JP2001048877A - Sulfur-containing compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having excellent optical characteristics, mechanical characteristics and thermal characteristics and improved productivity, useful as an optical material having a high refractive index. SOLUTION: This compound is shown by formula I (R1 and R2 are each H or an alkyl or may be mutually bonded to form a form a ring; R3 is H or methyl; X1 is O or S; (m) is 0-3; and (n) is 1-4) such as 2-(2'-bromoethyl)-1,3- dithiolan, etc. The compound is obtained by reacting a compound of formula II with a halopropionic aicd ester compound or its acid halide in a solventless state or in a solvent such as n-hexane, etc. at 78-150 deg.C for several minutes to about 100 hours to give a halopropionic acid ester compound, dehydrohalogeneting the compound with triethylamine, etc. as a dehydrohalogenating agent and making the resultant substance into a (meth) acrylic acid ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sulfur-containing (meth) acrylate compound and a sulfur-containing compound which is an intermediate for the synthesis thereof. Further, the present invention relates to a polymerizable composition containing the sulfur-containing (meth) acrylate compound, and an optical component obtained by polymerizing the polymerizable composition.

[0002] The sulfur-containing (meth) acrylate compound of the present invention is characterized by having a cyclic thioacetal structure in the molecule on the molecular structure, and is used for a photocurable polymerizable composition. Useful as a monomer. An optical component obtained by curing the polymerizable composition has excellent optical properties, thermal properties, and mechanical properties, and has good productivity, a high refractive index, and is represented by a corrective spectacle lens. It is useful as various plastic lenses, optical information recording medium substrates, plastic substrates for liquid crystal cells, optical fiber coating materials, and the like.

[0003]

2. Description of the Related Art Inorganic glass is used in a wide range of fields as a transparent optical material because of its excellent properties such as excellent transparency and small optical anisotropy. However, there are problems such as being heavy and easily damaged and poor productivity. In recent years, development of optical resins in place of inorganic glass has been actively carried out.

A fundamentally important property as an optical resin is transparency. Until now, polymethyl methacrylate (PMMA), a highly transparent industrial optical resin,
Bisphenol A polycarbonate (BPA-PC),
Polystyrene (PS), methyl methacrylate-styrene copolymer (MS), styrene-acrylonitrile copolymer (SAN), poly (4-methylpentene-
1) (TPX), polycycloolefin (COP), polydiethylene glycol bisallyl carbonate (EG
AC), polythiourethane (PTU) and the like are known.

[0005] PMMA has excellent transparency and weather resistance, and also has good moldability. However, there are disadvantages that the refractive index (nd) is as small as 1.49 and the water absorption is large.

[0006] BPA-PC is excellent in transparency, heat resistance, impact resistance and high refraction, but has large chromatic aberration and its field of use is limited.

[0007] Although PS and MS are excellent in moldability, transparency, low water absorption and high refractive index, they are poor in impact resistance, weather resistance and heat resistance, and are hardly practically used as optical resins.

[0008] SAN is said to have a relatively high refractive index and a good balance of mechanical properties, but it has some difficulty in heat resistance (heat deformation temperature: 80 to 90 ° C) and is hardly used as an optical resin. Not done.

TPX and COP are transparent, have low water absorption,
Although having excellent heat resistance, a low refractive index (nd = 1.47-
1.53), there is a problem that the impact resistance, gas barrier properties and dyeability are poor.

EGAC is a thermosetting resin having diethylene glycol bisallyl carbonate as a monomer,
Most commonly used for general-purpose spectacle lens applications. Although it is excellent in transparency and heat resistance and has extremely small chromatic aberration, it has a defect that it has a low refractive index (nd = 1.50) and is inferior in impact resistance.

PTU is a thermosetting resin obtained by reacting a diisocyanate compound with a polythiol compound, and is most often used for ultra-high refractive index spectacle lenses. This material is particularly excellent in transparency, impact resistance, and high refraction, and has a small chromatic aberration. It is the only material that has a shortcoming of long thermopolymerization molding time (1 to 3 days). Leaves a problem in terms.

A method of obtaining an optical lens by photopolymerization using an acrylic acid ester containing a bromine atom or a sulfur atom for the purpose of performing polymerization and curing in a short time to enhance the productivity (for example, JP-A-4-16141
0, JP-A-3-217412, etc.) and a method of obtaining an optical lens using a (meth) acrylate compound having a sulfur-containing alicyclic structure (for example, JP-A-3-2
No. 15801) has been proposed.

However, according to these methods, polymerization can be performed in a short period of time, but the obtained resin has never been satisfactory as an optical component. That is, for example, when used as a spectacle lens, a high-refractive-index lens has problems such as being brittle and fragile and having a large specific gravity. Therefore, development of a material that overcomes these problems has been strongly desired.

As described above, conventional optical resins have excellent characteristics, but at present, each has its own disadvantages to be overcome. Under these circumstances,
At present, there is a strong demand for the development of an optical resin having excellent optical properties, mechanical properties, and thermal properties, high productivity and high refractive index.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the conventional optical resin, to provide excellent optical properties, mechanical properties, and thermal properties, and to improve productivity. An object of the present invention is to provide a raw material monomer for an optical material having a high refractive index and an intermediate thereof.

[0016]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above problems, and as a result, have reached the present invention. That is, the present invention relates to a sulfur-containing (meth) acrylate compound represented by the formula (1).

[0017]

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and may combine with each other to form a ring, R ₃ represents a hydrogen atom or a methyl group, and X ₁ represents an oxygen atom or a sulfur atom. And m represents an integer of 0 to 3 and n represents an integer of 1 to 4)

Further, a polymerizable composition containing the sulfur-containing (meth) acrylate compound represented by the above formula (1), a cured product obtained by polymerizing the polymerizable composition, and a cured product thereof The present invention relates to an optical component made of an object.

Furthermore, the present invention relates to a sulfur-containing compound represented by the formula (2), which is useful as an intermediate for the synthesis of the sulfur-containing (meth) acrylate compound.

[0020]

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and may combine with each other to form a ring; X ₂ represents a halogen atom, a hydroxy group or a thiol group;
Represents an integer of 1 to 3, and n represents an integer of 1 to 4.)

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The sulfur-containing (meta) represented by the formula (1) of the present invention
The acrylate compound is a novel compound and is a (meth) acrylate compound having a cyclic thioacetal structure at the ester group.

In the formula (1), R ₁ and R ₂ represent a hydrogen atom or an alkyl group. Further, R ₁ and R ₂ may combine with each other to form a ring.

The substituents R ₁ and R ₂ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
More preferably, they are a hydrogen atom, a methyl group or an ethyl group. When R ₁ and R ₂ are combined to form a ring, the ring is preferably a cycloalkane ring, more preferably a cycloalkane ring having 5 to 7 carbon atoms, still more preferably cyclohexane It is a ring.

In the formula (1), m is an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1.

In the formula (1), n is an integer of 1 to 4, preferably 1 to 3, and more preferably 1 or 2.

In the formula (1), X ₁ represents an oxygen atom or a sulfur atom. In consideration of a high refractive index when used as a lens resin, preferably, X ₁ is a sulfur atom.

The sulfur-containing (meta) represented by the formula (1) of the present invention
Specific examples of the acrylate compound include the compounds shown in Table 1 below.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

[0034]

[Table 6]

[0035]

[Table 7]

[0036]

[Table 8]

The sulfur-containing (meta) represented by the formula (1) of the present invention
Among the compounds represented by the formula (2), the acrylate compound is obtained by using a compound in which X ₂ = hydroxyl group or X ₂ = thiol group as a raw material, and the reaction itself is known in various esterification methods (or thioesterification). Method). That is, a method of reacting a (meth) acrylic acid with a compound represented by the following formula (2-a) or the following formula (2-b); halopropionate compounds (for example, 3-chloropropionic acid) , 3-bromopropionic acid, 3-chloro-2-methylpropionic acid, 3-bromo-2-methylpropionic acid) or an acid halogen thereof,
A method of converting into a halopropionate compound, and then dehydrohalogenating the compound to form a (meth) acrylate ester;
The sulfur-containing (meth) acrylic acid ester compound represented by the formula (1) is produced by various known esterification methods (or thioesterification methods) such as those represented by specific examples.

[0038]

Embedded image (Wherein R ₁ , R ₂ , m and n are as defined above)

Among the above methods, the latter method is more preferable as a method for producing the sulfur-containing (meth) acrylate compound represented by the formula (1) of the present invention.

Hereinafter, as the most typical example of the above-mentioned methods, first, the above formula (2-a) or (2-b)
The method for reacting the sulfur-containing compound represented by the formula (II) with (meth) acrylic acids [(meth) acrylic acid, an ester derivative thereof, or an acid halide thereof] will be described in further detail.

That is, as the method, a known method,
For example, J. Org. Chem. , 45 volumes, 5364
(1980), Eur. Polym. J. , 19, 3
99 (1983).

For example, an acid halide of (meth) acrylic acid is added dropwise to the sulfur-containing compound represented by the formula (2-a) or (2-b) under stirring in the presence of a base. A dehydration reaction between the sulfur-containing hydroxy compound represented by the above formula (2-b) and (meth) acrylic acid in the presence of a catalyst, or a catalyst (acid catalyst Or a base catalyst) in the presence of the sulfur-containing hydroxy compound represented by the above formula (2-b) and (meth)
Acrylic ester derivatives [eg, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, etc.
For example, a transesterification reaction with an alkyl acrylate.

In the above reaction, a (meth) acrylic acid [for example, (meth) acrylic acid, which acts on the sulfur-containing compound represented by the above formula (2-a) or (2-b)
The ester derivative or the acid halide thereof is not particularly limited, but is usually 0.1 to 5 mol, preferably 0.25 mol, per 1 mol of the sulfur-containing compound. ~ 2.5 mol, more preferably
0.4-1.5 mol.

The reaction may be carried out without solvent or in an inert solvent for the reaction. Such solvents include, for example, hydrocarbon solvents such as n-hexane, benzene or toluene, ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone, ester solvents such as ethyl acetate or butyl acetate,
Ether solvents such as diethyl ether, tetrahydrofuran or dioxane, halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or perchrene, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide;
And polar solvents such as N, N-dimethylimidazolidinone. Two or more of these solvents may be used in combination.

The reaction temperature is not particularly limited, but is a temperature at which the raw material (meth) acrylic acid or the sulfur-containing (meth) acrylate compound of the reaction product is not polymerized.
−78 to 150 ° C., preferably -20 to
The temperature is 120 ° C, more preferably 0 to 100 ° C.

The reaction time depends on the reaction temperature, but is usually from several minutes to 100 hours, preferably from 30 minutes to 5 hours.
0 hour, more preferably 1 to 20 hours.
Further, it is also possible to stop the reaction at an arbitrary reaction rate while confirming the reaction rate by a known analysis means (for example, liquid chromatography, thin-layer chromatography, IR, etc.).

The reaction of the sulfur-containing compound represented by the above formula (2-a) or (2-b) with an acid halide of (meth) acrylic acid gives the sulfur-containing (meth) acrylate of the present invention. In producing the compound, hydrogen halide (eg, hydrogen chloride) is produced as a by-product. For example, triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.
2] octane (DABCO), organic base such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), or sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide ,
Inorganic bases such as potassium hydroxide, calcium hydroxide and magnesium oxide may be used as the dehydrohalogenating agent.

The amount of the dehydrohalogenating agent to be used is not particularly limited, but is 0.05 to 10 mol, preferably 1 to 10 mol, per 1 mol of the sulfur-containing compound represented by the above formula (2). , 0.1 to 5 mol, more preferably 0.1 to 5 mol.
5 to 3 mol.

The sulfur-containing (meth) acrylate compound represented by the formula (1) of the present invention is obtained by a dehydration reaction between the sulfur-containing hydroxy compound represented by the formula (2-b) and (meth) acrylic acid. It is preferable to use various known esterification catalysts when producing the. Examples of the catalyst include mineral acids (eg, hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, etc.) and organic acids (eg, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.). ), Lewis acids (for example, boron trifluoride, aluminum trichloride, titanium tetrachloride, titanium dichloride, tin dichloride, tin tetrachloride, etc.).

The amount of the catalyst used is not particularly limited, but is usually preferably 0.001 to 50% by mass, and more preferably 0.01 to 50% by mass, based on the reaction raw material mixture.
30% by mass.

In order to promote the progress of the reaction, it is preferable to remove by-product water out of the system. As such a method, for example, a solvent azeotropic with water (for example, Azeotropic dehydration using a hydrocarbon solvent such as benzene, toluene and xylene), a method using a dehydrating agent such as molecular sieve, or a method using these methods in combination.

In the above method, the above formula (2-a)
Or reacting a sulfur-containing compound represented by the formula (2-b) with a halopropionic acid or an acid halide thereof,
As a method for producing a halopropionate compound, followed by dehydrohalogenation to produce a sulfur-containing (meth) acrylate compound represented by the general formula (1), for example, JP-A-10-67736 And the like.

The sulfur-containing (meta) represented by the formula (1) of the present invention
When producing an acrylate compound, it is preferable to use a polymerization inhibitor in order to prevent polymerization of the product during or after the reaction. Examples of such a polymerization inhibitor include various known compounds such as 4-methoxyphenol, hydroquinone, and phenothiazine. The use amount of the polymerization inhibitor is not particularly limited, but is usually 0.01 to 5% by mass, preferably 0.05 to 3% by mass, based on the raw material mixture or the reaction product in the reaction system. is there.

After the completion of the reaction, the product (sulfur-containing (meth) acrylate compound represented by the formula (1)) of the present invention is subjected to known procedures and treatment methods (eg, neutralization, solvent extraction, water washing, Separation, evaporation of the solvent, etc.). Further, if necessary, the obtained sulfur-containing (meth) acrylate compound represented by the formula (1) is separated and purified by a known method (for example, distillation, recrystallization or chromatography), It can also be isolated as a highly pure compound.

The sulfur-containing compound of the present invention represented by the formula (2) is a novel compound, and is a halogen compound, a hydroxy compound or a thiol compound having a cyclic thioacetal structure in the molecule.

In the above formula (2), R ₁ and R ₂ each represent a hydrogen atom or an alkyl group, and R ₁ and R ₂
May combine with each other to form a ring.

The substituents R ₁ and R ₂ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
More preferably, they are a hydrogen atom, a methyl group or an ethyl group. When R ₁ and R ₂ are combined to form a ring, the ring is preferably a cycloalkane ring, more preferably a cycloalkane ring having 5 to 7 carbon atoms, and further preferably a cyclohexane ring. It is.

In the above formula (2), m is an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1.

In the above formula (2), n is 1 to 4
, Preferably 1 to 3, and more preferably 1 or 2.

In the above formula (2), X ₂ represents a halogen atom, a hydroxy group or a thiol group, preferably a halogen atom or a thiol group, and more preferably a thiol group.

Specific examples of the sulfur-containing compound represented by the formula (2) of the present invention include the compounds shown in Table 2 below.

[0062]

[Table 9]

[0063]

[Table 10]

[0064]

[Table 11]

[0065]

[Table 12]

[0066]

[Table 13]

[0067]

[Table 14]

In the sulfur-containing compound of the present invention represented by the formula (2), the compound in which X ₂ is a halogen atom is typically used as an aldehyde or a derivative thereof represented by the following formula (3). On the other hand, in the presence of an acid catalyst, the following formula (4)
By reacting dithiols represented by the formula (1).

[0069]

Embedded image (Wherein, X ₃ represents a halogen atom, and n represents an integer of 1 to 4)

[0070]

Embedded image (Wherein R ₁ , R ₂ and m are the same as above)

Further, the functional group X ₂ (halogen atom) in the cyclic thioacetal compound represented by the above formula (2) is
A known synthetic chemical method, for example, a method in which a halogen atom is alkali-hydrolyzed to be converted into a hydroxy group, or a method in which a thiourea is acted on a halogen atom to convert it to thiolonium, and then alkali-treated to form a thiol group In the formula (2) of the present invention, a compound in which X ₂ is a hydroxy group and a compound in which X ₂ is a thiol group can be suitably produced by a method of converting the compound into a thiol group.

Hereinafter, the aldehydes represented by the above formula (3) or derivatives thereof are reacted with dithiols represented by the above formula (4) in the presence of an acid catalyst, whereby The method for producing the compound in which X ₂ is a halogen atom in 2) will be described in more detail.

The aldehydes represented by the formula (3) or derivatives thereof include, for example, chloroacetaldehyde,
Haloalkyl aldehydes such as 3-chloropropionaldehyde, 3-bromopropionaldehyde, 4-chlorobutyraldehyde, 4-bromobutyraldehyde;
2-chloroacetaldehyde dimethyl acetal, 2-
Chloroacetaldehyde diethyl acetal, 2-chloropropionaldehyde dimethyl acetal, 2-chloropropionaldehyde diethyl acetal, 2-bromopropionaldehyde dimethyl acetal, 2-bromopropionaldehyde diethyl acetal, 2-bromopropionaldehyde ethylene acetal [or
2- (2'-bromoethyl) -1,3-dioxolane], 2-bromopropionaldehyde trimethylene acetal [or 2- (2'-bromoethyl) -1,
And dialkyl acetal derivatives or cyclic alkylene acetal derivatives of haloalkyl aldehydes such as [3-dioxane].

Examples of the dithiol derivative represented by the formula (4) include ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,2-butanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 1,2-pentanedithiol, 1,3
-Pentanedithiol, 1,4-pentanedithiol,
1,2-hexanedithiol, 1,3-hexanedithiol, 1,4-hexanedithiol, 1,2-heptanedithiol, 1,2-octanedithiol, 1,2-nonanedithiol, 1,2-decanedithiol and the like Chain alkanedithiols; cycloalkanedithiols such as cyclopentane-1,2-dithiol and cyclohexane-1,2-dithiol;

An aldehyde represented by the formula (3) or a derivative thereof is reacted with a dithiol represented by the formula (4) to obtain a compound wherein X ₂ is a halogen atom in the formula (2). Formula (4) used when manufacturing
The use amount of the dithiols represented by is not particularly limited, but is usually 0.5 to 5 mol per 1 mol of the aldehyde represented by the formula (3) or a derivative thereof, Preferably it is 0.8 to 2 mol, more preferably 0.9 to 1.2 mol.

In such a reaction, the reaction may be carried out under non-catalytic conditions, or a protic acid such as a mineral acid (for example, hydrochloric acid or sulfuric acid) or an organic acid (for example, acetic acid or propionic acid), or a Lewis acid. The reaction may be performed in the presence of a catalyst such as an acid. In consideration of the reaction temperature, the reaction time, and the like, it is preferable to carry out the reaction in the presence of a catalyst for the purpose of promoting the reaction.

As such a reaction catalyst, for example, sulfuric acid,
Protic acids such as hydrochloric acid, hydrobromic acid, nitric acid, acetic acid, propionic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid; titanium trichloride, titanium tetrachloride, tin dichloride, tin tetrachloride, Lewis acids such as boron fluoride ether complex and the like can be mentioned.

The amount of the reaction catalyst used is not particularly limited, but is usually 0.001 to 20 mol per 1 mol of the aldehyde represented by the formula (3) or a derivative thereof. , Preferably from 0.01 mol to 10 mol
Mol, more preferably 0.1 mol to 5 mol. These reaction catalysts may be used alone or as a mixture of two or more.

The reaction may be carried out without solvent or in the presence of a solvent. When a solvent is used, the solvent is not particularly limited as long as the solvent is inert to the reaction. Examples of the solvent include hydrocarbon solvents such as benzene, toluene, and xylene, methylene chloride, chloroform, and 1,2. −
Solvents such as halogen solvents such as dichloroethane, chlorobenzene and dichlorobenzene, and ether solvents such as diethyl ether, tetrahydrofuran, dioxane and diethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more.

The amount of the reaction solvent used is not particularly limited. However, if the amount is too large, it is not preferable in terms of production efficiency and the like. Usually, the aldehyde represented by the formula (3) or an acetal derivative thereof is used. Is 300 times by mass or less, preferably 100 times by mass or less.

The reaction may be carried out under an air atmosphere or an inert gas atmosphere. However, in order to suppress coloring of the reaction product, the reaction is carried out under an inert gas atmosphere such as nitrogen or argon. It is preferred.

The reaction temperature is not particularly limited, but is usually 0 ° C.
It is preferably carried out within the range of the boiling point of the solvent.

Although the reaction time varies depending on the reaction temperature, the reaction may be usually carried out within a range of several minutes to several tens of hours, and the reaction is followed by known analytical means (for example, liquid chromatography, thin layer chromatography, IR, etc.). Thus, the end point of the reaction can be determined.

In order to convert the substituent X ₂ (= halogen atom) in the compound represented by the formula (2) produced by the above method into a thiol group, a known method, for example, Journa
l of Organic Chemistry, Vol. 27, pp. 93-95 (19
62), Organic Synthesis, IV, pp. 401-403.
(1963) and the like. That is, in a typical method, a compound in which X ₂ = halogen atom in the formula (2) is reacted with thiourea and then hydrolyzed using a base such as aqueous ammonia or sodium hydroxide. In the formula (2), the compound wherein X ₂ is a thiol group is suitably produced.

The sulfur-containing compound of the present invention represented by the formula (2)
After the completion of the above reaction, the product is isolated from the reaction product by performing ordinary post-treatment operations (for example, neutralization, filtration, solvent extraction, water washing, liquid separation, solvent evaporation, and the like). In addition, the purity can be increased as necessary by a known operation and a purification method (for example, distillation, recrystallization, column chromatography, activated carbon treatment, and the like).

Next, the polymerizable composition containing the sulfur-containing (meth) acrylate compound represented by the formula (1) of the present invention will be described in detail.

The polymerizable composition of the present invention contains, as essential components, a sulfur-containing (meth) acrylate compound represented by the general formula (1) of the present invention, and a light and / or thermal polymerization initiator. I do. In this case, the above-mentioned sulfur-containing unsaturated carboxylate compound may be used alone, or a plurality of different sulfur-containing (meth) acrylate compounds may be used in combination.

Further, the polymerizable composition of the present invention may contain, if necessary, a sulfur-containing (meth) acrylate compound represented by the general formula (1) as long as the desired effect is not impaired. , A known polymerizable compound (such as a photo- or thermo-polymerizable monomer or oligomer).

The amount of the sulfur-containing (meth) acrylate compound represented by the general formula (1) contained in the polymerizable composition is not particularly limited, but is usually based on the total mass of the polymerizable composition. 10% by mass or more, preferably 2% by mass.
It is 0% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more.

The polymerization initiator used in the polymerizable composition of the present invention is not particularly limited, and various known thermal polymerization initiators or photopolymerization initiators can be used. Examples of the photopolymerization initiator include benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 1,1-dimethoxy-
1-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinol propan-1-one,
N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-ter
t-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-
Examples thereof include diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, and Michler's ketone. These can be used alone or in combination of two or more.

The amount of the photopolymerization initiator used is 0.001 to 50 parts by mass with respect to 100 parts by mass of the sulfur-containing (meth) acrylate compound represented by the formula (1). 0.01 to 30 parts by mass, more preferably,
0.1 to 10 parts by mass, more preferably 0.2 to 10 parts by mass.
To 5 parts by mass.

Examples of the thermal polymerization initiator include, for example, benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-
Examples include peroxides such as ethylhexyl peroxycarbonate and tert-butyl peroxypivalate, and azo compounds such as azobisisobutyronitrile.

The amount of the thermal polymerization initiator to be used is generally 0.001 to 50 parts by mass with respect to 100 parts by mass of the sulfur-containing (meth) acrylate compound represented by the formula (1).
Preferably, it is 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, still more preferably,
0.2 to 5 parts by mass.

Examples of known polymerizable compounds other than the sulfur-containing (meth) acrylate compound represented by the formula (1) as the polymerizable compound used in the polymerizable composition of the present invention include: Methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, ethyl carbitol (meth) acrylate, lauryl (meth) acrylate, tetracyclododecyl (meth) acrylate, phenoxyethyl (meth)
Acrylate, nonylphenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, Nn-butyl-O
-(Meth) acryloyloxyethyl carbamate, acryloyl morpholine, trifluoroethyl (meth) acrylate, tribromobenzyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate,

2,2-bis (4-acryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxyphenyl) propane, bis (4-acryloyloxyphenyl) methane, bis (4-methacryloyloxyphenyl) Methane, 4,4'-bis (acryloyloxy) diphenyl sulfide, 4,4'-bis (methacryloyloxy) diphenyl sulfide, 2,2-
Bis [4- (acryloyloxyethoxy) phenyl]
Propane, 2,2-bis [4- (methacryloyloxyethoxy) phenyl] propane, 2,2-bis [4-
(2-acryloyloxypropoxy) phenyl] propane, 2,2-bis [4- (2-methacryloyloxypropoxy) phenyl] propane, bis [4- (acryloyloxyethoxy) phenyl] methane, bis [4
-(Methacryloyloxyethoxy) phenyl] methane, bis [4- (2-acryloyloxypropoxy)
Phenyl] methane, bis [4- (2-methacryloyloxypropoxy) phenyl] methane, 4,4′-bis (2-acryloyloxyethoxy) diphenyl sulfide, 4,4′-bis (2-methacryloyloxyethoxy) Diphenyl sulfide, 4,4'-bis (2-
(Acryloyloxypropoxy) diphenyl sulfide, 4,4′-bis (2-methacryloyloxypropoxy) diphenyl sulfide, 4,4′-bis (2-
Acryloyloxyethoxy) diphenylsulfone,
4,4′-bis (2-methacryloyloxyethoxy) diphenylsulfone, 4,4′-bis (2-acryloyloxypropoxy) diphenylsulfone,
4,4'-bis (2-methacryloyloxypropoxy) diphenyl sulfone, ethylene oxide or propylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane di (meth) acrylate, bis (4-hydroxyphenyl) methane Ethylene oxide or propylene oxide adduct di (meth) acrylate, 4,4′-dihydroxyphenyl sulfide ethylene oxide or propylene oxide adduct di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylol tetraacrylate, dipentaerythritol hexaacrylate, 2- ( Data) acryloyloxyethyl tris isocyanurate, (meth) acryloxy propyl tris (methoxy) monofunctional or polyfunctional (meth) acrylates such as silane;

Phenol glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, resorcin diglycidyl ether, hydroquinone diglycidyl ether, bis (4
-Hydroxyphenyl) methane (commonly known as bisphenol F) diglycidyl ether, 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A) diglycidyl ether, 4,4′-bishydroxyphenyl sulfide diglycidyl ether, 4,4'-bishydroxyphenyl sulfone (commonly known as bisphenol S)
Diglycidyl ether, 4,4'-biphenol diglycidyl ether, 3,3 ', 5,5'-tetramethyl-
A (meth) acrylic acid compound is allowed to act on various known monovalent or divalent or higher-valent epoxy compounds such as 4,4′-biphenol diglycidyl ether and tris (2,3-epoxypropyl) isocyanurate. Epoxy (meth) acrylates obtained; (meth) acrylic acid compound acting on various known epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl resin type epoxy resin and bisphenol type epoxy resin Epoxy (meth) acrylates obtained by the reaction;

Vinyl compounds such as vinylbenzene, divinylbenzene, trivinylbenzene, isopropenylbenzene, diisopropenylbenzene, triisopropenylbenzene, N-vinylpyrrolidone and N-vinylcaprolactam; ethylene glycol diallyl carbonate;
Various known polymerizable monomers such as allyl group-containing compounds such as trimellitic acid triallyl ester and triallyl isocyanurate; or polyurethane (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates and poly Various known polymerizable oligomers such as ether (meth) acrylates are exemplified.

[0098] In order to further achieve the effects of the present invention, these amounts are usually used in an amount of 30 parts by mass per 100 parts by mass of the sulfur-containing (meth) acrylate compound represented by the formula (1).
It is 0 parts by mass or less, preferably 200 parts by mass or less, more preferably 100 parts by mass or less.

As a method for producing the polymerizable composition of the present invention,
Specifically, the sulfur-containing (meth) acrylate compound represented by the general formula (1) of the present invention is used, and if necessary, the above-mentioned known various polymerizable compounds are used in combination. It is obtained by mixing and dissolving after the addition. The polymerizable composition is used for polymerization and curing after removing insoluble matters and foreign substances by filtration before polymerization as required, and further sufficiently defoaming under reduced pressure.

When producing the polymerizable composition, an internal release agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a coloring pigment (for example, cyanine green, cyanine blue, etc.) may be used, if desired. It is also possible to add various known additives such as dyes, flow regulators, inorganic fillers (for example, talc, silica, alumina, barium sulfate, magnesium oxide, etc.).

The cured product of the present invention and an optical component comprising the cured product are obtained by polymerizing and curing the above polymerizable composition. As these methods, conventionally known various methods are adopted and suitably performed, but typically, the polymerizable composition obtained as described above is injected into a mold, and is started by heat or light. Cast polymerization using a radical polymerization reaction.

The mold is composed of two mirror-polished molds via a gasket made of, for example, polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride or the like. Examples of the mold include a combination of glass and glass, glass and a plastic plate, and glass and a metal plate. As the gasket, in addition to using the above-mentioned soft thermoplastic resin (polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, etc.), two molds may be fixed with a polyester adhesive tape or the like. Also,
A known treatment method such as a mold release treatment may be performed on the mold.

As the radical polymerization reaction, as described above, a polymerization reaction using heat (thermal polymerization), a polymerization reaction using light such as ultraviolet rays (photopolymerization), a polymerization reaction using gamma rays, or the like, Are exemplified.

When polymerization by light is performed, after the curing is completed,
The cured product obtained by releasing the mold or the optical component made of the cured product may be annealed for the purpose of removing internal stress and strain.

Among these methods, thermal polymerization requires several hours to several tens of hours, while photopolymerization using ultraviolet light or the like can be cured in a few seconds to several minutes. This is a preferable method in consideration of increasing productivity at the time.

In the case of performing thermal polymerization, the polymerization temperature is affected by the polymerization conditions such as the type of polymerization initiator, and is not limited, but is usually 25 to 200 ° C., preferably 50 to 170 ° C. .

As a method for molding an optical lens, as described above, for example, a method for obtaining a lens by performing cast polymerization using light or / and heat (for example, Japanese Unexamined Patent Publication No.
0-135901, JP-A-10-67736, JP-A-10-130250, etc.).

That is, the polymerizable composition containing the sulfur-containing (meth) acrylate compound represented by the formula (1) of the present invention produced by the above-mentioned method is optionally used,
After defoaming by a suitable method, it is preferably carried out by a method of injecting into a mold and polymerizing by irradiation of light. Further, the polymerization by heat is suitably performed by a method of performing polymerization by gradually heating from a low temperature to a high temperature.

After curing, the obtained optical lens may be subjected to an annealing treatment, if necessary. Further, if necessary, surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment, and / or the like for the purpose of imparting anti-reflection, imparting high hardness, improving abrasion resistance, imparting anti-fogging property or imparting fashionability. Various known physical or chemical treatments such as light treatment (for example, photochromic lens formation treatment) may be performed.

As a method for forming a substrate of an optical disk or a magneto-optical disk, for example, the formula (1) obtained by the above method is used.
A polymerizable composition containing a sulfur-containing (meth) acrylate compound represented by the formula is injected into a mold cavity for a disk substrate, and this is polymerized by a radical polymerization method or the like, and if necessary, post-heat treated ( JP-A-58-130450, JP-A-58-137150, and JP-A-62-28000.
No. 8), a method of photopolymerization in a double-sided glass mold (Japanese Patent Application Laid-Open No. 60-202557), and a method of thermally polymerizing a liquid resin by applying pressure after completion of vacuum casting or liquid injection (Japanese Patent Application Laid-Open No. 60-202557). -203414) and conventionally known methods.

The cured product obtained by photopolymerizing the polymerizable composition of the present invention, and the optical component comprising the cured product, require a few minutes to several hours for polymerization and curing, and use the existing polydiethylene glycol diallyl carbonate. One of the features is that it can be polymerized and molded in a shorter time and has higher productivity than a thermosetting optical resin represented by polythiourethane.

Further, the cured product and the optical component of the present invention are characterized by being excellent in optical properties, mechanical properties, and thermal properties and having a high refractive index. Specific examples of the optical component include various plastic lenses typified by corrective spectacle lenses, optical information recording medium substrates, plastic substrates for liquid crystal cells, and optical fiber coating materials.

The (meth) acrylate compound represented by the formula (1) of the present invention is a novel compound having a cyclic thioacetal structure in the molecule, and is used for optical members such as corrective spectacle lenses. It is a very useful compound as a resin raw material monomer.

[0114]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Synthesis Example of Sulfur-Containing Compound Represented by Formula (2) Example 1 [Exemplary Compound No. 2-2 in Table 2; Formula (2)
Where R ₁ = hydrogen atom, R ₂ = hydrogen atom, X ₂ = bromine atom, p = 0, q = 2 compound)] In a 500 ml glass reactor equipped with a stirrer, ethanedithiol 25. 4 g (0.27 mol), boron trifluoride ether complex 25 ml and toluene 10
0 g was added. To this mixture, 53.6 g of 2- (2'-bromoethyl) -1,3-dioxolane (0.2
(75 mol) was added dropwise at 20 ° C. over 1 hour. further,
After reacting at 20 ° C. for 5 hours, the reaction mixture was
Add 150 g of ice water and 50 g of toluene for 15 minutes,
After stirring, the mixture was allowed to stand and separated to extract a toluene phase. The toluene phase was alkali-washed with 150 g of a 3% aqueous sodium hydrogen carbonate solution, and further washed with water until the aqueous phase became neutral.
The toluene phase is separated and taken out.
The crude product obtained by evaporating at 0 ° C. was distilled under reduced pressure to obtain 51.8 g of 2- (2′-bromoethyl) -1,3-dithiolane as a colorless liquid.

Yield = 90%, Purity> 99% (Area method by gas chromatography analysis) Boiling point: 93-96 ° C./0.22 mmHg ¹ H-NMR δ (CDCl ₃ ): 2.2-2.3 ( m,
2H), 3.2 (s, 4H), 3.4 to 3.5 (m, 2
H) 4.6-4.7 (t, 1H) FD-MS: 212 (M), 214 (M + 2)

Example 2 [Exemplary Compound No. 2- in Table 2]
18; Synthesis of a compound of the formula (2) where R ₁ = hydrogen atom, R ₂ = hydrogen atom, X ₂ = thiol group, p = 0, q = 2] In a 500 ml glass reactor equipped with a stirrer Was charged with 32.0 g (0.42 mol) of thiourea and 175 g of ethanol. For this mixture, Example 1
44.8 g of 2- (2′-bromoethyl) -1,3-dithiolane prepared in the above was added dropwise at 50 ° C. over 35 minutes.
Further, the reaction was carried out at 80 ° C. for 4 hours to thiuronium chloride. The reaction solution was analyzed by high performance liquid chromatography to confirm that the raw material bromo compound had disappeared, and 200 g of 18% aqueous ammonia was added dropwise to the reaction mixture at 50 ° C over 10 minutes. For 2 hours to hydrolyze the thyuronium salt. Toluene 1
After adding and separating 00 g, the toluene phase was washed with water until the waste water phase became neutral, then the toluene phase was taken out, and the toluene was distilled off under reduced pressure at 40 ° C. to obtain a crude product. Was distilled under reduced pressure to obtain 31.6 g of colorless liquid 2- (2'-mercaptoethyl) -1,3-dithiolane.

Yield = 95%, Purity> 99% (Area method by gas chromatography analysis) Boiling point: 98-100 ° C./0.25 mmHg ¹ H-NMR δ (CDCl ₃ ): 1.7-1.8 ( br,
1H), 2.0 to 2.1 (m, 2H), 2.5 to 2.7
(M, 2H), 3.2-3.3 (m, 4H), 4.7-
4.8 (t, 1H) FD-MS: 166 (M)

Example 3 [Exemplary Compound No. 2- in Table 2]
32; Synthesis of a compound of the formula (2) where R ₁ = hydrogen atom, R ₂ = hydrogen atom, X ₂ = hydroxyl group, p = 0, q = 2] In a 100 ml glass reactor equipped with a stirrer 2- (2'-bromoethyl)-produced in Example 1
21.3 g (0.10 mol) of 1,3-dithiolane, 13.6 g (0.20 mol) of sodium formate and 1.61 g (0.005 mol) of tetramethylammonium bromide were added. The mixture is left at 110 ° C. for 1.5 hours,
The mixture was heated and stirred. After the completion of the reaction, 8.8 g of a 50% aqueous sodium hydroxide solution was added to the reaction mixture with stirring for 15 minutes.
Dropped over minutes. After the reaction product was extracted with toluene and washed with water, the toluene was distilled off at 40 ° C. under reduced pressure, and the obtained crude product was distilled under reduced pressure to obtain 2- (2′-hydroxyethyl)-as a colorless liquid. 13.5 g of 1,3-dithiolane was obtained.

Yield = 90%, Purity> 99% (Area method by gas chromatography analysis) Boiling point: 100-105 ° C./0.25 mmHg ¹ H-NMR δ (CDCl ₃ ): 2.0-2.1 ( m,
2H), 2.5-2.6 (br, 1H), 2.8-2.9
(M, 2H), 3.2-3.3 (m, 4H), 4.7-
4.8 (t, 1H) FD-MS: 150 (M)

Example 4 [Exemplary Compound No. 2- in Table 2]
5; in the formula (2), R ¹ = methyl group, R ₂ = hydrogen atom,
Synthesis of compound in which X ₂ = bromine atom, p = 0, q = 2] In the same manner as in Example 1, except that 1,2-propanedithiol is used instead of using ethanedithiol. Thus, 2- (2′-bromoethyl) -4-methyl-1,3-dithiolane as a colorless liquid was obtained. FD-MS: 226 (M), 228 (M + 2)

Example 5 [Exemplified Compound No. 2- in Table 2]
21; Synthesis of a compound of the formula (2) in which R ₁ = methyl group, R ₂ = hydrogen atom, X ₂ = thiol group, p = 0, q = 2] 2-
Instead of using (2'-bromoethyl) -1,3-dithiolane, use the 2- (2'-bromoethyl) -4-methyl-1,3-dithiolane prepared in Example 4 except for using. 2 and the colorless liquid 2- (2'-
(Mercaptoethyl) -4-methyl-1,3-dithiolane was obtained. FD-MS: 180 (M)

Example 6 [Exemplified Compound No. 2- in Table 2]
1; In the formula (2), R ₁ = hydrogen atom, R ₂ = hydrogen atom,
Synthesis of compound in which X ₂ = bromine atom, p = 0, q = 1] In Example 1, 2-bromomethyl-1,3 is used instead of using 2-bromoethyl-1,3-dioxolan.
-Colorless liquid 2-bromomethyl-4-methyl-1,3 except that dioxolane was used.
-Dithiolane is obtained. FD-MS: 198 (M), 200 (M + 2)

Example 7 [Exemplified Compound No. 2- in Table 2]
17; Synthesis of a compound of the formula (2) where R ₁ = hydrogen atom, R ₂ = hydrogen atom, X ₂ = thiol group, p = 0, q = 2] 2-
Instead of using (2'-bromoethyl) -1,3-dithiolane, 2-bromomethyl- produced in Example 6 was used.
Except that 1,3-dithiolane was used, the same procedure as in Example 2 was carried out to obtain colorless liquid 2-mercaptomethyl-4-methyl-1,3-dithiolane. FD-MS: 152 (M)

Synthesis of sulfur-containing (meth) acrylate compound represented by the formula (1) Example 8 [Exemplary Compound No. 1-2;
₁ = hydrogen atom, R ₂ = hydrogen atom, R ₃ = hydrogen atom, X ₁ = sulfur atom, synthesis of compound of m = 0, n = 2] Example 1 was placed in a glass 500 ml reaction vessel equipped with a stirrer. 2- (2'-mercaptoethyl) -1, produced by
100 g (0.60 mol) of 3-dithiolane is weighed,
On the other hand, 3-chloropropionic chloride 80 g
(0.63 mol) was added dropwise at 40 ° C. over 15 minutes. After further reacting with stirring at 40 ° C. for 8 hours, 200 g of toluene was added to the reaction mixture solution to dissolve the solution, and the solution was transferred to a separating funnel, and a 3% by mass aqueous sodium hydrogen carbonate solution 3 was added.
Washed three times with 00 g. Thereafter, the organic layer (toluene solution) was taken out after washing the aqueous layer with 300 g of pure water until neutral, and toluene was distilled off under reduced pressure to remove 2- [2- (3-chloropropionyl) as a colorless transparent liquid. Thio) ethyl]-
127 g of 1,3-dithiolane were obtained.

Then, into a 1-liter glass reaction vessel,
2- [2- (3-chloropropionylthio) ethyl] -1,3-dithiolane 127 obtained as above
g (0.49 mol) in a solution of 200 g of acetone, 74 g (0.73 mol) of triethylamine
Was added dropwise at 25 ° C. for 1 hour. Then, at 25 ° C, 6
After reacting with stirring for a period of time,
400 g of toluene and 400 g of water were added, and the toluene layer was separated and extracted and taken out. 5% by mass of the toluene solution
After washing with aqueous hydrochloric acid and further washing until the aqueous layer becomes neutral, toluene is distilled off under reduced pressure to give 2- (2′-acryloylthioethyl)-as the viscous colorless transparent liquid. 106 g of 1,3-dithiolane were obtained. Yield = 80%, Purity> 99% (Area method by liquid chromatography analysis) ¹ H-NMR δ (CDCl ₃ ); 2.0 to 2.1 (m,
2H), 2.5 to 2.7 (m, 2H), 3.2 to 3.3
(M, 4H), 4.7-4.8 (t, 1H), 5.0-
7.0 (m, 3H) FD-MS; 220 (M)

Example 9 [Exemplified Compound No. 1-44; In the formula (1), R ₁ = hydrogen atom, R ₂ = hydrogen atom, R ₃ =
Synthesis of compound in which methyl group, X ₁ = oxygen atom, m = 0, n = 2] 2- (2′-hydroxyethyl)-produced in Example 3
30.0 g (0.20 mol) of 1,3-dithiolane, 19.0 g (0.24 mol) of pyridine, chloroform 200
19.9 g (0.22 mol) of methacrylic acid chloride was added dropwise to the mixed solution (g) under ice-water cooling (10 ° C.). After the completion of the dropwise addition, the reaction was carried out by stirring at 10 ° C. for further 3 hours, and then the by-product pyridine hydrochloride was removed by filtration. The chloroform solution of the filtrate was further diluted with 200 g of diluted hydrochloric acid.
After washing with water, the solution was washed with water until the drainage layer became neutral, then separated, and the organic layer was taken out. Chloroform was distilled off at 60 ° C. under reduced pressure to obtain a crude product as a pale yellow transparent liquid. The crude product was purified by silica gel chromatography to obtain the target compound 2 as a viscous colorless transparent liquid.
-(2'-methacryloyloxyethyl) -1,3-
34.8 g of dithiolane were obtained. Yield = 80%, Purity> 99% (Area method by liquid chromatography analysis) ¹ H-NMR δ (CDCl ₃ ); 1.9 to 2.0 (s,
3H), 2.1 to 2.4 (m, 2H), 2.5 to 2.8
(M, 2H), 3.2-3.3 (m, 4H), 4.7-
4.8 (t, 1H), 5.0 to 7.0 (m, 2H) FD-MS; 218 (M)

Example 10 [Exemplified Compound No. 1-1; In the formula (1), R ₁ = hydrogen atom, R ₂ = hydrogen atom, R ₃ =
Synthesis of compound of hydrogen atom, X ₁ = sulfur atom, m = 0, n = 1] In Example 8, instead of using 2- (2′-mercaptoethyl) -1,3-dithiolane as a raw material, Except that the 2-mercaptomethyl-1,3-dithiolane prepared in Example 7 was used,
Acryloylthiomethyl-1,3-dithiolane was prepared. FD-MS; 206 (M)

Production of a polymerizable composition using a sulfur-containing (meth) acrylate compound represented by the formula (1) and production of a cured product by curing the composition.

The physical properties of the cured products or optical parts (lenses) produced in the following Examples and Comparative Examples were evaluated by the following methods. -Appearance: Color and transparency were visually confirmed. -Refractive index, Abbe number: 20 using a Pulfrich refractometer
Measured in ° C. Impact resistance: An iron ball of 28.7 g from a height of 127 cm was dropped on the center of a minus lens having a center thickness of 1.5 mm to check for cracks.

Example 11 30 g of the sulfur-containing acrylic acid ester compound (compound of Exemplified Compound No. 1-2) obtained in Example 8 was used as a photopolymerization initiator and treated with 2-hydroxy-2-methyl-1-. Phenylpropan-1-one (Darocur-117)
3, manufactured by Ciba-Geigy Co., Ltd.), mixed well, and dissolved. The resulting liquid was sufficiently defoamed under reduced pressure, and then poured into a mold composed of a glass mold and a gasket. Ultraviolet rays were irradiated for 60 seconds using a metal halide lamp (80 W / cm) to perform polymerization. After completion of the polymerization, the mixture was gradually cooled, and the formed cured product was taken out of the mold.

The obtained cured product was colorless and transparent, and no optical distortion was observed. The refractive index (nd) was 1.635 and the Abbe number was 36 (νd).

Example 12 In Example 11, instead of using the sulfur-containing (meth) acrylate compound of Exemplified Compound No. 1-2, the sulfur-containing (meth) acrylate of Exemplified Compound No. 1-44 produced in Example 9 was used. ) A polymerization composition was prepared and photo (ultraviolet) polymerization was carried out in the same manner as in Example 11 except that an acrylate compound was used.

The resulting cured product was colorless and transparent, and no optical distortion was observed. The refractive index (nd) was 1.615 and the Abbe number was 37 (νd).

Example 13 In Example 11, instead of using the sulfur-containing (meth) acrylate compound of Exemplified Compound No. 1-2, the sulfur-containing (meth) acrylate of Exemplified Compound No. 1-1 produced in Example 9 was used. )
Example 1 except that an acrylate compound was used
Preparation of polymer composition and light (ultraviolet light) in the same manner as in 1.
Polymerization was performed.

The obtained cured product was colorless and transparent, and no optical distortion was observed. The refractive index (nd) was 1.660 and the Abbe number was 35 (νd).

The sulfur-containing (meth) acrylate compound of the present invention could be cured (photopolymerized) by short-time light irradiation. The obtained cured product had a high refractive index and a high Abbe number, and the cured product had good heat resistance and impact resistance.

Example 14 To a mixture of 20 g of the sulfur-containing (meth) acrylate compound of Exemplified Compound No. 1-1 obtained in Example 10 and 5 g of epoxy acrylate of bisphenol A diglycidyl ether was added 2-hydroxy-2- 50 mg of methyl-1-phenylpropan-1-one (0.2% by mass with respect to the mass of the polymerizable compound) was added, mixed well, and dissolved.
After sufficiently degassing the obtained liquid, a mold consisting of a glass mold and tape (adjusted to minus lens shape)
Was injected. 60 UV rays by metal halide lamp
After irradiation for 2 seconds, annealing was performed by heating at 80 ° C. for 1 hour. After completion of the polymerization, the mixture was allowed to cool to room temperature, and had a diameter of 30 mm.
A colorless and transparent minus lens having a center thickness of 1.5 mm was obtained.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.645 and Abbe number (νd) was 35. As a result of the impact resistance test by the above method, no crack of the lens was recognized. The heat resistance of the lens was good.

Comparative Example 1 In Example 14, instead of using the sulfur-containing (meth) acrylate compound represented by the formula (1) of the present invention as a polymerizable compound, a known method was used (Japanese Patent Application Laid-Open No. 4-161410).
2, the acrylate compound described in
5-bis (acryloyloxyethylthiomethyl)-
Example 14 except that 24 g of 1,4-dithiane and 6 g of dimethylol tricyclodecane acrylate were used.
A polymerizable composition was prepared in the same manner as described in the above section to produce a lens.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.609 and Abbe number (νd) was 42. As a result of the impact resistance test by the above method, cracking of the lens was observed.

Comparative Example 2 In Example 14, instead of using the sulfur-containing (meth) acrylate compound represented by the formula (1) of the present invention as the polymerizable compound, a known compound was disclosed (JP-A-3-217412).
No. 1) is an acrylate compound described in
Polymerization was carried out in the same manner as in Example 14, except that 24 g of 4-bis (2-methacryloyloxyethylthio) xylylene and 6 g of 2,2-bis [4- (methacryloyloxyethoxy) phenyl] propane were used. A liquid composition was prepared to prepare a lens.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.588 and Abbe number (νd) was 39. As a result of the impact resistance test by the above method, cracking of the lens was observed.

Comparative Example 3 The procedure of Example 14 was repeated, except that the sulfur-containing (meth) acrylate compound represented by the formula (1) of the present invention was used as the polymerizable compound. 2-acryloyloxymethyl- described in Example 3
18 g of 1,4-dithiane, 6 g of benzyl methacrylate and ethylene glycol dimethacrylate
Example 1 except that a polymerizable compound consisting of 6 g was used.
A polymerizable composition was prepared in the same manner as in the method described in 4,
A lens was made.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.609 and Abbe number (νd) was 42. As a result of the impact resistance test by the method described above, cracks (cracks) were observed in the lens.

The cured product and the optical component obtained by polymerizing the polymerizable composition containing the sulfur-containing (meth) acrylate compound of the present invention have optical properties, thermal properties, and mechanical properties (impact resistance). , And can be polymerized and molded and cured in a short time (high productivity), and has a high refractive index.

[0147]

The sulfur-containing (meth) acrylate compound of the present invention is very useful as a monomer for a photocurable polymerizable composition in applications such as optical materials and dental materials. An optical component obtained by curing the polymerizable composition has excellent optical properties, thermal properties, and mechanical properties, and has good productivity, a high refractive index, and is represented by a corrective spectacle lens. It is useful as various plastic lenses, optical information recording medium substrates, plastic substrates for liquid crystal cells, optical fiber coating materials, and the like.

Further, according to the present invention, it has become possible to provide a sulfur-containing compound represented by the formula (2), which is very useful as a raw material intermediate for synthesizing a raw material monomer for such an optical resin.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masao Imai 580-32 Nagaura, Sodegaura-shi, Chiba In-house Mitsui Chemicals, Inc. Inventor Tadashi Okuma 580-32 Nagaura, Sodegaura-shi, Chiba Prefecture Mitsui Chemicals, Inc. (72) Inventor Rihoko 580, Nagaura, Sodegaura-shi, Chiba Prefecture 32 Inside Mitsui Chemicals, Inc. No. 32 Mitsui Chemicals, Inc.

Claims (5)

[Claims] 1. A sulfur-containing (meth) acrylate compound represented by the formula (1). Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and may combine with each other to form a ring, R ₃ represents a hydrogen atom or a methyl group, and X ₁ represents an oxygen atom or a sulfur atom. And m represents an integer of 0 to 3 and n represents an integer of 1 to 4) 2. A polymerizable composition containing the sulfur-containing (meth) acrylate compound according to claim 1. 3. A cured product obtained by polymerizing the polymerizable composition according to claim 2. 4. An optical component comprising the cured product according to claim 3. 5. A sulfur-containing compound represented by the formula (2). Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and may combine with each other to form a ring; X ₂ represents a halogen atom, a hydroxy group or a thiol group;
Represents an integer of 1 to 3, and n represents an integer of 1 to 4.)