KR100241989B1 - Thiourethane prepolymer compound - Google Patents

Abstract

The present invention relates to a thiourethane prepolymer compound obtained by reacting a trifunctional polythiol compound having a sulfide bond in a molecule and a polyisocyanate compound with a -SH / -NCO molar ratio in the range of 3.0 to 7.0. Since the compound has a high refractive index, it has a high refractive index and can be used as an optical purpose for the raw material of the composition for optical resins having excellent balance of transparency, optical deformation, heat resistance, dyeing resistance, impact resistance and the like.

Description

Thioethane prepolymer compound

The present invention relates to a thiourethane prepolymer compound which has a high refractive index and is used for optical purposes such as a raw material of an optical resin composition which imparts a balanced resin such as transparency, optical deformation, heat resistance, dyeing resistance and impact resistance.

At present, thermosetting optical resins and monomers thereof which have been put to practical use for spectacle lenses are classified into two types. One is of polycondensation type represented by thiourethane resin, and the other is of radical type represented by acryl and vinyl compound.

The thiourethane resin has advantages such as high refractive index and excellent impact resistance, and is widely used as an optical resin mainly for spectacle lenses. However, since a urethane bond is produced | generated by the condensation reaction of thiol and an isocyanate, and resin is manufactured, in order to superpose | polymerize, maintaining optical uniformity, long time, for example, 24 hours or more is required. Therefore, although sulfur-containing urethane resin is excellent in the performance as resin, it is considered that there is still room for improvement in productivity.

On the other hand, the (meth) acrylate resin is capable of high-speed polymerization of monomers by radical reaction, and thus has excellent productivity. However, in view of physical properties as a resin, not only does it have a fatal flaw in that impact resistance is inferior, but the refractive index cannot be improved much except when some thioacrylate is used. Similarly, the resin obtained by the polyene-polythiol reaction has one aspect of high productivity because the monomer can be polymerized at high speed by the radical reaction. However, it also has the drawback that the volume shrinkage rate at the time of curing (polymerization) is large and precise mold polymerization is difficult. Moreover, even in view of physical properties as a resin, since it is generally soft, the use is naturally limited. Moreover, in order to improve the refractive index of resin, the content rate of the thiol in a monomer must be increased, but when content of a thiol compound is increased, the resin obtained by superposition | polymerization will become rubbery shape and cannot be used as an optical product.

That is, it can be said that the thiourethane resin excellent in physical properties has a problem in terms of productivity, and the radical polymer type resin having high productivity remains in physical properties. In order to balance the productivity (high-speed polymerization) and the physical properties of this resin, there have been several reports of a method of combining a urethane bond with radical polymerization of polyene, (meth) acrylate or thiol. For example, Japanese Unexamined Patent Publication No. 62-29692 discloses a prepolymer obtained from a polythiol compound and a polyisocyanate, and a polyene compound in order to solve the problem of brittleness of the resin composed only of the polyene compound and the volume shrinkage during polymerization. The polymerizable composition to contain is proposed. However, this composition mainly provides a casting material for electronics, and it is difficult to use it as a high refractive index optical resin which requires no optical description and requires optical uniformity. For example, when tolylene diisocyanate is used in the isocyanate exemplified in this publication, light resistance is insufficient, when other aromatic isocyanate is used, Abbe number is insufficient, and when hexamethylene diisocyanate is used, the refractive index is lowered. In the case where the mercaptocarboxylic acid ester, which is recommended as the best among these publications, is used in the thiol compound, the refractive index is low, and there is a problem in realizing a high refractive index optical resin.

Moreover, only about 1.5-50 are described about the equivalence ratio of SH group and NCO group, and special consideration is not recognized. However, this equivalence ratio is an important parameter that determines the properties of the prepolymer and requires strict management. In other words, if the ratio is too small, the obtained prepolymer becomes very high in viscosity and cannot be mixed with other polyene compounds. If the ratio is too large, sufficient prepolymer effect cannot be obtained. In addition, although the ratio of excess SH group and unsaturated group is described as 1: 1, the obtained resin tends to become rubbery if the unsaturated group is not sufficiently excessive. Therefore, when the prepolymerized thiol is used for optical resin production, a value that is appropriate enough for the ratio of the excess SH group and the unsaturated group must be selected. As a result, unless an appropriate monomer compound and its ratio are selected, it is impossible to obtain an optical resin having high refractive index and high Abbe's number and excellent in hardness and impact resistance.

Japanese Patent Laid-Open Nos. 63-199210 and 63-207805 disclose the production of optical resins by radical polymerization of a polyene compound and a polythiol compound having a urethane bond. Generally, however, in polyene and polythiol reactions, when the ratio of polythiol is raised, the resin obtained tends to become rubbery. Therefore, if the polyene compound containing a urethane bond is made to react with polythiol, and the resin which has sufficient intensity | strength is obtained, the ratio of the polythiol which occupies for the whole resin must be suppressed considerably low. Therefore, sulfur content of resin obtained is low, and it is difficult to implement | achieve a high refractive index resin (refractive index about 1.6).

On the other hand, Japanese Patent Laid-Open No. 5-25240 discloses a composition for high refractive index optical resin composed of a mixture of polyisocyanate and polythiol and a radical polymerizable unsaturated compound. However, this publication does not consider the importance of prepolymerization at all. This is apparent even when the impact resistance of the obtained resin is 21 g to 31 g (falling test). In order to obtain sufficient prepolymerization effect, only mixing polyisocyanate and polythiol is insufficient, and clear conditions for reacting SH group and NCO group must be selected.

Moreover, although the ratio of SH group and NCO group is 0.5-2, if sufficient prepolymerization is performed at this ratio, the obtained prepolymer will become very high viscosity, and it will be difficult to mix with the compound which has a subsequent unsaturated polymerizable group. Do. Therefore, inevitably, this composition cannot be judged as a simple mixture of a simple isocyanate, a thiol, and a monomer having an unsaturated group. In this case, this composition must be cured by simultaneously performing radical reaction and completely different types of reactions called urethane condensation. Therefore, in order to always maintain the ratio of the urethane bond in resin obtained by superposition | polymerization, it is essential to strictly manage a superposition | polymerization reaction. In other words, depending on the polymerization conditions, the urethane bond generation reaction, which is slow in reaction, lags behind, and the SH group is consumed first by the 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 the health problems of the resin cutting process or the effect on the lens post-processing (coating or staining) occur.

In addition, it is considered that the abundance ratio of chemical bonds in the resin also varies depending on the amplitude of slight polymerization conditions. That is, when the management of polymerization conditions is insufficient, there is a concern that the physical properties of the resin product become uneven. In addition, since individual reaction advances simultaneously at the time of superposition | polymerization, it is necessary to pay sufficient attention also to the optical deformation and optical nonuniformity of resin produced by superposition | polymerization. Moreover, since a urethane condensation reaction is performed at the time of mold polymerization, a mold release agent is also needed.

Further, Japanese Patent Laid-Open No. 7-228659 discloses a polymerizable composition comprising a mixture of polythiol and polyisocyanate and a compound having both hydroxyl groups or unsaturated groups such as mercapto groups and (meth) acryl in one molecule. have. When polythiol having a high sulfur content exemplified here is used, it is possible to surely obtain a high refractive index resin. However, even in this publication, no clear prepolymerization has been proposed, and the necessity of tightly controlling the polymerization remains. Moreover, since the monomer which has an unsaturated bond group has a thiol group or a hydroxyl group at the same time, although heat resistance of resin becomes high, dyeability tends to fall.

An object of the present invention is to provide a high refractive index thiourethane prepolymer compound which has a high refractive index and is useful as a raw material for a composition for an optical resin having excellent balance of transparency, optical deformation, heat resistance, dyeing resistance, impact resistance and the like.

Moreover, using the said thiourethane prepolymer compound of this invention,

(1) It is possible to polymerize in a short time by heating or light, to enable high productivity of the resin,

(2) to produce a resin having high refractive index, excellent transparency, heat resistance, dyeing property and impact resistance, and having very little optical deformation or nonuniformity,

(3) To provide an optical resin that is easy to produce a lens with a stable quality and a low residual monomer, that is, excellent in physical properties and productivity, and an optical resin composition therefor and a lens using the same. It becomes possible.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors obtained the component obtained by prepolymerizing the polythiol compound of a specific structure with the polyisocyanate compound, and confirmed that this component is a high rate of reduction, A resin obtained by polymerizing and curing a composition comprising a component consisting of a (meth) acrylate compound having a specific structure and a component copolymerizable with them is suitably used as a high refractive index optical resin, and this resin is an optical lens. In addition, the present inventors have found that curing of the composition is possible for curing for a short time by heating or photopolymerization with ultraviolet rays.

That is, the present invention,

(1) a thiourethane prepolymer compound obtained by reacting a trifunctional polythiol compound having a sulfide bond in a molecule and a polyisocyanate compound with a -SH / -NCO molar ratio in the range of 3.0 to 7.0;

(2) the thiourethane prepolymer compound according to the above ①, wherein the polythiol compound is a compound represented by the following formula (1) or (2);

(3) The polyisocyanate compound according to the above (1) or (2), wherein the polyisocyanate compound is selected from the group consisting of α, α, α ', α'-tetramethylxylylene diisocyanate, xylylene diisocyanate, hydrogenated MDI and norbornene diisocyanate. It relates to a thiourethane prepolymer compound, characterized in that at least one.

Further, according to the present invention, additionally, 10 to 50% by weight of the thiourethane prepolymer compound (hereinafter referred to as A component), 35 to 70% by weight of the following B component and 5 to 30% by weight of the following C component are contained. Optical resin compositions can also be obtained:

Component B: at least one bifunctional (meth) acrylate compound.

Component C: A compound capable of radical copolymerization with component A and component B.

Since the thiourethane prepolymer compound of the present invention has a high refractive index, the optical resin composition using the raw material is a resin composition which can be cured in a short time by heating or ultraviolet rays, and by curing the composition, it has a high refractive index, transparency, It is possible to provide an optical lens having excellent balance of optical deformation, heat resistance, dyeing resistance, impact resistance, and the like and an excellent optical lens.

Hereinafter, the present invention will be described in detail.

The component A, which is the thiourethane prepolymer compound of the present invention, is obtained by reacting a trifunctional polythiol compound having a sulfide bond in a molecule with a polyisocyanate compound in the range of -SH / -NCO molar ratio of 3.0 to 7.0. will be.

Since the polythiol compound used in the preparation of A component is used as a thiourethane prepolymer compound, it is preferable that it is high refractive index and low viscosity, and in order to ensure the heat resistance of the obtained resin, it is a trifunctional polythiol It is preferable that it is a compound. As the polythiol compound suitable for this purpose, a trifunctional polythiol compound having an increased refractive index by sulfide bonds in a molecule is preferably 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, formula (1) or (2 The compound represented by) is mentioned, The compound represented by said Formula (1) or Formula (2) is used more suitably.

The polythiol compound represented by the formula (1) is prepared by the method described in JP-A-2-270859, that is, by reacting epihalohydrin and 2-mercaptoethanol and then reacting urea. It is easily manufactured.

Moreover, the polythiol compound represented by Formula (2) is sulfided with the method of Unexamined-Japanese-Patent No. 7-252207, ie, the diol body obtained by making epichlorohydrin and 2-mercaptoethanol react. A tetraol body is obtained by reacting with sodium, and this tetraol body is then easily produced by a method of reacting with thiourea in hydrochloric acid and hydrolyzing with aqueous ammonia.

Moreover, as long as the polyisocyanate compound used for preparation of A component is a compound which has two or more isocyanate groups which can react with a thiol group in a molecule | numerator, it can be used without a restriction | limiting in particular. Specifically, hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), α, α, α ', α'-tetramethyl xylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hydrogenated XDI (H-XDI), hydrogenated MDI (H-MDI), norbornene diisocyanate

Aliphatic, alicyclic polyisocyanates such as (NBDI), aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tridine diisocyanate (TODI), etc. Can be mentioned. The isocyanate used herein may be selected from modified substances such as trimerization or multimerization from the viewpoint of final improvement of physical properties of the resin.

Among these isocyanate compounds, aliphatic and cycloaliphatic polyisocyanates are more preferably used from the weather resistance of the resin obtained, Abbe's number, etc., and considering the refractive index of the resin, XDI, NBDI, TMXDI, H-MDI and the like are most suitable. .

The component A is a thiourethane prepolymer obtained by reacting the polythiol compound and the polyisocyanate compound with a -SH / -NCO molar ratio of 3.0 to 7.0, preferably 3.5 to 6.5, more preferably 4.0 to 6.0. Compound. When the molar ratio of -SH / -NCO is less than 3.0, the viscosity of the obtained prepolymer is too large to be difficult to handle, and in extreme cases, it may be impossible to mix with other monomer compounds or crystals may be generated. Moreover, when the molar ratio of -SH / -NCO is larger than 7.0, the concentration of thiourethane bonds contained in the prepolymer is too low, so that the effect of the prepolymer is not sufficiently expressed in the final cured product. Reaction of a polythiol compound and a polyisocyanate compound is performed by a well-known urethanation reaction, for example. In that case, tin system, such as dibutyltin dilaurate and dibutyltin dichloride, or N, N- dimethylcyclohexylamine, N, N-di-n-butylethanolamine, triethyl in an inert gas. It is preferable to carry out over a sufficient time by raising reaction temperature to 40 degreeC or more using reaction catalysts, such as amines, such as an amine.

The completion of the prepolymerization reaction can be confirmed, for example, by taking a portion of the reactant and measuring the integrated FT-IR spectrum until sufficient sensitivity is obtained, thereby losing the absorption of the NCO group. The equivalent number of free SH groups in the obtained prepolymer can be determined by dissolving the accurately weighed prepolymer in a suitable solvent and titrating with an iodine standard solution. In addition, the refractive index can be measured with an Abbe refractometer or the like.

The B component is at least one bifunctional (meth) acrylate compound capable of radical copolymerization and capable of radical addition of a thiol group of the A component. Here, radical addition means addition reaction of thiol to the unsaturated bond of a polyene compound or a (meth) acryl compound, and addition reaction of unsaturated bonds with radical copolymerization.

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] cyclotriphosphogen Neopentyl glycol 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-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, the following general formula ( The compound represented by 3), etc. are mentioned.

In consideration of the general physical property balance of the resin obtained, it is preferable that B component contains the compound represented by following General formula (3).

(Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents —CH ₂ —, —C (CH ₃ ) ₂ — or —SO ₂ —, and m and n each represent an integer of 0 to 4). M + n is 0 to 4).

Specifically as a compound represented by General formula (3), 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 C component is not particularly limited as long as it is a compound capable of radical copolymerization with the A component and the B component. From the viewpoint of the viscosity of the monomer and the refractive index of the final 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, methyl styrene, chloro styrene, dichloro styrene, bro Mostyrene, dibromostyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylic Elate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyl allyl ether, etc. can be illustrated, Especially, divinylbenzene is used more suitably.

The ratio of each component of A component, B component, and C component in the composition for optical resins which is one of the application examples of this invention can be determined uniformly according to the refractive index and viscosity of each component, the various physical properties of resin obtained, etc. None, but the range of 10 to 50% by weight of A component, 35 to 70% by weight of B component, and 5 to 30% by weight of C component, preferably 15 to 35% by weight of A component and 45 to 65% of B component. It is preferable to mix weight% and C component in 10-25 weight%. Moreover, the composition for optical resins, if necessary, in the range that does not impair the effects of the present invention, for example, UV absorbers, antioxidants, yellowing agents, bluing agents, pigments, dyes, functional colorants, release agents, etc. An additive can also be mix | blended and the desired physical property and function can be expressed.

The high refractive index optical resin which is one of the other application examples of this invention is obtained by superposing | polymerizing and hardening the said composition for optical resins, and has refractive index (nd) 1.58 or more.

The curing method is performed by, for example, casting polymerization using known radical polymerization. Specifically, for example, a radical generating agent such as a radical polymerization initiator and a photopolymerization initiator is added to the composition for the optical resin, mixed well, filtered, and sufficiently degassed under reduced pressure, and then injected into a mold. Perform radical polymerization.

The mold is composed of, for example, two mirror-polished molds via a gasket made of polyethylene, ethylene-vinyl acetate copolymer, vinyl chloride, or the like. Here, as the molds, there are combination molds such as glass and glass, glass and plastic plates, and glass and metal plates. As the gasket, in addition to using the above-mentioned soft thermoplastic resin, two molds may be fixed with a polyester adhesive tape or the like. Moreover, you may perform mold release process etc. to a mold.

The radical generator in thermal polymerization, ie, the radical polymerization initiator, is not particularly limited, and known benzoyl peroxide, p-chlorobenzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-t-butyl peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylperoxy pivalate, t-butylperoxy-2-ethylhexaneoate, t-butylperoxybenzoate And azo compounds such as peroxides such as bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, t-butylperoxyisopropylcarbonate and azobisisobutyronitrile. These 1 type, or 2 or more types of mixtures are 0.005-5 weight part with respect to a total of 100 weight part of the mixture of A component, B component, and C component, Preferably it is used in the ratio of 0.01-3 weight part. The polymerization temperature and the polymerization time in the case of curing by the thermal polymerization method are determined depending on the radical polymerization initiator used, the size of the cured product, and the like.

The radical generating agent in photopolymerization by ultraviolet-ray, ie, a photoinitiator, is not specifically limited, Well-known 4-phenoxydichloroacetophenone, 4-t-butyl- dichloro acetophenone, 4-t-butyl- trichloro Acetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl propane-1-one, 1- (4-isopropyl phenyl) -2-hydroxy-2-methylpropane- 1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl ) Ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]-2-morpholino-1-propanone, benzoin, benzoin methyl ether, benzoin ethyl Ether, benzoin propylether, benzoin butyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-dimethylaminobenzoic acid methyl, p-dimethylaminobenzoic acid isoamyl, 4-phenyl benzophenone, hydroxybenzo Paddy, 4,4'-diethylaminobenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-dichlorothioxanthone, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbone Carbonyl) oxime, 2,4,6-trimethylbenzoyldiphenylhispinoxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrequinone, camphorquinone, dibenzosuberon, 2-ethylanthraquinone, 4 ', 4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, etc. are used. These 1 type, or 2 or more types of mixtures are used in the ratio of 0.005-5 weight part, Preferably it is 0.01-3 weight part with respect to a total of 100 weight part of the mixture of A component, B component, and C component. Moreover, the radical polymerization initiator mentioned above can also be used together with the said photoinitiator.

In the polymerization by gamma rays, no radical polymerization initiator is required.

After the completion of curing, after cooling, the mold is released and the resin is taken out. The removed resin may be subjected to an annealing treatment to remove internal stress as necessary.

The optical lens which is another example of application of the present invention is obtained by polymerizing and curing the composition for optical resin in the same manner as above, and the refractive index (nd) is 1.58 or more. In addition, the said lens may be manufactured by casting-polymerizing using a lens mold, or may be manufactured by the method of grinding the bulk optical resin obtained by carrying out polymerization hardening. In the case of casting polymerization, an annealing treatment may be carried out as necessary after curing. In addition, the optical lens may be subjected to physical polishing such as surface polishing, antistatic treatment, hard coat treatment, anti-reflective coating treatment, and dyeing treatment, in order to improve reflection prevention, high hardness, or fashion impartment, as necessary. Or chemical treatment can be performed.

Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited at all by this. In addition, all the parts shown in the Example are a weight part. In Examples and Comparative Examples, physical property evaluation of the resin and the lens was performed by the method described below.

(1) Transparency: It observed visually and made it good that there was no color, haze, and deformation.

(2) Refractive index, Abbe's number: Measured by a Fleurich refractometer. However, the refractive index of the prepolymer was measured by the Abbe refractometer.

(3) Impact resistance: A lens having a center thickness of 1.5 mm was subjected to a test of falling ball (according to the FDA standard) using a 67 g steel ball, and the passed and the failed were made into x.

(4) Heat resistance: TMA by the penetration method was measured, and the thing with a strain point below 80 degreeC was made into (circle) and 80 degreeC or more.

(5) Dyeing: In the dyeing bath, dyeing was performed simultaneously with the diethylene glycol bisallylcarbonate resin, and the ones that were dyed equally or more by visual observation were defined as ○ and falling ones ×.

Example 1

21.9 parts (0.090 mol) of (alpha), (alpha), (alpha) ', (alpha)'-tetramethyl xylylene diisocyanate were added and mixed with 78.1 parts (0.300 mol) of the trithiol compounds represented by said Formula (1). While stirring this, 0.1 part of N, N- dimethylcyclohexylamine was added and mixed at 40 degreeC under nitrogen atmosphere.

The reaction temperature was raised to 60 ° C, stirred for 6 hours to react, thereby obtaining a thiourethane prepolymer compound (TUPP-1) as a colorless transparent viscous liquid. When the IR spectrum of this compound was measured, absorption of the isocyanate group was lost and it was confirmed that the reaction was completed. About 5 g of this prepolymer was accurately weighed, dissolved in 50 ml of chloroform: methanol = 1: 1 solution, and the free mercapto group was quantified by titration of a standard iodine standard solution at 7.2 m equivalent / g. Moreover, the refractive index of this prepolymer compound was 1.63.

Example 2

In Example 1, 78.1 parts of the trithiol compound were 80.7 parts (0.220 mol) of the tetrathiol compound represented by the formula (2), and 21.9 parts of α, α, α ', α'-tetramethylxylylene diisocyanate. A thiourethane prepolymer compound (TUPP-2) was obtained as a colorless transparent viscous liquid except that it was changed to 19.3 parts (0.074 mol) of hydrogenated MDI. About 5 g of this prepolymer was accurately weighed, dissolved in 50 ml of chloroform: methanol = 1: 1 solution, and the free mercapto group was quantified by titration of a standard iodine standard solution to find that it was 7.3 m equivalent / g. Moreover, the refractive index was 1.62.

Example 3

0.1 part of dibutyltin dichloride was added and dissolved in 78.2 parts (0.30 mol) of the trithiol compounds represented by said Formula (1). While stirring this, 20.8 parts (0.11 mol) of xylylene diisocyanate were dripped at 40 degreeC over 15 minutes in nitrogen atmosphere. After completion of the dropwise addition, the reaction temperature was raised to 60 ° C, stirred for 6 hours to react, thereby obtaining a thiourethane prepolymer compound (TUPP-3) as a colorless transparent viscous liquid. When the IR spectrum of this compound was measured, absorption of the isocyanate group was lost and it was confirmed that the reaction was completed. About 5 g of this prepolymer was precisely weighed, dissolved in 50 ml of chloroform: methanol = 1: 1 solution, and the free mercapto group was quantified by titration of one standard iodine standard solution to obtain a 6.9 m equivalent / gdl. The refractive index was 1.64.

Example 4

In Example 3, 78.2 parts of the trithiol compound were similarly performed except having replaced 20.8 parts of xylylene diisocyanate with 23.5 parts (0.09 mol) of hydrogenated MDI in 76.5 parts (0.21 mol) of tetrathiol compounds represented by said Formula (2). As a colorless transparent viscous liquid, a thiourethane prepolymer compound (TUPP-4) was obtained. About 5 g of this prepolymer was accurately weighed and dissolved in 50 ml of chloroform: methanol = 1: 1 solution, and the free mercapto group was quantified by titration of a standard iodine standard solution to find that it was 6.6 m equivalent / g. Moreover, the refractive index was 1.62.

Synthesis Example 1

In Example 1, 78.1 parts of trithiol compounds were added to 88.6 parts (0.181 mol) of pentaerythritol tetrakismercaptopropionate, and 21.9 parts of α, α, α ', α'-tetramethylxylylene diisocyanate. Except having changed into 11.4 parts (0.061 mol) of isocyanates, it carried out similarly and obtained the thiourethane prepolymer compound (TUPP-5) as a colorless and transparent viscous liquid. About 5 g of this prepolymer was accurately weighed, dissolved in 50 ml of chloroform: methanol = 1: 1 solution, and the free mercapto group was quantified by titration of a standard iodine standard solution to 6.0 m equivalent / g. Moreover, the refractive index was 1.58.

Synthesis Example 2

In Example 3, 78.2 parts of trithiol compounds were similarly performed except having replaced 80.8 parts (0.18 mol) of pentaerythritol tetrakismercaptopropionate and 20.8 parts of xylylene diisocyanate to 13.4 parts (0.07 mol), and was colorless and transparent. As a viscous liquid, a thiourethane prepolymer compound (TUPP-6) was obtained. About 5 g of this prepolymer was accurately weighed and dissolved in 50 ml of chloroform: methanol = 1: 1 solution, and the free mercapto group was 5.8 m equivalent / g by titration of a standard iodine standard solution. Moreover, the refractive index was 1.58.

Example 5

20.0 parts of thiourethane prepolymer compound (TUPP-1) of Example 1, 45.0 parts of 2,2-bis (4-acryloxydiethoxyphenyl) methane, 15.0 parts of trimethylolpropane trimethacrylate, and 20.0 parts of divinylbenzene The mixture is mixed well, 0.2 part of bis (4-t-butyl cyclohexyl) peroxydicarbonate and 0.2 part of t-butylperoxy-2-ethylhexane hydrate are added as a radical polymerization initiator, mixed and degassed, and the composition for an optical resin is prepared. Got it.

The composition was poured into a concave lens mold having an outer diameter of 80 mm, a center thickness of 1.5 mm, and a peripheral thickness of 10 mm, which consisted of a glass mold and a gasket, and then heated and cured for 3 hours from 50 ° C to 130 ° C. Heat-cured at 1 hour.

After cooling to room temperature, the lens was released from the glass to obtain a colorless and transparent concave lens. Table 1 shows the results of the measurement of the physical properties of the lens.

Example 6

30.0 parts of thiourethane prepolymer compound (TUPP-2) of Example 2, 20.0 parts of 2,2-bis (4-acryloxydiethoxyphenyl) propane, 30.0 parts of tris (acryloxyethyl) isocyanurate, divinyl 20.0 parts of benzene were mixed well, 0.2 part of bis (4-t-butylcyclohexyl) peroxydicarbonate and 0.2 part of t-butyl peroxy-2-ethyl hexane oate were added as a radical polymerization initiator, mixed and defoaming, and optical water A fat composition was obtained. This composition was hardened in the same manner as in Example 5 to obtain a colorless and transparent concave lens. Table 1 shows the results of the measurement of the physical properties of the lens.

Example 7

20.0 parts of the thiourethane prepolymer compound (TUPP-1) of Example 1, 45.0 parts of 2, 2-bis (4-acryloxy diethoxyphenyl) methane, 15.0 parts of triethylene glycol diacrylates, and 20.0 parts of divinylbenzene well After mixing, 0.2 part of lauroyl peroxide and 0.2 part of t-butyl peroxy-2-ethyl hexane oate were added as a radical polymerization initiator, and it mixed and defoamed, and the composition for optical resins was obtained.

This composition was hardened in the same manner as in Example 5 to obtain a colorless and transparent concave lens. Table 1 shows the results of the measurement of the physical properties of the lens.

Example 8

32.0 parts of the thiourethane prepolymer compound (TUPP-3) of Example 3, 58.0 parts of tris (acryloyloxyethyl) isocyanurate, and 10.0 parts of divinylbenzene were mixed well, and 2-hydroxy as a photopolymerization initiator was added thereto. 0.04 parts of -2-methyl-1-phenyl propane-1-ones were added, mixed and degassed, and the composition for optical resins was obtained.

The composition was injected into a concave lens mold having an outer diameter of 80 mm, a center thickness of 1.5 mm, and a peripheral thickness of 10 mm formed of two glass-type and polyester adhesive tapes, and light of 80 W / cm high-pressure mercury lamp, Irradiation for 5 minutes at a distance of 15 cm cured. After cooling to room temperature, the adhesive tape was peeled off, the lens was released from the glass to obtain a colorless and transparent concave lens. Table 1 shows the results of the measurement of the physical properties of the lens.

Example 9

33.0 parts of the thiourethane prepolymer compound (TUPP-3) of Example 3, 57.0 parts of tris (acryloyloxyethyl) isocyanurate, 5.0 parts of ethylene glycol dimethacrylate, and 5.0 parts of divinylbenzene were mixed well, As a photoinitiator, 0.04 part of 2-hydroxy-2-methyl-1- phenyl propane- 1-one was added, mixed, and defoaming, and the composition for optical resins was obtained.

This composition was hardened in the same manner as in Example 8 to obtain a colorless and transparent concave lens. Table 1 shows the results of the measurement of the physical properties of the lens.

Example 10

45.0 parts of the thiourethane prepolymer compound (TUPP-4) of Example 4, 35.0 parts of trimethylolpropane triacrylate, and 20.0 parts of divinylbenzene were mixed well, and 2-hydroxy-2-methyl-1 as a photopolymerization initiator was added thereto. 0.04 parts of -phenyl propane-1-one was added, mixed and degassed, and the composition for optical resins was obtained. This composition was hardened in the same manner as in Example 8 to obtain a colorless and transparent concave lens. Table 1 shows the results of the measurement of the physical properties of the lens.

Example 11

20.0 parts of the thiourethane prepolymer compound (TUPP-3) of Example 3, 45.0 parts of 2,2-bis (4-acryloxydiethoxyphenyl) methane, 15.0 parts of ethylene glycol dimethacrylate, and 20.0 parts of divinylbenzene well It mixed, 0.10 part of 2-hydroxy-2-methyl-1- phenyl propane- 1-one as a photoinitiator was added, mixed, and defoaming, and the composition for optical resins was obtained. This composition was hardened in the same manner as in Example 8 to obtain a colorless and transparent concave lens. Table 1 shows the results of the measurement of the physical properties of the lens.

Comparative Example 1

30.0 parts of thiourethane prepolymer compound (TUPP-5) of the synthesis example 1, 20.0 parts of 2, 2-bis (4-acryloxy diethoxy phenyl) propane, 30.0 parts of tris (acryloxyethyl) isocyanurate, divinyl 20.0 parts of benzene were mixed well, 0.2 part of bis (4-t-butylcyclohexyl) peroxydicarbonate and 0.2 part of t-butyl peroxy-2-ethyl hexane oate were added as a radical polymerization initiator, mixed and defoaming, and optical water A fat composition was obtained.

This composition was hardened in the same manner as in Example 5 to obtain a colorless and transparent concave lens. Table 2 shows the results of the measurement of the physical properties of the lens.

Comparative Example 2

Except having changed 20.0 parts of thiourethane prepolymer compounds (TUPP-1) of Example 1 into 20.0 parts of trithiol compounds represented by said Formula (1), it hardened like Example 5 and obtained the colorless and transparent concave lens.

Table 2 shows the results of the measurement of the physical properties of the lens.

Comparative Example 3

20.0 parts of the thiourethane prepolymer compound (TUPP-1) of Example 1 were replaced with 15.6 parts (0.06 mol) of the trithiol compound represented by the formula (1), and α, α, α ', α'-tetramethylk 4.4 parts (0.018 mole) of silylene diisocyanate, 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, and a radical polymerization initiator 0.2 parts of bis (4-t-butylcyclohexyl) peroxydicarbonate and 0.2 parts of t-butylperoxy-2-ethylhexanoate as the urethane reaction catalyst, 0.03 parts of dibutyltin dichloride as the urethane reaction catalyst, and dioctyl acidity as the internal release agent. 0.1 part of phosphate ester was added, it mixed, and was defoamed.

This composition was hardened in the same manner as in Example 5 to obtain a colorless and transparent concave lens.

Table 2 shows the results of the measurement of the physical properties of the lens.

Comparative Example 4

45.0 parts of the thiourethane prepolymer compound (TUPP-6) of the synthesis example 2, 35.0 parts of trimethylol propane triacrylates, and 20.0 parts of divinylbenzene were mixed well, and 2-hydroxy-2-methyl-1 as a photoinitiator was added here. 0.04 parts of -phenyl propane-1-one was added, mixed and degassed, and the composition for optical resins was obtained. This composition was hardened in the same manner as in Example 8 to obtain a colorless and transparent concave lens. Table 2 shows the results of the measurement of the physical properties of the lens.

Comparative Example 5

Except having changed 32.0 parts of thiourethane prepolymer compounds (TUPP-3) of Example 3 into 32.0 parts of trithiol compounds represented by said Formula (1), it hardened like Example 8 and obtained the colorless and transparent concave lens.

Table 2 shows the results of the measurement of the physical properties of the lens.

Comparative Example 6

30.0 parts of the thiourethane prepolymer compound (TUPP-3) of Example 3 and 70.0 parts of 2,2-bis [4- (methacryloyloxydiethoxy) phenyl] propane were mixed, and 2-hydroxy as a photopolymerization initiator was added thereto. 0.04 parts of oxy-2-methyl-1-phenylpropan-1-one was added, mixed, and defoaming.

After hardening | curing this composition similarly to Example 8, the adhesive tape was peeled off and water-cooled, but resin did not mold-release in rubber form.

Comparative Example 7

26.1 parts of trithiol compounds represented by the formula (1), 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 Mix well and add 0.04 parts of 2-hydroxy-2-methyl-1-phenylpropane-1-one as a photoinitiator, 0.03 parts of dibutyltin dichloride as a urethane reaction catalyst, and dioctyl acid phosphate ester 0.1 as an internal mold release agent. Part was added, mixed and defoamed.

The composition was cured in the same manner as in Example 8, and then the adhesive tape was peeled off and beaten with a wedge to release. The obtained lens had a smoother surface. Table 2 shows the results of the measurement of the physical properties of the lens.

Transparency Refractive index Abbe Number Impact resistance Heat resistance Dyeability Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Good good good good good good good good 1.5901.5981.5881.5921.5871.6011.590 35.336.135.338.540.538.135.8 ○○○○○○○ ○○○○○○○ ○○○○○○○

Transparency Refractive index Abbe Number Impact resistance Heat resistance Dyeability Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 7 Good nursing care good 1.5731.5931.5911.5631.5941.585 37.036.535.441.740.540.8 ○○○○○ × ○ ×× ○ ×× ○○○○○○

Description of Table 1 and Table 2: The resin of Comparative Example 1 obtained by thermal polymerization using a prepolymer obtained from a thiol of thiocarboxylic acid ester type has a low refractive index and is insufficient compared with the resin of the present application. The resin of Comparative Example 2 obtained by thermal polymerization by directly using the trithiol compound without prepolymerization lacks heat resistance. In the resin of Comparative Example 3 obtained by reacting an isocyanate compound, a thiol compound and a polyene compound at the same time by thermal polymerization, striae was confirmed and the heat resistance was insufficient.

Moreover, the result was the same also about resin of Comparative Examples 4-7 obtained by photopolymerization. That is, in the resin of Comparative Example 4, the refractive index is insufficient. The resin of the comparative example 5 lacks heat resistance. The resin of Comparative Example 7 had insufficient curing and lacked impact resistance and heat resistance.

As described above, the thiourethane prepolymer compound according to the present invention has a high refractive index, and thus has a high refractive index, and is used as a raw material for an optical resin composition which provides a balanced resin such as transparency, optical deformation, heat resistance, dyeing, and impact resistance. Very useful.

Claims (3)

A thiourethane prepolymer compound obtained by reacting a trifunctional polythiol compound having a sulfide bond in a molecule and a polyisocyanate compound with a -SH / -NCO molar ratio in the range of 3.0 to 7.0. The thiourethane prepolymer compound according to claim 1, wherein the polythiol compound is a compound represented by the following formula (1) or (2). The polyisocyanate compound according to claim 1 or 2, wherein the polyisocyanate compound is selected from the group consisting of α, α, α ', α'-tetramethylxylylene diisocyanate, xylylene diisocyanate, hydrogenated MDI and norbornene diisocyanate. A thiourethane prepolymer compound, characterized in that at least one.