be obtained. Further, it is described that the ratio of excess SH groups to unsaturated groups is generally 1: 1. However, if the unsaturated groups are not excessively excessive, the obtained resin tends to be rubbery. Therefore, when a prepolymerized thiol is used for the production of an optical resin, this excess SH
Sufficiently appropriate values must also be selected for the ratio of groups to unsaturated groups. As a result, unless an appropriate monomer compound and its ratio are selected, an optical resin having a high refractive index and a high Abbe number and excellent in hardness and impact resistance cannot be obtained.

Further, Japanese Patent Application Laid-Open No. 63-199210,
JP-A-63-207805 discloses the production of an optical resin by radical polymerization of a polyene compound having a urethane bond and a polythiol compound. But in general,
In the reaction between polyene and polythiol, when the ratio of polythiol is increased, the obtained resin tends to easily become rubbery. Therefore, if it is desired to obtain a resin having sufficient strength by reacting a polythiol with a polyene compound containing a urethane bond, the proportion of the polythiol in the entire resin must be suppressed to a considerably low level. Thus, the resulting resin has a low sulfur content and a high refractive index resin (refractive index about 1.
It is difficult to realize 6).

On the other hand, JP-A-5-25240 discloses that
A composition for a high refractive index optical resin comprising a mixture of a polyisocyanate and a polythiol and a radically polymerizable unsaturated compound is disclosed. However, the publication does not give any consideration to the importance of prepolymerization. This is clear from the fact that the impact resistance of the obtained resin is as low as 21 g to 31 g (drop test). In order to obtain a sufficient prepolymerization effect, it is not sufficient to simply mix the polyisocyanate and the polythiol, and clear conditions must be selected for the reaction between the SH group and the NCO group. Further, the ratio of SH group to NCO group is 0.5 to
However, if sufficient prepolymerization is performed at this ratio, the resulting prepolymer has an extremely high viscosity, and it is difficult to mix with the compound having an unsaturated polymerizable group thereafter. Therefore, inevitably, the composition must be judged as a mere mixture of isocyanate, thiol, and a monomer having an unsaturated group.

In this case, the composition must be cured by simultaneously performing radically different types of reactions, ie, radical reaction and urethane condensation. Therefore, in order to always maintain a constant urethane bond ratio in the resin obtained by polymerization, it is essential to strictly control the polymerization reaction. That is, depending on the polymerization conditions, the urethane bond forming reaction that is slow in reaction is left behind, and the SH group is consumed first by radical addition. As a result, there is a concern that unreacted isocyanate remains in the resin. If the isocyanate group remains, serious problems such as a health problem of a resin cutting operator and an influence on post-processing of the lens (uneven coating and dyeing) occur. Also, due to the slight amplitude of polymerization conditions,
It is conceivable that the abundance ratio of chemical bonds in the resin also varies. That is, if the control of the polymerization conditions is insufficient, there is a concern that the physical properties of the resin product may vary. In addition, since different reactions proceed simultaneously during polymerization, it is necessary to pay sufficient attention to optical distortion and optical nonuniformity of the resin obtained by polymerization. In addition, a release agent is also required for performing a urethane condensation reaction during the casting polymerization.

Further, JP-A-7-228659 discloses a polymerizable composition comprising a mixture of a polythiol and a polyisocyanate, and a compound having both a hydroxyl group or a mercapto group and an unsaturated group such as (meth) acryl in one molecule. Is disclosed. If a polythiol having a high sulfur content as exemplified here is used, it is possible to obtain a high refractive index resin. However, no clear prepolymerization is proposed in this publication, and there is a need to strictly control the polymerization reaction. Further, since the monomer having an unsaturated bond group has a thiol group or a hydroxyl group at the same time, the heat resistance of the resin is increased, but the dyeability tends to be reduced.

[0010]

The object of the present invention is to provide (1)
Polymerization can be performed in a short time by heating or light, and high productivity of resin can be achieved. (2) High refractive index, excellent transparency, heat resistance, dyeability, impact resistance, optical distortion and (3) To easily produce a lens with stable quality and little residual monomer. That is, an object of the present invention is to provide an optical resin excellent in physical properties and excellent productivity, an optical resin composition therefor, and a lens using the same.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, a component obtained by prepolymerizing a polythiol compound having a specific structure with a polyisocyanate compound, a specific structure A resin obtained by polymerizing and curing a component comprising a component comprising a (meth) acrylate compound and a component comprising a compound copolymerizable therewith is suitably used as a high refractive index optical resin. The present inventors have found that the resin is suitable for an optical lens, and that the composition can be cured in a short time by heating or photopolymerized by ultraviolet rays, and have reached the present invention.

That is, the present invention relates to the following A component:
The present invention relates to a composition for an optical resin which contains about 50% by weight, 35 to 70% by weight of a component B, and 5 to 30% by weight of a component C. Component A: thiourethane obtained by reacting a polythiol compound having a sulfide bond in the molecule with a trifunctional or higher functional compound and a polyisocyanate compound in a molar ratio of -SH / -NCO of 3.0 to 7.0. Prepolymer compound, B component: at least one bifunctional or higher (meth) acrylate compound, C component: a compound capable of radical copolymerization with A component and B component

In the present invention, the polythiol compound used in the preparation of the component A may be represented by the following formula (1) or (2):
A composition for an optical resin, which is a compound represented by the following formula (4):
The present invention relates to an optical resin composition in which the component B contains a compound represented by the general formula (3) (Formula 5).
Still further, the present invention provides a method wherein the C component is divinylbenzene,
Optical resin composition which is any one of diisopropenylbenzene, styrene, nuclear-substituted styrene, and monofunctional (meth) acrylate compound, refractive index (nd) 1.58 or more obtained by polymerizing and curing the above various compositions And a high refractive index optical resin having the following.

[0014]

Embedded image

[0015]

Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents —CH ₂ —, —C (CH ₃ ) ₂ — or —SO ₂ —,
m and n each represent an integer of 0 to 4;
Is)

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The composition for an optical resin of the present invention comprises, as Component A, a tri- or more functional polythiol compound having a sulfide bond in the molecule and a polyisocyanate compound, -SH / -NC
The thiourethane prepolymer compound obtained by reacting the O molar ratio in the range of 3.0 to 7.0 is 10 to 50% by weight,
As the B component, at least one kind of bifunctional or higher (meth)
It contains 35 to 70% by weight of an acrylate compound and 5 to 30% by weight of a compound capable of being radically copolymerized with Component A and Component B as Component C.

Since the polythiol compound used in the preparation of the component A is used as a thiourethane prepolymer compound, the polythiol compound preferably has a high refractive index and a low viscosity, and ensures the heat resistance of the obtained resin. To 3
It is preferably a functional or higher polythiol compound.
As a polythiol compound suitable for this purpose, a polythiol compound having three or more functional groups whose refractive index is increased by a sulfide bond in the molecule is suitably used. For example, 2
-Mercapto-3-thiahexane-1,6-dithiol, 5,5-bis (mercaptomethyl) -3,7-dithianonane-1,9-dithiol, 2,4,5-tris (mercaptomethyl) -1,3 -Dithiolane, 5- (2
-Mercaptoethyl) -3,7-dithianonane-1,9
-Dithiol, a compound represented by the formula (1) or (2), and a compound represented by the formula (1) or (2) is more preferably used.

The polythiol compound represented by the formula (1) can be easily produced by a method described in JP-A-2-270859, that is, a method of reacting epihalohydrin with 2-mercaptoethanol and then reacting thiourea. Is done. Further, the polythiol compound represented by the formula (2) can be prepared by the method described in JP-A-7-252207,
That is, epichlorohydrin and 2-mercaptoethanol are reacted, and the obtained diol form is further reacted with sodium sulfide to obtain a tetraol form. Then, the tetraol form is reacted with thiourea in hydrochloric acid to obtain ammonia water. Easily produced by the method of hydrolysis in

The polyisocyanate compound used in the preparation of the component A can be used without any particular limitation as long as it has two or more isocyanate groups capable of reacting with a thiol group in the molecule. Specifically, hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXD
I), aliphatics such as isophorone diisocyanate (IPDI), hydrogenated XDI (H-XDI), hydrogenated MDI (H-MDI), norbornene diisocyanate (NBDI),
Examples thereof include alicyclic polyisocyanate, aromatic polyisocyanate such as 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), and trizine diisocyanate (TODI). In some cases, the isocyanate used here is modified after trimming or multiplying from the viewpoint of improving the physical properties of the final resin. Among these isocyanate compounds, aliphatic and alicyclic polyisocyanates are more preferably used from the viewpoint of the weather resistance and Abbe number of the obtained resin, and further considering the refractive index of the resin, XD
Most preferred are I, NBDI, TMXDI, H-MDI, and the like.

The component A is obtained by mixing the above-mentioned polythiol compound and polyisocyanate compound with a -SH / -NCO molar ratio of 3.0 to 7.0, preferably 3.5 to 6.5, more preferably 4.0. A thiourethane prepolymer compound obtained by reacting in the range of from 6.0 to 6.0. -SH / -N
When the molar ratio of CO is less than 3.0, the viscosity of the obtained prepolymer is too large and it is easy to handle, and in extreme cases, it may not be mixed with other monomer compounds or crystals may be generated. . Also, -SH / -N
When the molar ratio of CO is larger than 7.0, the concentration of thiourethane bonds contained in the prepolymer is too low, and the effect of the prepolymer tends not to be sufficiently exhibited in the final cured product. The reaction between the polythiol compound and the polyisocyanate compound is performed, for example, by a known urethane reaction. In that case, in an inert gas, dibutyltin dilaurate, tin-based such as dibutyltin dichloride, or,
N, N-dimethylcyclohexylamine, N, N-di-
It is preferable to carry out the reaction over a sufficient time by raising the reaction temperature to 40 ° C. or higher using a reaction catalyst such as an amine-based catalyst such as n-butylethanolamine and triethylamine.

The termination of the prepolymerization reaction is performed, for example, by collecting a part of the reaction product, measuring the integrated FT-IR spectrum until a sufficient sensitivity is obtained, and disappearing the absorption of the NCO group. Can be confirmed by the following method. Also, the equivalent number of free SH groups in the obtained prepolymer is as follows:
The accurately weighed prepolymer can be determined by a method in which the prepolymer is dissolved in an appropriate solvent and titrated with an iodine standard solution. The refractive index can be measured with an Abbe refractometer or the like.

The component B is capable of undergoing radical copolymerization, and
It is at least one bifunctional or higher functional (meth) acrylate compound to which a thiol group of a component is capable of radical addition. Here, the radical addition means a thiol addition reaction to an unsaturated bond of a polyene compound or a (meth) acrylic compound, and the radical copolymerization means an addition reaction between unsaturated bonds. Specifically, trimethylolpropane tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,1,3,3 , 5
5-hexa [(meth) acryloxy] cyclotriphosphogen, 1,1,3,3,5,5-hexa [(meth) acryloxyethylenedioxy] cyclotriphosphone, neopentylglycol di (meth) acrylate ,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) A) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and compounds represented by the following general formula (3) (formula 6). In consideration of the overall balance of physical properties of the obtained resin, the B component preferably contains a compound represented by the general formula (3).

[0023]

Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents —CH ₂ —, —C (CH ₃ ) ₂ — or —SO ₂ —,
m and n each represent an integer of 0 to 4;
Is)

The compound represented by the general formula (3) includes
Specifically, 2,2-bis [4- (meth) acryloxyphenyl] propane, 2,2-bis [4- (meth) acryloxyphenyl] methane, 2,2-bis [4- (meth) Acryloxyphenyl] sulfone, 2,2-bis [4- (meth) acryloxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloxyethoxyphenyl] methane, 2,2-bis [4- (Meth) acryloxyethoxyphenyl] sulfone, 2,2-bis [4- (meth) acryloxydiethoxyphenyl] propane, 2,2-bis [4- (meth) acryloxydiethoxyphenyl] methane, 2, 2-bis [4- (meth) acryloxydiethoxyphenyl] sulfone and the like.

The component C is not particularly limited as long as it is a compound which can be radically copolymerized with the components A and B. From the viewpoint of the viscosity of the monomer and the final refractive index of the resin, divinylbenzene, diisopropenylbenzene, styrene, nucleus-substituted styrene, monofunctional (meth) acrylate, and the like are preferable. Specifically, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, m-diisopropenylbenzene, p-diisopropenylbenzene, styrene, methylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene , Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth)
Acrylate, glycidyl (meth) acrylate, glycidyl allyl ether and the like can be exemplified, and among them, divinylbenzene is more preferably used.

The proportion of each of the components A, B, and C in the composition for an optical resin of the present invention is uniformly determined by the refractive index and viscosity of each component, and various physical properties of the obtained resin. But not in the range of 10 to 50% by weight of component A, 35 to 70% by weight of component B, 5 to 30% by weight of component C,
Preferably, the A component is 15 to 35% by weight and the B component is 45% by weight.
It is preferable to mix the C component in a range of 10 to 25% by weight. Further, in the composition for an optical resin of the present invention, as long as the effects of the present invention are not impaired, for example, an ultraviolet absorber, an antioxidant, an anti-yellowing agent, a bluing agent, a pigment, a dye, Various additives such as a coloring material and a release agent can be blended to exhibit desired physical properties and functions.

The high refractive index optical resin of the present invention is obtained by polymerizing and curing the composition for an optical resin of the present invention, and has a refractive index (n _d ) of 1.58 or more. The curing method is performed by, for example, cast polymerization using known radical polymerization. Specifically, for example, a radical generator such as a radical polymerization initiator and a photopolymerization initiator is added to the optical resin composition of the present invention, mixed well, filtered, and sufficiently removed under reduced pressure. After foaming, the mixture is injected into a mold to perform radical polymerization. The mold is composed of two mirror-polished molds via a gasket made of, for example, polyethylene, ethylene-vinyl acetate copolymer, vinyl chloride, or the like. Here, the mold includes a combination of glass and glass, glass and plastic plate, glass and metal plate, and the like. As the gasket, the above-mentioned soft thermoplastic resin may be used, or two molds may be fixed with a polyester adhesive tape or the like. The mold may be subjected to a release treatment or the like.

The radical generator in the thermal polymerization, that is, the radical polymerization initiator is not particularly limited, and known benzoyl peroxide, p-chlorobenzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-t-butyl peroxide are known. , 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, t
-Butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, t-butyl A peroxide such as peroxyisopropyl carbonate and an azo compound such as azobisisobutyronitrile are used. The mixture of one or more of these components is 0.005 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the total of the mixture of the component A, the component B, and the component C. Used in The polymerization temperature and the polymerization time for curing by the thermal polymerization method are determined by the radical polymerization initiator used, the size of the cured product, and the like.

The radical generator in the photopolymerization by ultraviolet rays, that is, the photopolymerization initiator is not particularly limited.
-Phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 1-
(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone,
2-methyl-1- [4- (methylthio) phenyl] -2
-Morpholino-1-propanone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, methyl 4-dimethylamino benzoate, p-dimethyl Isoamyl aminobenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothio Xanson, 2-
Methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 1-phenyl-1,2-propanedione-2 (o-ethoxycarbonyl) oxime, 2,4 , 6
Trimethylbenzoyldiphenyl phosphine oxide, methylphenylglyoxylate, benzyl, 9,
10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4''
-Diethylisophthalophenone, 3,3 ', 4,4'-
Tetra (t-butylperoxycarbonyl) benzophenone or the like is used. The mixture of one or more of these components is 0.005 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the total of the mixture of the component A, the component B, and the component C. Used in Further, the above-mentioned radical polymerization initiator may be used in combination with the photopolymerization initiator. Gamma-ray polymerization does not require a radical polymerization initiator or the like. After curing, after cooling,
The mold is released and the resin is removed. The removed resin is
If necessary, an annealing process for removing internal stress may be performed.

The optical lens of the present invention is obtained by polymerizing and curing the optical resin composition of the present invention in the same manner as described above, and has a refractive index (nd) of 1.58 or more. In addition,
The lens of the present invention may be manufactured by casting polymerization using a lens mold, or may be manufactured by a method of grinding a bulk optical resin obtained by polymerization and curing. In the case of casting polymerization, annealing may be performed after curing, if necessary. Further, the optical lens of the present invention, if necessary,
Physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coat treatment, and dyeing treatment can be performed to improve antireflection, impart high hardness, impart fashionability, and the like.

[0031]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto. All parts shown in the examples are parts by weight. Example,
In the comparative examples, the physical properties of the resin and the lens were evaluated by the methods described below. (1) Transparency: Observed visually, and those without color, turbidity or distortion were evaluated as good. (2) Refractive index, Abbe number: Measured by a Pulfrich refractometer. However, the refractive index of the prepolymer was measured using an Abbe refractometer. (3) Impact resistance: A ball having a center thickness of 1.5 mm was subjected to a falling ball (according to FDA standard) test using a steel ball of 67 g. (4) Heat resistance: TMA was measured by a penetration method, and those having a deformation point at 80 ° C or lower were evaluated as ×, and those at 80 ° C or higher as ○.
And (5) Dyeing property: In the dyeing bath, dyeing was performed simultaneously with diethylene glycol bisallyl carbonate resin, and those that were visually or equally dyed were evaluated as ○,
An inferior thing was evaluated as x.

Example 1 To 78.1 parts (0.300 mol) of the trithiol compound represented by the above formula (1), 21.9 parts of α, α, α ′, α′-tetramethylxylylene diisocyanate (01.9 parts) were added. .09
0 mol) was added and mixed. While stirring this, N, N
-0.1 part of dimethylcyclohexylamine was added and mixed at 40 ° C under a nitrogen atmosphere. The reaction temperature was raised to 60 ° C., and the mixture was stirred and reacted for 6 hours. As a colorless transparent viscous liquid, a thiourethane prepolymer compound (TUPP-
1) was obtained. When the IR spectrum of this compound was measured, it was confirmed that the absorption of the isocyanate group had disappeared and the reaction was completed. Also, about 5 g of this prepolymer was accurately weighed, and chloroform: methanol =
It was dissolved in 50 ml of a 1: 1 solution, and the free mercapto group was quantified by titration with a 1N standard iodine solution. The result was 7.2 meq / g. The refractive index of this prepolymer compound was 1.63.

Example 2 In Example 1, 78.1 parts of the trithiol compound was added to 80.7 parts (0.220 mol) of the tetrathiol compound represented by the formula (2), and α, α, α ′ , Α'-tetramethylxylylene diisocyanate was replaced with 19.3 parts (0.074 mol) of hydrogenated MDI in the same manner, and as a colorless transparent viscous liquid, a thiourethane prepolymer compound (TUPP-2) was used. ) Got. About 5 g of this prepolymer was accurately weighed, dissolved in 50 ml of a 1: 1 chloroform: methanol solution, and the free mercapto group was quantified by titration with a 1N standard iodine standard solution to give 7.3 meq / g. Was. The refractive index is 1.62
Met.

Example 3 To 78.2 parts (0.30 mol) of the trithiol compound represented by the formula (1), 0.1 part of dibutyltin dichloride was added and dissolved. With stirring, 20.8 parts (0.11 mol) of xylylene diisocyanate was added dropwise at 40 ° C. over 15 minutes under a nitrogen atmosphere. After completion of the dropwise addition, the reaction temperature was raised to 60 ° C., and the mixture was stirred and reacted for 6 hours to obtain a thiourethane prepolymer compound (TUPP-3) as a colorless transparent viscous liquid. I of this compound
When the R spectrum was measured, it was confirmed that the absorption of the isocyanate group had disappeared, and the reaction was completed. About 5 g of the prepolymer was accurately weighed, dissolved in 50 ml of a 1: 1 chloroform: methanol solution, and the free mercapto group was quantified by titration with a 1N iodine standard solution to give 6.9 meq / g. Was. The refractive index was 1.64.

Example 4 In Example 3, 78.2 parts of the trithiol compound was replaced with
76.5 tetrathiol compound represented by the formula (2)
Parts (0.21 mol) of xylylene diisocyanate 2
A thiourethane prepolymer compound (TUPP-4) was obtained in the same manner as described above, except that 0.8 part was replaced with 23.5 parts (0.09 mol) of hydrogenated MDI.
I got About 5 g of this prepolymer was accurately weighed, dissolved in 50 ml of a 1: 1 chloroform: methanol solution, and the free mercapto group was quantified by titration with a 1N iodine standard solution to give 6.6 meq / g. Was. The refractive index was 1.62.

Synthesis Example 1 In Example 1, 78.1 parts of the trithiol compound was added to 88.6 parts (0.181 mol) of pentaerythritol tetrakismercaptopropionate, and α, α, α ′,
α'-tetramethylxylylene diisocyanate 21.
9 parts of xylylene diisocyanate 11.4 parts (0.0
61 mol), and as a colorless transparent viscous liquid, a thiourethane prepolymer compound (TUP
P-5) was obtained. Also, about 5 g of this prepolymer was accurately weighed, and chloroform: methanol = 1: 1 solution 50 was used.
The resulting solution was dissolved in 1 ml of a solution, and the free mercapto group was quantified by titration with a 1N standard iodine solution. The result was 6.0 meq / g. Further, the refractive index was 1.58.

Synthesis Example 2 In Example 3, 78.2 parts of the trithiol compound was replaced with
To 86.7 parts (0.18 mol) of pentaerythritol tetrakismercaptopropionate, 20.8 parts of xylylene diisocyanate and 13.4 parts (0.07 mol)
The procedure is the same except that the colorless transparent viscous liquid is used.
A thiourethane prepolymer compound (TUPP-6) was obtained. About 5 g of this prepolymer was accurately weighed, dissolved in 50 ml of a 1: 1 chloroform: methanol solution, and the free mercapto group was quantified by titration with a 1N iodine standard solution to give 5.8 meq / g. Was. Also,
The refractive index was 1.58.

Example 5 The thiourethane prepolymer compound of Example 1 (TUPP
-1) 20.0 parts, 45.0 parts of 2,2-bis (4-acryloxydiethoxyphenyl) methane, 15.0 parts of trimethylolpropane trimethacrylate, and 20.0 parts of divinylbenzene are mixed well to form a radical. As a polymerization initiator, 0.2 parts of bis (4-t-butylcyclohexyl) peroxydicarbonate and 0.2 parts of t-butylperoxy-2-ethylhexanoate are added, mixed, defoamed, and used for an optical resin. A composition was obtained. This composition is composed of a glass mold and a gasket, having an outer diameter of 80 mm and a center thickness of 1.5 m.
m, into a concave lens mold with 10 mm edge thickness, 50
After raising the temperature from 130 ° C. to 130 ° C. for 3 hours, it was further heated and cured at 130 ° C. for 1 hour. After allowing to cool to room temperature, the lens was released from the glass mold to obtain a colorless and transparent concave lens. Table 1 (Table 1) shows the measurement results of the physical properties of the lens.

Example 6 The thiourethane prepolymer compound of Example 2 (TUPP
-2) 30.0 parts, 20.0 parts of 2,2-bis (4-acryloxydiethoxyphenyl) propane, 30.0 parts of tris (acryloxyethyl) isocyanurate and 20.0 parts of divinylbenzene are thoroughly mixed. Then, 0.2 parts of bis (4-t-butylcyclohexyl) peroxydicarbonate and t-butyl peroxy-
0.2 parts of 2-ethylhexanoate was added, mixed and defoamed to obtain a composition for an optical resin. This composition was prepared in Example 5
Curing was performed in the same manner as in the above to obtain a colorless and transparent concave lens. Table 1 shows the measurement results of the physical properties of the lens.

Example 7 The thiourethane prepolymer compound of Example 1 (TUPP
-1) 20.0 parts of 25.0 parts of 2,2-bis (4-acryloxydiethoxyphenyl) methane, 15.0 parts of triethylene glycol diacrylate, and 20.0 parts of divinylbenzene are mixed well to form a radical. 0.2 parts of lauroyl peroxide and 0.2 parts of t-butylperoxy-2-ethylhexanoate were added and mixed as a polymerization initiator,
Defoaming was performed to obtain a composition for an optical resin. This composition was cured in the same manner as in Example 5 to obtain a colorless and transparent concave lens. Table 1 shows the measurement results of the physical properties of the lens.

Example 8 The thiourethane prepolymer compound of Example 3 (TUPP
-3) 32.0 parts, tris (acryloyloxyethyl)
58.0 parts of isocyanurate, divinylbenzene
0 parts were mixed well, and 0.04 part of 2-hydroxy-2-methyl-1-phenylpropan-1-one was added as a photopolymerization initiator, mixed and defoamed to obtain a composition for an optical resin. Was. This composition was composed of two glass molds and a polyester pressure-sensitive adhesive tape, having an outer diameter of 80 mm and a center thickness of 1.
Inject into 5mm, concave lens mold with 10mm edge thickness,
80 w / cm high pressure mercury lamp light at a distance of 15 cm
Irradiated for minutes and cured. After cooling to room temperature, the adhesive tape was peeled off, and the lens was released from the glass mold to obtain a colorless and transparent concave lens. The results of the physical property measurement of this lens are shown in Table.
1 is shown.

Example 9 The thiourethane prepolymer compound of Example 3 (TUPP
-3) 33.0 parts, tris (acryloyloxyethyl)
57.0 parts of isocyanurate, 5.0 parts of ethylene glycol dimethacrylate, and 5.0 parts of divinylbenzene are mixed well, and 2-hydroxy-
2-methyl-1-phenylpropan-1-one 0.04
The resulting mixture was mixed and defoamed to obtain a composition for an optical resin. This composition was cured in the same manner as in Example 8 to obtain a colorless and transparent concave lens. The results of the physical property measurement of this lens are shown in Table.
1 is shown.

Example 10 The thiourethane prepolymer compound of Example 4 (TUPP
-4) 45.0 parts, 35.0 parts of trimethylolpropane triacrylate and 20.0 parts of divinylbenzene were mixed well, and 2-hydroxy-2 was used as a photopolymerization initiator.
0.04 parts of -methyl-1-phenylpropan-1-one was added, mixed, and defoamed to obtain a composition for an optical resin. This composition was cured in the same manner as in Example 8 to obtain a colorless and transparent concave lens. Table 1 shows the measurement results of the physical properties of the lens.
It was shown to.

Example 11 The thiourethane prepolymer compound of Example 3 (TUPP
-3) 20.0 parts, 2,2-bis (4-acryloxydiethoxyphenyl) methane 45.0 parts, ethylene glycol dimethacrylate 15.0 parts, divinylbenzene 2
0.0 part was mixed well, and 2 parts were added as a photopolymerization initiator.
-Hydroxy-2-methyl-1-phenylpropane-1
0.10 parts of -ON was added, mixed and defoamed to obtain a composition for an optical resin. This composition was cured in the same manner as in Example 8 to obtain a colorless and transparent concave lens. Table 1 shows the measurement results of the physical properties of the lens.

Comparative Example 1 The thiourethane prepolymer compound of Synthesis Example 1 (TUPP
-5) 30.0 parts, 20.0 parts of 2,2-bis (4-acryloxydiethoxyphenyl) propane, 30.0 parts of tris (acryloxyethyl) isocyanurate and 20.0 parts of divinylbenzene are thoroughly mixed. Then, 0.2 parts of bis (4-t-butylcyclohexyl) peroxydicarbonate and t-butyl peroxy-
0.2 parts of 2-ethylhexanoate was added, mixed and defoamed to obtain a composition for an optical resin. This composition was prepared in Example 5
Curing was performed in the same manner as in the above to obtain a colorless and transparent concave lens. Table 2 (Table 2) shows the measurement results of the physical properties of the lens.

Comparative Example 2 The thiourethane prepolymer compound of Example 1 (TUPP
-1) Curing was carried out in the same manner as in Example 5 except that 20.0 parts of the trithiol compound represented by the formula (1) was used instead of 20.0 parts, to obtain a colorless and transparent concave lens. Table 2 shows the measurement results of the physical properties of the lens.

Comparative Example 3 The thiourethane prepolymer compound of Example 1 (TUPP
-1) 20.0 parts were replaced with 15.6 parts (0.06 mol) of the trithiol compound represented by the formula (1), and α, α,
α ', α'-tetramethylxylylene diisocyanate 4.4 parts (0.018 mol), 2,2-bis (4-acryloxydiethoxyphenyl) methane 45.0 parts, trimethylolpropane trimethacrylate 15.0 And 20.0 parts of divinylbenzene, and 0.2 parts of bis (4-tert-butylcyclohexyl) peroxydicarbonate and 0.1 part of t-butylperoxy-2-ethylhexanoate as radical polymerization initiators. Two parts, 0.03 part of dibutyltin dichloride as a urethane reaction catalyst, and 0.1 part of dioctyl acid phosphate as an internal release agent were added, mixed and defoamed. This composition was cured in the same manner as in Example 5 to obtain a colorless and transparent concave lens. Table 2 shows the measurement results of the physical properties of the lens.

Comparative Example 4 The thiourethane prepolymer compound of Synthesis Example 2 (TUPP
-6) 45.0 parts, 35.0 parts of trimethylolpropane triacrylate, and 20.0 parts of divinylbenzene are mixed well, and 2-hydroxy-2 is used as a photopolymerization initiator.
0.04 parts of -methyl-1-phenylpropan-1-one was added, mixed, and defoamed to obtain a composition for an optical resin. This composition was cured in the same manner as in Example 8 to obtain a colorless and transparent concave lens. Table 2 shows the measurement results of the physical properties of the lens.
It was shown to.

Comparative Example 5 The thiourethane prepolymer compound of Example 3 (TUPP
-3) Curing was carried out in the same manner as in Example 8, except that 32.0 parts of the trithiol compound represented by the formula (1) was used instead of 32.0 parts, to obtain a colorless and transparent concave lens. Table 2 shows the measurement results of the physical properties of the lens.

Comparative Example 6 The thiourethane prepolymer compound of Example 3 (TUPP
-3) 30.0 parts and 70.0 parts of 2,2-bis [4- (methacryloyloxydiethoxy) phenyl] propane were mixed well, and 2-hydroxy-2-methyl was used as a photopolymerization initiator. -1-phenylpropan-1-one 0.0
4 parts were added, mixed and defoamed. This composition was prepared in Example 8
After curing in the same manner as described above, the pressure-sensitive adhesive tape was peeled off and cooled with water, but the resin was rubbery and did not release. Comparative Example 7 Trithiol Compound 26.1 Represented by Formula (1)
Parts, 6.9 parts of xylylene diisocyanate, 57.0 parts of tris (acryloyloxyethyl) isocyanurate,
5.0 parts of ethylene glycol dimethacrylate and 5.0 parts of divinylbenzene are well mixed, and 0.04 part of 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photopolymerization initiator is reacted with a urethane reaction. 0.03 part of dibutyltin dichloride as a catalyst and 0.1 part of dioctyl acid phosphate as an internal releasing agent were added, mixed and defoamed. After the composition was cured in the same manner as in Example 8, the adhesive tape was peeled off and the wedge was punched and released. The surface of the obtained lens was still soft. Table 2 shows the measurement results of the physical properties of the lens.

[0051]

[Table 1]

[0052]

[Table 2] Description of Table-1 and Table-2: The resin of Comparative Example 1 obtained by thermal polymerization using a prepolymer obtained from a thiocarboxylic acid ester type thiol has a lower refractive index than the resin of the present application and is insufficient. is there. The resin of Comparative Example 2 obtained by thermal polymerization using a trithiol compound directly without forming a prepolymer has insufficient heat resistance. In the resin of Comparative Example 3 obtained by thermal polymerization by simultaneously reacting an isocyanate compound, a thiol compound and a polyene compound,
Striae were confirmed, and heat resistance was insufficient. Also,
Similar results were obtained for the resins of Comparative Examples 4 to 7 obtained by photopolymerization. That is, the resin of Comparative Example 4 has an insufficient refractive index. The resin of Comparative Example 5 has insufficient heat resistance. The resin of Comparative Example 7 is insufficiently cured, and has insufficient impact resistance and heat resistance.

[0053]

The composition of the present invention is a resin composition which can be cured in a short time by heating or ultraviolet rays. By curing the composition, it has a high refractive index, transparency, optical distortion and heat resistance. It is an object of the present invention to provide an optical resin having an excellent balance of properties, dyeing properties, impact resistance and the like, and an optical lens having excellent performance.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masao Imai 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Kenichi Fujii 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Inside the corporation

Claims (11)

[Claims] 1. An optical resin composition comprising 10 to 50% by weight of the following component A, 35 to 70% by weight of component B, and 5 to 30% by weight of component C. Component A: thiourethane obtained by reacting a polythiol compound having a sulfide bond in the molecule with a trifunctional or higher functional compound and a polyisocyanate compound in a molar ratio of -SH / -NCO of 3.0 to 7.0. Prepolymer compound B component: At least one bifunctional or higher (meth) acrylate compound C component: Compound capable of radical copolymerization with A component and B component 2. The optical resin composition according to claim 1, wherein the polythiol compound as the component A is a compound represented by the following formula (1) or (2). Embedded image 3. The composition according to claim 1, wherein the component B contains a compound represented by the following general formula (3).
3. The composition for an optical resin according to item 1. Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents —CH ₂ —, —C (CH ₃ ) ₂ — or —SO ₂ —,
m and n each represent an integer of 0 to 4;
Is) 4. The optical resin according to claim 1, wherein the C component is any one of divinylbenzene, diisopropenylbenzene, styrene, nucleus-substituted styrene, and a monofunctional (meth) acrylate compound. Composition. 5. A high-refractive-index optical resin having a refractive index (n _d ) of 1.58 or more, obtained by polymerizing and curing the composition according to claim 1. 6. The high refractive index optical with claim refractive index, characterized in that the polymerization curing by photopolymerization with ultraviolet rays of the composition according to any one of claims 1~4 (n _d) 1.58 or more Method of manufacturing resin. 7. An optical lens having a refractive index (n _d ) of 1.58 or more obtained by polymerizing and curing the composition according to claim 1. 8. The refractive index (n _d ), wherein the composition according to claim 1 is injected into a lens mold and then polymerized and cured by photopolymerization using ultraviolet rays.
A method for producing an optical lens of 58 or more. 9. Thio obtained by reacting a polythiol compound having three or more functional groups having a sulfide bond in a molecule with a polyisocyanate compound in a molar ratio of -SH / -NCO in the range of 3.0 to 7.0. Urethane prepolymer compounds. 10. The polythiol compound represented by the following formula (1)
Or (2) a compound represented by the formula (3).
3. The thiourethane prepolymer compound according to item 1. Embedded image 11. The method according to claim 11, wherein the polyisocyanate compound is α,
The thiourethane prepolymer compound according to claim 9 or 10, which is at least one selected from α, α ', α'-tetramethylxylylene diisocyanate, xylylene diisocyanate, hydrogenated MDI and norbornene diisocyanate. .