JPH08176235A - High-refractive-index resin material - Google Patents

Abstract

PURPOSE: To obtain a resin material having a high refractive index, low disper sion, a low specific gravity and improved impact resistance by polymerizing and curing a polymerizable composition containing specified unsaturated monomers by the action of heat and/or actinic radiation. CONSTITUTION: A mixture of 10-99 pts.wt. urethane-bond- or thioether-bond- containing unsaturated monomer represented by formula I (R<1> is H or CH<3> ; and R<2> is a group of any one of formulas II-VI) with 99-1 pt.wt. compound having at least one ethylenically unsaturated bond in the molecule is mixed with 0.01-5wt.% photopolymerization initiator or heat polymerization initiator. The obtained polymerizable mixture is heated to 20-150 deg.C for 1-30hr or is irradiated with an actinic radiation at a dose of 0.01-300J/m<2> to obtain a polymer being a high-refractive-index resin material having a refractive index of 1.55 or above, an Abbe's number of 30 or above and a specific gravity of 1.35 or below.

Description

Detailed Description of the Invention

[Background of the Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin material which is polymerized and cured by the action of heat and / or active energy rays. More specifically, the present invention relates to a resin material suitable for manufacturing optical components such as lenses, prisms, mirrors and optical disks.

[0002]

2. Description of the Related Art Conventionally, various resins for plastic lenses have been studied as a substitute for inorganic glass. For example, a resin material obtained by polymerizing a monomer containing methyl methacrylate or diethylene glycol bisallyl carbonate as a main component is used as a lens. Widely used as an optical component. This resin has advantages such as excellent impact resistance and transparency, and good light dispersion characteristics. However, since the refractive index is 1.50, which is lower than that of glass, the lens becomes thick. It seems that weight saving is not enough.

On the other hand, various diacrylates or dimethacrylates are known to be easily radically polymerized to give a lens resin having excellent transparency. For example, di (meth) acrylates having a bromine-containing bisphenol A skeleton (JP-A-59-184210 and JP-A-59).
No. 193915), di (meth) acrylates having a sulfur-containing aromatic skeleton (JP-A-60-26010).
It is known that the resin for lenses obtained from Japanese Patent Laid-Open No. 62-195357 and Japanese Patent Laid-Open No. 62-195357) has a high refractive index and excellent optical characteristics with a high balance of Abbe numbers.

However, as far as the present inventors know, these compounds are radically polymerized to form a highly crosslinked structure, and on the other hand, they exhibit excellent heat resistance and polishing properties. There is a problem that the cured product is brittle and the impact resistance is not sufficient. As a method for improving these points, a method of converting a bromine-containing bisphenol A derivative into a urethane (meth) acrylate is disclosed in Japanese Patent Laid-Open No.
As disclosed in 0-51706, since the produced resin composition contains a bromine atom, the specific gravity becomes large,
It seems inevitable that the weather resistance will deteriorate.

[0005]

DISCLOSURE OF THE INVENTION The present invention is an improvement over the problems of the prior art such as resins for plastic lenses described above, and has a high refractive index, low dispersion, low specific gravity and excellent impact resistance. Another object of the present invention is to provide a resin material suitable for manufacturing optical components, for example. [Outline of the Invention]

[0006]

[Means for Solving the Problems]

<Summary> The resin material according to the present invention comprises a composition for polymerization containing an unsaturated monomer having a urethane bond and a thioether bond represented by the following formula [I], which is treated with heat and / or active energy rays. It is characterized by being polymerized and cured by the action.

[0007]

Embedded image (In the formula, each R ¹ is hydrogen or CH ₃ ,
R ² is

[0008]

[Chemical 4] <Effect> The resin material according to the present invention is suitable for manufacturing optical parts and the like, has a high refractive index, a low dispersion, a low specific gravity, and is excellent in impact resistance. This is a solution to the problems found in plastic lenses for plastics. DETAILED DESCRIPTION OF THE INVENTION The resin material according to the present invention comprises a composition for polymerization containing an unsaturated monomer having a urethane bond and a thioether bond represented by the following formula [I]:
It is characterized by being polymerized and cured by the action of heat and / or active energy rays.

[0009]

Embedded image (In the formula, R ¹ is hydrogen or CH ₃ ,
² is

[0010]

[Chemical 6] Here, “comprising” means that, in addition to the components listed above, that is, the unsaturated monomer of the formula [I], auxiliary components are included unless they detract from the gist of the present invention. (Details below) may be included. [Detailed Description of the Invention] [Unsaturated Monomer] <Definition> The unsaturated monomer represented by the formula [I] contained in the resin material according to the present invention is symmetrical about the group R ^2. Appear, but include asymmetric compounds. That is,
R ¹ and R ² can be all combinations possible by definition, and therefore, the unsaturated monomer represented by the formula [I] in the present invention can be any of the above R ^{1 to} R ² . Includes compounds shown by all combinations. Specifically, the alkenyl groups (that is, vinyl group (R ¹ ═H) or isopropenyl group (R ¹ ═CH ₃ )) present on the phenyl groups at both ends of the compound of formula [I] are of the type and ( Or) The binding positions may be the same or different. That is, two R ^{1 s} are the same,
It goes without saying that the position of the bond on the phenyl group may be different, and it may be any position of the ortho, meta and para (in relation to the position of the methylenethioether group following the urethane bond). ) May be sufficient.

The unsaturated monomer in the present invention, as long as it is represented by the above formula [I], is a mixture of compounds different in the kind of the alkenyl group and / or the bonding position thereof. May be.

A preferred group of compounds represented by the formula [I] is (a) in which R ¹ is hydrogen,
(B) R ²

[0013]

[Chemical 7] And (c) an alkenyl group is present in the meta or para position or a compound thereof.

The following are particularly preferred unsaturated monomers according to the present invention.

[0015]

Embedded image

[0016]

[Chemical 9]

[0017]

[Chemical 10] <Production of Unsaturated Monomer> Unsaturated monomer having urethane bond and thioether bond in the present invention (formula [I])
Can be prepared by any method which is versatile with respect to attachment and / or the formation of substituents.

That is, as the unsaturated monomer in the present invention, if the compound of the formula [I] having the specific structure is obtained as a single product or if the compounds of two or more structures are obtained as a mixture. , Can be manufactured by any method. As a preferable production method in industrial practice from the viewpoint of excellent economical efficiency and operability and high product quality and stability, for example, a method comprising reacting an alcohol compound and a diisocyanate compound as described below, (B) There is a method comprising reacting a bisthiol compound having a urethane bond with a halomethylstyrene derivative.

(A) Manufacturing method (1) The manufacturing method (first manufacturing method) of the unsaturated monomer in the present invention is as follows:
It comprises reacting an alcohol compound represented by the following general formula [II] with a diisocyanate compound represented by the following formula [IV].

[0020]

[Chemical 11] (The definitions of R ¹ and R ² are as described above.) This alcohol compound [II] is prepared by dehydrohalogenating a halomethylstyrene derivative represented by the following formula [III] and 2-mercaptoethanol in the presence of an alkali. It can be synthesized by carrying out a reaction, and it is also one of the preferable methods.

[0021]

[Chemical 12] (The definition of R ¹ is, as described above, X is Cl or Br). Therefore, a preferred method for producing an unsaturated monomer having a urethane bond and a thioether bond represented by the formula [I] according to the first production method is preferable. In an embodiment, a halomethylstyrene derivative represented by the formula [III] is reacted with 2-mercaptoethanol to produce an alcohol compound represented by the formula [II], and the alcohol compound is then represented by the formula [IV]. Consisting of reacting with a diisocyanate compound.

From this point of view, the first manufacturing method will be described below in accordance with this preferred embodiment.

Since the reaction between the halomethylstyrene derivative which is one reactant and 2-mercaptoethanol which is the other reactant is a dehydrohalogenation reaction, an alcohol compound (formula [II] ) Is 2- (alkenylbenzylthio) ethanol mainly corresponding to the halomethylstyrene derivative used.

This halomethylstyrene derivative has the formula [III
], But correspondingly to the definition including compounds with respect to R ¹ and the position of substitution of the alkenyl group, the present invention provides a mixture of compounds within this definition. It includes the case of using it as a starting reactant. Thus, the present invention allows the reaction with 2-mercaptoethanol to be carried out using, for example, a mixture of p-halomethylstyrene and m-halomethylstyrene, in which case the product is p-, m -Is a mixture of isomers.

The alcohol compound of the formula [II] thus obtained can be isolated from the above dehydrohalogenation reaction product by solvent extraction and / or crystallization or other means.

Alcohol compound [II] obtained in this way or by another process (if desired, if desired)
As a solution or dispersion as the above dehydrohalogenation reaction product as it is, or after treatment such as removal of by-product sodium halide (when the alkali is a sodium group base), (Optionally) can be reacted with a diisocyanate compound of formula [IV] to produce a compound of formula [I].

Of the halomethylstyrene derivatives represented by the formula [III], a particularly preferred example is p.
-Chloromethylstyrene, p-bromomethylstyrene,
Examples thereof include m-chloromethylstyrene, m-bromomethylstyrene, p-chloromethyl-α-methylstyrene and the like.

A halomethylstyrene derivative of the formula [III] and 2-mercaptoethanol (HS-CH ₂ CH ₂ -O
Since the reaction with H) is accompanied by dehydrohalogenation, this reaction is usually carried out in the presence of a dehalogenating agent or an alkali according to a conventional method for dehalogenation reaction. Yes, and also preferred.

As the alkali used in the dehydrohalogenation reaction, an alkali metal hydroxide or carbonate, preferably, for example, sodium hydroxide, potassium hydroxide, potassium carbonate or the like is used.

This reaction is preferably carried out in a solvent, and it is preferable to use a solvent in which at least one of both reactants is soluble, particularly an alcohol, a water-alcohol mixed system or a ketone system solvent.

This dehydrohalogenation reaction is preferably carried out by reacting the above-mentioned styrene derivative [III] and 2-mercaptoethanol in stoichiometrically equivalent amounts or before and after the reaction, more preferably 2-mercaptoethanol. It is preferable to add a slight excess of ethanol so as to be 1.1 to 1.2 equivalents. The reaction temperature is 0 ° C to 60 ° C, particularly 10 ° C to 3 ° C.
0 ° C. is preferred. If the reaction temperature in this case is too high,
This may cause coloration of the product.

The reaction between the alcohol compound [II] and the diisocyanate compound [IV] can be carried out using a known technique. That is, if necessary, a metal compound such as dibutyltin dilaurate or a Lewis base such as tertiary amine or tertiary phosphine is added as a catalyst, and the unsaturated monomer of the formula [I] is stirred by stirring at room temperature or under heating. Can be synthesized.

In the production of the unsaturated monomer [I] in the present invention, the alcohol compound [II] and the diisocyanate compound [IV] are mixed at a ratio of the --OH group of the alcohol compound to the --NCO group of the diisocyanate compound. It is common to use 1: 1 or around 1: 1.

The amount of catalyst used depends on the alcohol compound [I
It is 0.01 to 1.0 part by weight, preferably 0.05 to 0.2 part by weight, based on 100 parts by weight of the total amount of I] and the diisocyanate compound [IV].

This reaction is preferably carried out under heating at about 40 ° C. in an inert gas atmosphere or dry air.

The diisocyanate compound [IV] is selected according to the desired unsaturated monomer [I]. Specific examples include 1,3-cyclohexylmethylene diisocyanate (that is, 1,3-di (cyanatomethyl) cyclohexane), isophorone diisocyanate, 2,4,4.
-Trimethylhexamethylene diisocyanate, 2,
There are 2,4-trimethylhexamethylene diisocyanate and 1,3-di (2-isocyanato-2-propyl) benzene. These can also be mixed and used.

(B) Production Method (Part 2) The production method (second production method) of the unsaturated monomer having a urethane bond and a thioether bond in the present invention is a urethane represented by the following formula [V]: A bisthiol compound having a bond is reacted with a halomethylstyrene derivative represented by the general formula [III].

[0038]

[Chemical 13] (The definitions of R ¹ , R ² and X are as described above.) The bisthiol compound [V] can be synthesized by reacting the diisocyanate compound of the formula [IV] with 2-mercaptoethanol. And
That is the preferred method.

That is, for example, if necessary, a metal compound such as dibutyltin dilaurate or a Lewis base such as a tertiary amine or a tertiary phosphine is added as a catalyst, and both reactants are stirred at room temperature or under heating to obtain the above-mentioned substances. Unsaturated monomers of formula [I] can be synthesized.

In producing the bisthiol compound represented by the formula [V], the ratio of 2-mercaptoethanol and diisocyanate compound [IV] to the chemical ratio of the 2-OH group of 2-mercaptoethanol and the -NCO group of the diisocyanate compound is chemical. It is usually used in a stoichiometrically equivalent amount, or around the same amount.

The amount of the catalyst used is 0.01 to 1.0 parts by weight, preferably 0.05 to 0.2 parts by weight, based on 100 parts by weight of the total amount of 2-mercaptoethanol and diisocyanate compound [IV]. Parts by weight.

This reaction may be carried out preferably under heating at about 40 ° C. in an inert gas atmosphere or dry air.

Specific examples of the diisocyanate compound [IV] used are the same as those described above for the first production method.

Recovery of the desired product [V] from the reaction product can be carried out by any purposeful method. Specific examples include distillation, crystallization, and the like.

Thus, the urethane group-containing bisthiol compound of the formula [V] can be obtained.

The reaction between the urethane group-containing bisthiol compound [V] and the halomethylstyrene derivative [III] as the reaction mixture of 2-mercaptoethanol and the diisocyanate compound [IV] as it is or as recovered from it is It can be synthesized by carrying out a dehydrohalogenation reaction in the presence of any purposeful method.

Specific examples of particularly preferred halomethylstyrene derivatives represented by the formula [III] are the same as those described above for the first production method.

Specific examples of the alkali and the solvent used in the dehydrohalogenation reaction are the same as those described above for the first production method.

The reaction is preferably carried out by reacting the above-mentioned styrene derivative [III] and bisthiol compound [V] in stoichiometric amounts or before and after the reaction, more preferably from 1.1 to bisthiol compound [V]. It is preferable to make a slight excess so that the amount becomes 1.2 equivalents. The reaction temperature is 0 ° C to
60 degreeC, especially 10 degreeC-30 degreeC are preferable. If the reaction temperature in this case is too high, the product may be colored.

It is the same as in the first production method that a plurality of halomethylstyrene derivatives of the formula [III] may be used with respect to the bonding position of R ¹ and the alkenyl group, and the bisthiol compound [V] is also R. ^Two or more kinds of ² may be used. [Use of Unsaturated Monomer (1)] The unsaturated monomer in the present invention has two ethylenically unsaturated bonds in one molecule. Thus, this compound copolymerizes with itself or with an ethylenically unsaturated monomer copolymerizable therewith to form a polymer.

Since the unsaturated monomer in the present invention has two ethylenically unsaturated bonds, the polymer produced has a crosslinked structure.

The unsaturated monomer of the formula [I], as its homopolymer or copolymer, gives a high refractive index resin which solves the problems found in conventional optical resins. I have just done it.

The polymerization of the unsaturated monomer of the present invention represented by the formula [I] can be carried out in a manner essentially the same as that conventionally used for the polymerization of ethylenically unsaturated monomers. .

Although such conventional manners are well known, reference is made to the description below regarding the copolymerization for the explanation in accordance with the monomer of the present invention. [Use of Unsaturated Monomer (Part 2)] The unsaturated monomer represented by the formula [I] is useful for polymerizing the unsaturated monomer to produce a high refractive index resin, and in that case, As described above, it is preferable to copolymerize with a monomer.

Therefore, a preferred embodiment of the unsaturated monomer represented by the formula [I] is a composition for polymerization containing this monomer as the component (A) and the comonomer as the component (B). (Incidentally, it is apparent from the above that a "composition for polymerization comprising the component (A)" which does not contain the component (B) as an essential component is also one embodiment of the present invention).

In the resin material according to one of the preferred embodiments of the present invention, the composition for polymerization comprises the following component (A) and component (B). Component (A): an unsaturated monomer having a urethane bond and a thioether bond represented by the formula [I]. Component (B): A compound having at least one ethylenically unsaturated bond in the molecule.

The term "comprising" as used herein means that in addition to the components listed above, that is, the components (A) and (B), the components of the present invention are included. Other polymerizable components and / or
It means that an auxiliary component (detailed later) may be contained.

The content of the unsaturated monomer having a urethane bond and a thioether bond represented by the formula [I] of the component (A) is optional as long as the gist of the present invention is not impaired. A) + component (B) 100 parts by weight), preferably 10 to 99 parts by weight, more preferably 5 parts by weight.
It is preferable to use 0 to 99 parts by weight.

Component (B) is a compound having at least one ethylenically unsaturated bond in one molecule. As such an ethylenically unsaturated compound, a general radical polymerizable monomer can be used.

Such monomers are well known in radical polymerization, and any desired monomer can be selected and used in the present invention. Examples of monomers useful as component (B) include:

(1) Vinyl compounds, specifically, styrene derivatives such as styrene, vinyltoluene, methoxystyrene, chlorostyrene, bromostyrene, dichlorostyrene, dibromostyrene, divinylbenzene, vinylnaphthalene, and (2) (meta). ) Acrylate compounds, specifically their phenyl or phenylmethyl substitutions, ie phenylmethacrylate and benzylmethacrylate, bisphenol compounds (eg bisphenol A) or their ethylene oxide adducts (eg 1 mol of ethylene oxide each) (meth).
Acrylates such as 2,2-bis (4- (meth) acryloyloxyphenyl) propane, its halogen derivatives, 2,2-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) propane, xylylenethioglycol To (meth) acrylate of bismercaptomethylbenzene or its ethylene oxide adduct (for example, 1 mol of ethylene oxide each adduct (preferably the latter)), specifically p-bis (β- (meth) acryloyloxyethylthio) xylylene, m-bis (β-
(Meth) acryloyloxyethylthio) xylylene and the like. Here, "(meth) acrylate" means both "acrylate" and "methacrylate", and "(meth) acryloyl" means both "acryloyl" and "methacryloyl". . These polymerizable monomers may be used either individually or in combination of two or more.

The content of the radical-polymerizable monomer of the component (B) is arbitrary as long as the gist of the present invention is not impaired, but it is based on the resin composition (component (A) + component (B) 100 parts by weight). , Preferably 1 to 90 parts by weight, more preferably 1 to 50 parts by weight.

The physical properties and viscosity of the resin material can be adjusted by blending these radically polymerizable monomers with the unsaturated monomer of the present invention.

In order to polymerize and cure the composition for polymerization when obtaining the resin material according to the present invention, polymerization by heat, polymerization by active energy rays, and a method of using these in combination are adopted.

In the case of polymerization by heat, a thermal polymerization initiator is used, and in the case of polymerization by active energy rays such as ultraviolet rays,
It is preferable to use a photo (ultraviolet) polymerization initiator.

In addition to these polymerization initiators, a radical generator may be used in combination, and this radical generator may overlap with the above-mentioned polymerization initiator. Further, the polymerization initiator includes a case where it is an oxidizing agent and is combined with a reducing agent to form a so-called redox system.

More specifically, in the case of thermal polymerization, a thermal polymerization initiator such as benzoyl peroxide, diisopropyl peroxycarbonate, lauroyl peroxide, t-butylperoxy (2-ethylhexa) is added to the composition for polymerization. Noate), t-butylperoxyisobutyrate, azoisobutyronitrile, etc., preferably lauroyl peroxide, t-butylperoxy (2-ethylhexanoate), t-butylperoxyisobutyrate, etc. Is preferably added and dissolved, and the polymerization and curing reaction is preferably performed at a temperature in the range of 20 to 150 ° C. for 1 to 30 hours.
The reaction atmosphere may be the air or an inert gas. Further, in the case of ultraviolet polymerization, a photopolymerization initiator such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, diethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or the like is preferably added to the composition for polymerization. Benzophenone benzoin isopropyl ether, 2,
4,6-Trimethylbenzoyldiphenylphosphine oxide or the like is added and dissolved, and ultraviolet rays are irradiated in the atmosphere or an inert gas to cause a polymerization and curing reaction. The amount of irradiation light of ultraviolet rays at that time is appropriately selected depending on the types of the composition and the photopolymerization initiator, but is generally 0.01 to 30.
0 J / cm ² is preferred. As the light source, a chemical lamp, a xenon lamp, a low-pressure (or high-pressure) mercury lamp, a metal halide lamp, or the like is used, and active energy rays other than ultraviolet rays, such as an electron beam, can be polymerized without a photopolymerization initiator.

The amount of the photopolymerization initiator and the thermal polymerization initiator used is about 0.01 to 5% by weight based on the total weight of the composition,
It is preferably in the range of 0.03 to 2% by weight. If the amount used is too small, curing will be inadequate, and if it is too large, the resin produced will easily turn yellow and control of polymerization will be difficult.

In such a composition for polymerization, a radical polymerization accelerator, a polymerization regulator, an ultraviolet absorber, a release agent, an antioxidant, and other additives can be added as an auxiliary agent. As these additives, known commercial products can be used, but phosphorus-based antioxidants are particularly preferable as the antioxidant. [Polymerization Product / High Refractive Index Resin Material] The polymerization product of the composition for polymerization containing the unsaturated monomer represented by the formula [I] as at least one component of the monomer is an unsaturated compound of the formula [I]. This is a resin material having a large refractive index, mainly corresponding to that the monomer has a urethane bond and a thioether bond.

This resin also has low dispersion and low specific gravity and is excellent in impact resistance.

That is, the high refractive index resin material obtained by the present invention has a high refractive index of 1.55 or more and a high Abbe number of 30 or more, and has a low specific gravity of 1.35 and is also resistant to impact. According to the test method described later, it is an excellent optical material in which no breakage is observed.

From such physical properties, particularly optical physical properties, the high refractive index resin material according to the present invention is useful as a material for lenses, prisms and other optical elements.

Such an optical element is manufactured by directly manufacturing a desired shape by a mold having a cavity corresponding to the contour, or by once manufacturing a lump and cutting it into a desired shape. It can be manufactured by the method.

[0074]

EXAMPLES The following examples and comparative examples serve to further explain the present invention. In these examples "part"
Means parts by weight. The physical properties of the resins in these examples are measured by the following test methods.

Appearance Regarding the appearance, the transparency and surface condition of the test piece were visually evaluated. Refractive Index / Abbe Number The refractive index and Abbe number were measured with an Abbe refractometer (measurement temperature 25 ° C.). Impact resistance As for impact resistance, a hard sphere (weight: 16.3 g, diameter: 15.9 mm) is applied to a flat test piece with a thickness of 2 mm based on the FDA standard.
It was evaluated by dropping from a height of 27 cm. When there was no breakage, it was marked with ◯, and when it was broken, it was marked with x. Specific gravity Specific gravity was measured with a pycnometer.

<Unsaturated Monomer> The unsaturated monomers (1) to (3) having a urethane bond and a thioether bond used in Examples 1 to 3 are obtained as follows. Is.

Preparation of unsaturated monomer (1) 2-mercaptoethanol 93.7 g (1.2 mol)
And 49.0 g (1.1 mol) of sodium hydroxide are dissolved in 100 ml of methanol, and 152.6 g of chloromethylstyrene (m, p mixture, m: p = 7: 3) is dissolved therein.
(1 mol) was added dropwise while maintaining the temperature of the reaction system at 20 ° C. After the reaction, the reaction product was extracted with toluene, washed with an aqueous sodium hydroxide solution and water, 200 mg of methoxyhydroxynone was added as a polymerization inhibitor, and then toluene was distilled off, followed by crystallization in hexane. 19
8 g of 2-hydroxyethylthiomethylstyrene (m,
p mixture, m: p = 7: 3) was obtained (yield 97%).

48.6 g (0.25 mol) of the obtained 2-hydroxyethylthiomethylstyrene was dissolved in dry tetrahydrofuran and heated to 40 ° C. under a nitrogen gas atmosphere. 55 mg of dibutyltin dilaurate was added in 5 portions over 1 hour. The atmosphere is dry air and 45 ℃
For 3 hours. Insoluble matter was removed by filtration, reprecipitation was performed with hexane, and the product was separated by filtration to obtain 62 g (0.11 mol) of the compound (1) represented by the following constitutive formula (yield 8
5%).

When the bending ratio of the obtained compound was measured, the bending ratio was 1.59 and the Abbe number was 35.

[0080]

Embedded image Manufacture of unsaturated monomer (2) In the same manner as in the manufacture of unsaturated monomer (1), p-chloromethylstyrene was used in place of the m, p mixture of chloromethylstyrene, and was synthesized in the same manner. The compound (2) was obtained (yield 89%). Refractive index 1.59, Abbe number 3
It was 5.

[0081]

[Chemical 15] Manufacture of unsaturated monomer (3) was synthesized in the same manner using 2,4,4-trimethylhexamethylene diisocyanate instead of cyclohexyl methylene diisocyanate in the manufacture of unsaturated monomer (1), and is represented by the following structural formula. A compound (3) was obtained (yield 82%).
The refractive index was 1.57 and the Abbe number was 38.

[0082]

Embedded image <Example 1> In 100 parts of the compound represented by the formula (1), t-
Add 0.3 parts of butyl peroxy-2-ethylhexanoate (trade name "Perbutyl O" manufactured by NOF CORPORATION),
After defoaming, it was poured into a mold having a thickness of 2 mm in which the upper and lower surfaces were made of glass plates and the side surfaces were made of silicon rubber. Next, this mold is heated from 30 ° C to 100 ° C.
The temperature was raised to ° C over 15 hours.

After removing the obtained cured product from the mold, the physical properties of this cured product were measured. The results obtained are
It is as shown in Table 1.

<Example 2> 20 parts of the compound represented by the above formula (2) and 80 parts of p-bis (β-methacryloyloxyethylthio) xylylene were mixed and stirred to obtain 2,4,6-trimethylbenzoyldiphenylphosphine. Oxide 0.1 part and t-butylperoxy-2-ethylhexanoate (Nippon Yushi Co., trade name "Perbutyl O")
After 0.2 part was added and degassed, it was poured into a 2 mm-thick mold in which the upper and lower surfaces were made of glass plates and the side surfaces were made of silicon rubber. Next, the mold was irradiated with light from a high pressure mercury lamp having an output of 80 W / cm located 40 cm away from the mold for 3 minutes in an atmosphere of 110 ° C.

After removing the obtained cured product from the mold, the physical properties of this cured product were measured. The results obtained are
It is as shown in Table 1.

<Example 3> 20 parts of the compound represented by the above formula (3) and 80 parts of p-bis (β-methacryloyloxyethylthio) xylylene were mixed and stirred to obtain 2,4,6-trimethylbenzoyldiphenylphosphine. Oxide 0.1 part and t-butylperoxy-2-ethylhexanoate (Nippon Yushi Co., trade name "Perbutyl O")
After 0.2 part was added and degassed, it was poured into a 2 mm-thick mold in which the upper and lower surfaces were made of glass plates and the side surfaces were made of silicon rubber. Next, the mold was irradiated with light from a high pressure mercury lamp having an output of 80 W / cm located 40 cm away from the mold for 3 minutes in an atmosphere of 110 ° C.

After removing the obtained cured product from the mold, the physical properties of this cured product were measured. The results obtained are
It is as shown in Table 1.

<Comparative Example 1> 2,4,6 in 100 parts of p-bis (β-methacryloyloxyethylthio) xylylene
-Trimethylbenzoyldiphenylphosphine oxide (0.1 part) and t-butylperoxy-2-ethylhexanoate (manufactured by NOF CORPORATION, trade name "Perbutyl O") (0.2 part) were added, and after defoaming, It was poured into a 2 mm-thick mold in which the upper and lower surfaces were made of glass plates and the side surfaces were made of silicon rubber. Next, the mold was irradiated with light from a high pressure mercury lamp having an output of 80 W / cm located 40 cm away from the mold for 3 minutes in an atmosphere of 110 ° C.

After removing the obtained cured product from the mold, the physical properties of this cured product were measured. The results obtained are
It is as shown in Table 1.

[0090]

[Table 1]

[0091]

INDUSTRIAL APPLICABILITY The resin material according to the present invention is suitable for manufacturing optical parts and the like, has a high refractive index, low dispersion, low specific gravity and excellent impact resistance, and is found in conventional plastic lens resins and the like. The problem that was solved is that
It has been described above in the "Summary of Invention" section.

Claims (2)

[Claims] 1. A polymerization composition comprising an unsaturated monomer having a urethane bond and a thioether bond represented by the following formula [I] is polymerized and cured by the action of heat and / or active energy rays. A high-refractive-index resin material characterized in that Embedded image (In the formula, each R ¹ is hydrogen or CH ₃ ,
R ² is Is either) 2. The resin material according to claim 1, wherein the composition for polymerization comprises the following component (A) and component (B). Component (A): The unsaturated monomer having a urethane bond and a thioether bond according to claim 1. Component (B): A compound having at least one ethylenically unsaturated bond in the molecule.