JP2002128827A - Sulfur-containing (meth)acrylic acid thioester compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly refractive optical resin excellent in optical characteristics, mechanical characteristics, and thermal characteristics and also having good productivity. SOLUTION: This sulfur-containing (meth)acrylic acid thioester compound is represented by general formula (1) [wherein, R1 to R8 represent each independently H, an alkyl group, an alkoxy group, a nitro group or a halogen atom; R9 and R12 represent each independently H or an alkyl group; R10 and R13 represent each a substituent containing S; R11 and R14 represent each independently H or a methyl group; Y1 is a single bond and represents -C (R15)(R16) group (R15 and R16 represent each independently H, an alkyl group or an aryl group.), O, S or -SO2- group; Z1 and Z2 represent each independently O or S]. A polymerizable composition contains this acrylic acid thioester compound. A cured substance is obtained by polymerization of the polymerizable composition. An optical part comprises the cured substance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sulfur-containing (meth) acrylic acid thioester compound. Further, the present invention relates to a polymerizable composition containing the sulfur-containing (meth) acrylic acid compound, and an optical component obtained by polymerizing the polymerizable composition. The sulfur-containing (meth) acrylic acid thioester compound of the present invention is structurally characterized in that it contains a sulfur atom in the molecule, and is useful as a monomer for a photocurable polymerizable composition. 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.

[0002]

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 material is transparency. Up to the present, polymethyl methacrylate (PMMA), bisphenol A polycarbonate (BPA-PC), polystyrene (PS), methyl methacrylate-styrene copolymer (MS), styrene-acrylonitrile Polymerized polymer (SAN), poly (4-methylpentene-1)
(TPX), polycycloolefin (COP), polydiethylene glycol bisallyl carbonate (EGA)
C), polythiourethane (PTU) and the like are known.

[0004] PMMA has excellent transparency and weather resistance, and also has good moldability. However, there is a disadvantage that the refractive index (nd) is as small as 1.49 and the water absorption is large.
BPA-PC is excellent in transparency, heat resistance, impact resistance and high refraction, but has large chromatic aberration and its application field is limited. PS and MS are excellent in moldability, transparency, low water absorption and high refractive index, but are inferior in impact resistance, weather resistance and heat resistance and are hardly practically used as optical resins. SAN is considered to have a relatively high refractive index and a good balance of mechanical properties, but has some difficulty in heat resistance (heat deformation temperature: 80 to 90 ° C.) and is hardly used as an optical resin. .

[0005] 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 impact resistance, gas barrier properties and dyeability are poor. EGAC is a thermosetting resin containing diethylene glycol bisallyl carbonate as a monomer, and is most often used for general-purpose spectacle lenses. 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 a reaction between a diisocyanate compound and a polythiol compound, and is most frequently used for an ultra-high refractive index spectacle lens. Although it is particularly excellent in transparency, impact resistance, high refraction, and small in chromatic aberration, it is an extremely excellent material,
There is a drawback that the heat polymerization molding time is long (1 day to 3 days), and there remains a problem in productivity.

A method of obtaining an optical lens by photopolymerization using a (meth) acrylate containing a bromine atom or a sulfur atom for the purpose of polymerizing and curing in a short time to enhance the productivity. (For example, see Japanese Patent Laid-Open No. 4-1
No. 61410, JP-A-3-217412, etc.) or a method of obtaining an optical lens by photopolymerization using a sulfur atom-containing (meth) acrylic acid thioester (for example, US Pat. No. 4,931,521, USP
4810812). However, according to this method, although polymerization can be performed in a short time, the obtained resin is not always satisfactory as an optical component. For example, when used as a spectacle lens, those with a high refractive index are fragile and fragile,
There are problems such as high specific gravity, and the development of a material that overcomes these problems has been strongly desired.

As described above, the 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 a high-refractive optical resin having excellent optical properties, mechanical properties, and thermal properties and high productivity.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the drawbacks of conventional optical resins and to provide a high-refractive optical resin which is excellent in optical properties, mechanical properties and thermal properties and has good productivity. To provide.

[0009]

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) acrylic acid thioester compound represented by the following general formula (1), and a polymerizable composition containing the sulfur-containing (meth) acrylic acid thioester compound, The present invention relates to a cured product obtained by polymerizing a polymerizable composition, and further relates to an optical component comprising the cured product.

[0010]

Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a substituent containing a sulfur atom, R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a methyl group, Y ¹ represents a single bond, —C (R ¹⁵ ) (R ¹⁶ )-
Groups (R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and in the case of an alkyl group or an aryl group, may combine to form a ring), an oxygen atom, a sulfur atom,- Represents an SO ₂ — group, and Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom]

Further, the present invention relates to a sulfur-containing dimercapto compound represented by the following general formula (2), which is a raw material compound for the sulfur-containing (meth) acrylic acid thioester compound.

[0012]

Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a substituent containing a sulfur atom, Y ¹ is a single bond, a —C (R ¹⁵ ) (R ¹⁶ ) — group (R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, Represents an alkyl group or an aryl group, and in the case of an alkyl group or an aryl group, may combine to form a ring.), An oxygen atom, a sulfur atom, a —SO ₂ — group, and Z ¹ and Z ² represent Each independently represents an oxygen atom or a sulfur atom]

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The sulfur-containing (meth) acrylic acid thioester compound of the present invention is represented by the general formula (1), has a substituent containing a sulfur atom in the molecule, and has a secondary or tertiary thiol (meth) It is a novel compound characterized in that it is an acrylic acid thioester.

In the general formula (1), R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom, and preferably have a hydrogen atom or a substituent. Represents a straight-chain, branched or cyclic alkyl group, a straight-chain, branched or cyclic alkoxy group, a nitro group or a halogen atom which may have a substituent, and more preferably a hydrogen atom or a substituent. 1 to 2 carbon atoms which may be
0 represents a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, a nitro group or a halogen atom.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R
Specific examples of ⁷ and R ⁸ include, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, isobutyl group, sec-butyl group, tert
-Butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-
Dodecyl group, n-tetradecyl group, n-octadecyl group, cyclopentyl group, cyclohexyl group, 4-ter
t-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclohexylmethyl, cyclohexylethyl, tetrahydrofurfuryl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 3-methoxy Propyl, 3-ethoxypropyl, 3-n-propoxypropyl, 3-n-butoxypropyl, 3-n-hexyloxypropyl, 2
-Methoxyethoxyethyl group, 2-ethoxyethoxyethyl group, 2-phenoxymethyl group, 2-phenoxyethoxyethyl group, chloromethyl group, 2-chloroethyl group,
3-chloropropyl group, 2,2,2-trichloroethyl group,

Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, n-pentyloxy, n-
Hexyloxy group, 2-ethylhexyloxyl group, n-
Octyloxy group, n-decyloxy group, n-dodecyloxy group, n-tetradecyloxy group, n-octadecyloxy group, cyclopentyloxy group, cyclohexyloxy group, 4-tert-butylcyclohexyloxy group, cycloheptyloxy group, Cyclooctyloxy group, cyclohexylmethoxy group, cyclohexylethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-butoxyethoxy group, 3-methoxypropoxy group, 3-ethoxypropoxy group, 3-n-propoxy Propoxy group, 3-n-butoxypropoxy group, 3-
n-hexyloxypropoxy group, 2-methoxyethoxyethoxy group, 2-phenoxymethoxy group, 2-phenoxyethoxyethoxy group, chloromethoxy group, 2-chloroethoxy group, 3-chloropropoxy group, 2,2,2-
Examples thereof include a trichloroethoxy group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ and R ⁸ are more preferably a hydrogen atom and carbon number 1
Unsubstituted linear or branched alkyl group having 10 to 10 carbon atoms, unsubstituted linear or branched alkoxy group having 1 to 10 carbon atoms, nitro group, chlorine atom, bromine atom, more preferably hydrogen atom, methyl Group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, ter
t-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, nitro group, chlorine atom and bromine atom. The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
A hydrogen atom and a methyl group are particularly preferred as R ⁶ , R ⁷ and R ⁸ .

In the general formula (1), the substituents R ⁹ and R ¹²
Each independently represents a hydrogen atom or an alkyl group,
More preferably, they are a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. Further, in the general formula (1), the substituents R ¹⁰ and R ¹³ each independently represent a substituent containing a sulfur atom, and the structure of the substituent contains at least one sulfur atom. And Specific examples of the substituents R ¹⁰ and R ¹³ include the substituents represented by the following formula (a) or (b). R ¹⁷ -O- (a) R ¹⁸ -S- (b) (wherein, R ¹⁷ represents a monovalent organic group containing at least one sulfur atom, and R ¹⁸ contains a sulfur atom. Represents a good monovalent organic group)

In the above formula, the substituent R ¹⁷ preferably represents an alkyl group, an aralkyl group, an aryl group or an acyl group which may have a substituent containing at least one sulfur atom. The substituent R ¹⁷ also includes a heterocyclic-containing group. In the above formula, the substituent R ¹⁸ preferably represents an alkyl group, an aralkyl group, an aryl group or an acyl group which may have a substituent. further,
In order to obtain a high refractive index, it is more preferable that these substituents contain a sulfur atom.

The above-mentioned substituents R ¹⁰ and R ¹³ are preferably a chain or cyclic alkoxy group containing a sulfur atom, an aralkyloxy group containing a sulfur atom, or an aryl containing a sulfur atom. An oxy group, an acyloxy group containing a sulfur atom, a chain or cyclic alkylthio group optionally containing a sulfur atom, an aralkylthio group optionally containing a sulfur atom, containing a sulfur atom. Arylthio group and acylthio group optionally containing a sulfur atom.

The substituents R ¹⁰ and R ¹³ include, for example, methylthioethoxy, ethylthioethoxy, propylthioethoxy, butylthioethoxy, methylthioethylthioethoxy, methylthioethylthioethylthioethoxy, 2 , 2-dimethylthioethoxy group, 2,2
-Diethylthioethoxy group, 2,2-dipropylthioethoxy group, 2,2-dibutylthioethoxy group, 3,3-
Dimethylthiopropoxy group, 3,3-diethylthiopropoxy group, 3,3-dipropylthioethoxy group, 3,3
-Dibutylthioethoxy group, (1,3-dithiolane-2
-Yl) methoxy group, 2- (1,3-dithiolan-2-
Yl) ethoxy group, 3- (1,3-dithiolan-2-yl) propoxy group, (1,3-dithiolan-4-yl)
Methoxy group, 2- (1,3-dithiolan-4-yl) ethoxy group, 3- (1,3-dithiolan-4-yl) propoxy group, (1,4-dithian-2-yl) methoxy group, A-(1,4-dithian-2-yl) ethoxy group,
3- (1,4-dithian-2-yl) propoxy group,
(1,3,5-trithian-2-yl) methoxy group, 2
A-(1,3,5-trithian-2-yl) ethoxy group,
3- (1,3,5-trithian-2-yl) propoxy group,

A 4-methylthiobenzyloxy group, a 3-methylthiobenzyloxy group, a 2-methylthiobenzyloxy group, a 2,4-dimethylthiobenzyloxy group,
4-dimethylthiobenzyloxy group, 2,4,6-trimethylthiobenzyloxy group, 4-methylthiophenylethoxy group, 3-methylthiophenylethoxy group, 2-
Methylthiophenylethoxy group, 2,4-dimethylthiophenylethoxy group, 3,4-dimethylthiophenylethoxy group, 2,4,6-trimethylthiophenylethoxy group, 4-methylthiophenyloxy group, 3-methylthiophenyloxy group , 2-methylthiophenyloxy group, 2,4-dimethylthiophenyloxy group, 2,5-
Dimethylthiophenyloxy group, 2,6-dimethylthiophenyloxy group, 3,4-dimethylthiophenyloxy group, 3,5-dimethylthiophenyloxy group, 2,
4,6-trimethylthiophenyloxy group, 2,3
4,5,6-pentamethylthiophenyloxy group,

Methylthio, ethylthio, propylthio, butylthio, methoxyethylthio, butoxyethylthio, methoxypropylthio, cyclohexylthio, 2-methylthioethylthio, 2-ethylthioethylthio, 2 -Propylthioethylthio group, 2-
Butylthioethylthio, methylthioethylthioethylthio, methylthioethylthioethylthioethylthio, 2,2-dimethylthioethylthio, 2,2-diethylthioethylthio, 2,2-dipropylthioethyl Thio group, 2,2-dibutylthioethylthio group, 3,3-
Dimethylthiopropylthio group, 3,3-diethylthiopropylthio group, 3,3-dipropylthioethylthio group,
3,3-dibutylthioethylthio group, (1,3-dithiolan-2-yl) methylthio group, 2- (1,3-dithiolan-2-yl) ethylthio group, 3- (1,3-dithiolan-2 -Yl) propylthio group, (1,3-dithiolan-4-yl) methylthio group, 2- (1,3-dithiolan-4-yl) ethylthio group, 3- (1,3-dithiolan-4-yl) propylthio Group, (1,3-dithiane-
2-yl) methylthio group, 2- (1,3-dithiane-2)
-Yl) ethylthio group, 3- (1,3-dithiane-2-
Yl) propylthio group, (1,4-dithian-2-yl) methylthio group, 2- (1,4-dithian-2-yl) ethylthio group, 3- (1,4-dithian-2-yl) propylthio group , (1,3,5-trithiane-2-
Yl) methylthio group, 2- (1,3,5-trithiane-
2-yl) ethylthio group, 3- (1,3,5-trithian-2-yl) propylthio group,

Benzylthio, 4-methylbenzylthio, 4-methoxybenzylthio, 4-methylthiobenzylthio, 3-methylthiobenzylthio, 2-methylthiobenzylthio, 2,4-dimethylthiobenzylthio A 3,4-dimethylthiobenzylthio group, 2,
4,6-trimethylthiobenzylthio, 4-methylthiophenylethylthio, 3-methylthiophenylethylthio, 2-methylthiophenylethylthio, 2,
4-dimethylthiophenylethylthio group, 3,4-dimethylthiophenylethylthio group, 2,4,6-trimethylthiophenylethylthio group, phenylthio group, 4-methylphenylthio group, 4-methoxyphenylthio group, 4
-Methylthiophenylthio group, 3-methylthiophenylthio group, 2-methylthiophenylthio group, 2,4-dimethylthiophenylthio group, 2,5-dimethylthiophenylthio group, 2,6-dimethylthiophenylthio group, 3,
4-dimethylthiophenylthio group, 3,5-dimethylthiophenylthio group, 2,4,6-trimethylthiophenylthio group, 2,3,4,5,6-pentamethylthiophenylthio group, thiazoline-2- Ilthio group,

A methylthiomethylcarbonyloxy group, a methylthioethylcarbonyloxy group, a (1,3-dithiolan-2-yl) carbonyloxy group, a (1,3-dithiolan-4-yl) carbonyloxy group, a (1,3- (Dithian-2-yl) carbonyloxy group, (1,4-dithian-2-yl) carbonyloxy group, (1,3,5
-Trithian-2-yl) carbonyloxy group, 4-methylthiobenzoyloxy group, thiophen-2-carbonyloxy group, thiazole-2-carbonyloxy group,
Methylthiomethylcarbonylthio group, methylthioethylcarbonylthio group, (1,3-dithiolan-2-yl)
Carbonylthio group, (1,3-dithiolan-4-yl)
Carbonylthio group, (1,3-dithian-2-yl) carbonylthio group, (1,4-dithian-2-yl) carbonylthio group, (1,3,5-trithian-2-yl)
Examples include a carbonylthio group, a benzoylthio group, a 4-methylthiobenzoylthio group, a thiophen-2-carbonylthio group, and a thiazole-2-carbonylthio group, but are not limited thereto.

In the general formula (1), R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

In the general formula (1), Y ¹ is a single bond,
^{-C (R 15) (R 16} ) - group (R ^15, R ^{1 6} are each independently a hydrogen atom, an alkyl group, an aryl group, an alkyl group, in the case of aryl groups to form a ring or), oxygen atom, sulfur atom, -SO ₂ -. represents a group, preferably a single bond, -CH ₂ - group, -C (CH _{3) 2} -
Group, a sulfur atom and a 9-fluorenylidene group.

In the general formula (1), Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom, and preferably both Z ¹ and Z ² are an oxygen atom or both are a sulfur atom.

As the sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) of the present invention, the following formulas (1-A), (1-B), (1-C) or (1-C) −
D), and is preferably a structure represented by the formula (1-
A), (1-B) or a structure represented by the formula (1-C), and particularly preferred is a sulfur-containing (meth) acrylic acid thioester compound represented by the formula (1-B).

[0030]

Embedded image (In the above formula, R ^{1 to} R ¹⁶ , Z ¹ and Z ² are the same as described above.)

Specific examples of the sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) of the present invention include the compounds shown in Table 1 below. It is not limited.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

[Table 6]

[0038]

[Table 7]

[0039]

[Table 8]

[0040]

[Table 9]

[0041]

[Table 10]

[0042]

[Table 11]

[0043]

[Table 12]

[0044]

[Table 13]

[0045]

[Table 14]

[0046]

[Table 15]

[0047]

[Table 16]

[0048]

[Table 17]

[0049]

[Table 18]

[0050]

[Table 19]

[0051]

[Table 20]

[0052]

[Table 21]

[0053]

[Table 22]

[0054]

[Table 23]

[0055]

[Table 24]

[0056]

[Table 25]

[0057]

[Table 26]

[0058]

[Table 27]

[0059]

[Table 28]

[0060]

[Table 29]

[0061]

[Table 30]

[0062]

[Table 31]

[0063]

[Table 32]

[0064]

[Table 33]

The sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) of the present invention is a novel compound and is produced according to a known reaction method. The sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) of the present invention is typically suitably produced by the route represented by the following scheme (c).

[0066]

Embedded image (Wherein R ^{1 to} R ¹⁴ , Y ¹ , Z ¹ and Z ² are the same as above)

That is, as described later in detail, a compound containing a sulfur atom represented by R ¹⁰ -H or R ¹³ -H is added to the bisepithiopropyl compound represented by the general formula (3) ( (Sulfur-containing compound) to produce a sulfur-containing dimercapto compound of the present invention represented by the general formula (2) as a synthetic intermediate. For example, a method of reacting a (meth) acrylic acid with the sulfur-containing dimercapto compound represented by the general formula (2), a halopropionic acid (for example, 3-chloropropionic acid, 3-bromopropionic acid, Chloro-2-methylpropionic acid, 3-bromo-2-methylpropionic acid, etc.) or an acid halide thereof to give a halopropionic acid ester compound, and then dehydrohalogenated to give a (meth) acrylic acid thioester. The sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) of the present invention is suitably produced by various known esterification methods, such as a typical method. Sulfur-containing (meta) represented by the general formula (1) of the present invention
Using an acrylic acid thioester compound, the polymerizable composition of the present invention, when producing a cured product or an optical component obtained by polymerizing the polymerizable composition, without separation and purification of these mixtures Can be used as is.

The dimercapto compound represented by the general formula (2) of the present invention includes the following general formulas (2-A) and (2-A).
B), a structure represented by formula (2-C) or formula (2-D), preferably a structure represented by formula (2-A), (2-B) or formula (2-C) In particular, the formula (2-B)
The dimercapto compound represented by is particularly preferable.

[0069]

Embedded image (Wherein R ^{1 to} R ¹⁴ , Y ¹ , Z ¹ and Z ² are the same as above)

Specific examples of the dimercapto compound represented by the general formula (2) of the present invention include the compounds shown in Table 2 below, but the present invention is not limited thereto.

[0071]

[Table 34]

[0072]

[Table 35]

[0073]

[Table 36]

[0074]

[Table 37]

[0075]

[Table 38]

[0076]

[Table 39]

[0077]

[Table 40]

[0078]

[Table 41]

[0079]

[Table 42]

[0080]

[Table 43]

[0081]

[Table 44]

[0082]

[Table 45]

[0083]

[Table 46]

[0084]

[Table 47]

[0085]

[Table 48]

[0086]

[Table 49]

[0087]

[Table 50]

[0088]

[Table 51]

[0089]

[Table 52]

[0090]

[Table 53]

[0091]

[Table 54]

[0092]

[Table 55]

[0093]

[Table 56]

[0094]

[Table 57]

[0095]

[Table 58]

[0096]

[Table 59]

[0097]

[Table 60]

[0098]

[Table 61]

[0099]

[Table 62]

[0100]

[Table 63]

[0101]

[Table 64]

[0102]

[Table 65]

[0103]

[Table 66]

First, the method for producing the sulfur-containing dimercapto compound represented by the general formula (2) in the above scheme (c) will be described in detail.

The sulfur-containing dimercapto compound represented by the general formula (2) of the present invention is different from the bisepithiopropyl compound represented by the general formula (3) by the general formula (4-a) or (4-a) The compound is suitably produced by reacting the sulfur-containing compound represented by b) with a ring-opening addition to an episulfide group. The reaction method itself is known and is carried out according to conventionally known reaction conditions. For example, if necessary, the reaction is suitably carried out in the presence of a suitable catalyst (eg, an acid catalyst, a base catalyst, etc.). Will be

[0106]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ ,
R ¹⁰ , R ¹² , R ¹³ , Y ¹ , Z ¹ and Z ² are the same as described above)

In such a reaction, the amount of the sulfur-containing compound used to act on the bisepithiopropyl compound represented by the general formula (3) is not particularly limited. The amount is 0.1 to 10 mol, preferably 0.5 to 5 mol, and more preferably 1 to 3 mol, per 1 mol of the represented bisepithiopropyl compound.

The reaction may be carried out without solvent or in a solvent. The solvent is not particularly limited as long as it is a solvent inert to the reaction, and examples thereof include hydrocarbon solvents such as n-hexane, benzene, and toluene;
Acetone, ketone solvents such as 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, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or Halogen-based solvents such as perchrene are exemplified. Two or more of these solvents may be used in combination. The reaction temperature is not particularly limited,
Usually, it is in the range of 0 ° C to 200 ° C, preferably 0 to 1
00 ° C. The reaction time depends on conditions such as the reaction temperature, but is usually from several minutes to several tens of hours.

Next, a method for producing the sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) of the present invention using the sulfur-containing dimercapto compound represented by the general formula (2) as a raw material will be described. It will be described in detail. As described above, as a method of converting a sulfur-containing dimercapto compound represented by the general formula (2) into a sulfur-containing (meth) acrylic acid thioester, typically, the following general formulas (5-a) and (5-a) b)
Reacting with (meth) acrylic acid or an acid halide thereof represented by the formula: after reacting with chloropropionic acid or an acid halide thereof to obtain a chloropropionate compound, dehydrohalogenating the (meth) acrylic acid And a method for preparing an acid thioester compound.

[0110]

Embedded image (In the formula, R ¹¹ and R ¹⁴ are the same as above. X represents a hydroxyl group or a halogen atom.)

Hereinafter, as the most typical examples of the above-mentioned methods, a dimercapto compound represented by the general formula (2) and a (meth) compound represented by the general formulas (5-a) and (5-b)
The method of reacting acrylic acid or its acid halide will be described in more detail. That is, as the method, a known method, for example, US Pat.
2, J. Org. Chem. , 45, 5364 (198
0), Eur. Polym. J. , 19, 399 (19
A method similar to the method described in 83) can be used. For example, under stirring, the dimercapto compound represented by the general formula (2) is reacted with the general formulas (5-a) and (5-a).
(b) dropping an acid halide of (meth) acrylic acid represented by the above method,
Alternatively, a method of performing a dehydration reaction between the dimercapto compound represented by the general formula (2) and the (meth) acrylic acids represented by the general formulas (5-a) and (5-b) is exemplified.

In the above reaction, a compound of the general formula (5-a) acting on the dimercapto compound represented by the general formula (2)
The amount of the (meth) acrylic acid or the acid halide thereof represented by the formula (5) and (5-b) is not particularly limited, but is usually based on 1 mol of the dimercapto compound.
It is 0.1 to 10 mol, preferably 0.5 to 5 mol, and more preferably 1 to 3 mol.

The reaction may be carried out without a solvent or in a solvent inert to the reaction. Examples of such a solvent include hydrocarbon solvents such as n-hexane, benzene, xylene, and toluene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; Amide solvents such as -dimethylformamide, N, N-dimethylacetamide or 1,3-dimethyl-2-imidazolidinone, ether solvents such as diethyl ether, tetrahydrofuran or dioxane,
Dichloromethane, chloroform, carbon tetrachloride, 1,2-
Halogen-based solvents such as dichloroethane or perchrene,
And the like. Two or more of these solvents may be used in combination.

Although the reaction temperature is not particularly limited, it is a temperature at which the (meth) acrylic acid as a raw material or the (meth) acrylic acid thioester compound as a reaction product is not polymerized.
−78 to 150 ° C., preferably -20 to
It is 100 degreeC, More preferably, it is -10-80 degreeC. The reaction time depends on the reaction temperature, but is usually several minutes to
It is 100 hours, preferably 30 minutes to 50 hours, 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 dimercapto compound represented by the general formula (2) with an acid halide of a (meth) acrylic acid represented by the general formulas (5-a) and (5-b) provides the present invention. When a sulfur-containing (meth) acrylic acid thioester compound is produced, hydrogen halide (e.g., hydrogen chloride) is by-produced. For example, triethylamine,
Pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.
0] Organic bases such as undec-7-ene (DBU), or sodium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium oxide, etc. An inorganic base may be used as the dehydrochlorination agent. The amount of the dehydrohalogenating agent to be used is not particularly limited, but is 0.1 to 10 mol, preferably 0.5 to 10 mol, per 1 mol of the dimercapto compound represented by the general formula (2). -5 mol, more preferably 1-3
Is a mole.

The dimercapto compound represented by the general formula (2) and the (meth) acrylic acid represented by the general formulas (5-a) and (5-b) are subjected to a dehydration reaction to obtain the compound represented by the general formula (1) When the (meth) acrylic acid thioester compound represented by the formula (1) is produced, it is preferable to use various known esterification catalysts. Examples of the catalyst include mineral acids (eg, hydrochloric acid, sulfuric acid), organic acids (eg, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid), Lewis acids (eg, boron trifluoride, aluminum trichloride) ) And the like. The use amount of such a catalyst is not particularly limited, but is usually 0.001 to 50% by mass, preferably 0.01 to 30% by mass, based on the reaction raw material mixture. In order to promote the progress of the reaction, it is preferable to remove by-product water out of the system. For example, a solvent azeotropic with water (for example, benzene, toluene, or the like) may be used or a molecular solvent may be used. A method using a dehydrating agent such as sieves may be used.

In the above-mentioned method, the dimercapto compound represented by the general formula (2) is reacted with a halopropionic acid or an acid halide thereof to form a halopropionic ester compound, and then dehydrohalogenated. General formula (1)
As a method for producing the (meth) acrylic acid thioester compound represented by, for example, JP-A-10-67736
For example, a method described in Japanese Unexamined Patent Publication (Kokai) No. HEI 10-301 is exemplified.

In the production of the (meth) acrylic acid thioester compound represented by the general formula (1), it is preferable to use a polymerization inhibitor in order to prevent polymerization of the product during or after the reaction. That is. 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 sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) of the product 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) acrylic acid thioester derivative represented by the general formula (1) is separated and purified by a known method (for example, distillation, recrystallization or chromatography). Can be isolated as a highly pure compound.

Next, the polymerizable composition containing the sulfur-containing (meth) acrylic acid thioester derivative represented by the general 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) acrylic acid thioester compound represented by the general formula (1) of the present invention, and a light and / or thermal polymerization initiator. In this case, the (meth) acrylic acid thioester compound may be used alone, or a plurality of different (meth) acrylic acid thioester compounds may be used in combination.

Further, the polymerizable composition of the present invention may contain, if necessary, a sulfur-containing (meth) acrylic acid thioester 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) acrylic acid thioester compound represented by the general formula (1) contained in the polymerizable composition is not particularly limited, but is usually 10 to the mass of the entire polymerizable composition. % By mass, preferably 20% by mass or more, more preferably 30% by mass or more, 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. As the photopolymerization initiator, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-
2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2
-Morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone ,
2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone And the like.
These can be used alone or in combination of two or more.

The amount of the photopolymerization initiator used is determined by the general formula (1)
It is 0.001 to 50 parts by mass, preferably 0.01 to 30 parts by mass, more preferably 0.01 to 30 parts by mass, based on 100 parts by mass of the acrylic acid thioester compound represented by
0.1 to 10 parts by mass, more preferably 0.2 to 10 parts by mass.
To 5 parts by mass. Further, it is preferable to simultaneously use one or more of these photopolymerization initiators and known photosensitizers. Examples of the photosensitizer include N, N-dimethylaminobenzoic acid ethyl ester,
N, N-dimethylaminobenzoic acid isoamyl ester,
Triethanolamine, triethylamine and the like can be mentioned.

Preferred combinations of the photopolymerization initiator and the photosensitizer include a combination of 2,4-diethylthioxanthone or 2-isopropylthioxanthone and N, N-dimethylaminobenzoic acid ethyl ester, Preferred combinations of the agents are 2
-Methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one and a combination of 2,4-diethylthioxanthone or 2-isopropylthioxanthone.

As the thermal polymerization initiator, 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 used is represented by the general formula (1)
(Meth) acrylic acid thioester compound 10 represented by the following formula:
With respect to 0 parts by mass, it is usually 0.001 to 50 parts by mass, preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, further preferably, 0.2 to 5 parts by mass.

As the polymerizable compound used in the polymerizable composition of the present invention, a known polymerizable compound other than the (meth) acrylic acid thioester compound represented by the general formula (1) is, for example, methyl (Meth) acrylate,
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl carbitol (meth) acrylate, lauryl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxy Propyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, Nn-butyl-O- (meth) acryloyloxyethyl carbamate, acryloylmorpholine, trifluoroethyl (meth) acrylate, tribromobenzyl Monofunctional (meth) acrylates such as (meth) acrylate and perfluorooctylethyl (meth) acrylate; silicon such as (meth) acryloxypropyltris (methoxy) silane Containing (meth) acrylates;
Alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate;

Polyalkylene glycol di (meth) acrylates such as triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate; bisphenol F , Bisphenol A, di (meth) acrylates of alkylene oxide adducts of bisphenol derivatives such as hydrogenated bisphenol A; trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Polyfunctional (meth) acrylates such as ditrimethylol tetraacrylate and dipentaerythritol hexaacrylate; Di (meth) acrylate Ji glycol diglycidyl ether, di (meth) acrylate of propylene glycol diglycidyl ether, (meth) acrylate of phenol glycidyl ether,
Epoxy (meth) acrylates such as (meth) acrylate of resorcin diglycidyl ether, di (meth) acrylate of bisphenol A diglycidyl ether, and (meth) acrylate of 4,4'-bishydroxyphenyl sulfide diglycidyl ether;

Reaction product of an epoxy compound such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, tris (2,3-epoxypropyl) isocyanurate with acrylic acid or methacrylic acid Epoxy acrylates; monofunctional vinyl compounds such as vinylbenzene, divinylbenzene, N-vinylpyrrolidone, and N-vinylcaprolactam; allyl groups such as ethylene glycol diallyl carbonate, triallylic acid triallyl ester, and triallyl isocyanurate Known polymerizable monomers such as contained compounds, or polyurethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) a Various known polymerizable oligomers such relations are exemplified. The amount of these is usually 300 parts by mass or less based on 100 parts by mass of the sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) in order to further achieve the effects of the present invention. , Preferably 200 parts by mass or less, more preferably 100 parts by mass.
Not more than parts by mass.

As a method for producing the polymerizable composition of the present invention,
Specifically, the sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) of the present invention is used, and if necessary, the above-mentioned known 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. Further, when producing the polymerizable composition, if desired, an internal release agent,
Light stabilizer, UV absorber, antioxidant, coloring pigment (eg, cyanine green, cyanine blue, etc.), dye, flow regulator, inorganic filler (eg, talc, silica, alumina, barium sulfate, magnesium oxide, etc.) It is also possible to add various known additives such as.

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. Further, 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. Among these methods, thermal polymerization requires several hours to several tens of hours, whereas photopolymerization using ultraviolet light or the like can be cured in a matter of seconds to several minutes. This is a preferable method in consideration of enhancing the properties. When performing thermal polymerization, the polymerization temperature is affected by polymerization conditions such as the type of polymerization initiator, and is not limited.
° C, preferably 50 to 170 ° C.

As a method of molding an optical lens, as described above, for example, a method of obtaining a lens by performing cast polymerization using light or / and heat (for example, Japanese Patent Application Laid-Open No.
0-135901, JP-A-10-67736, JP-A-10-130250, etc.). That is, the general formula (1) of the present invention produced by the method described above
After defoaming the polymerizable composition containing the sulfur-containing (meth) acrylic acid thioester compound represented by the following formula, if necessary, inject into a mold, and usually irradiate with light. It is preferably carried out by a method of polymerizing. 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. The obtained optical lens may be subjected to surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat, if necessary, for the purpose of anti-reflection, imparting high hardness, improving abrasion resistance, imparting anti-fog properties or imparting fashionability. Various known physical or chemical treatments such as a treatment, a staining treatment, and a light control treatment (for example, a photochromic lens formation treatment) may be performed.

As a method for molding a substrate of an optical disk or a magneto-optical disk, for example, a polymerizable composition containing a sulfur-containing (meth) acrylic acid thioester compound represented by the general formula (1) obtained by the above method may be used. A method of injecting the mixture into a disk substrate mold cavity, polymerizing the mixture by a radical polymerization method or the like, and performing post-heat treatment as necessary (Japanese Patent Laid-Open No. 58-13 / 1983)
Nos. 0450 and 58-137150 and 62
JP-A-280008), 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 injection (Japanese Patent Application Laid-Open No. No. 60-203414) and conventionally known methods.

The cured product obtained by photopolymerization of the polymerizable composition of the present invention, and the optical component comprising the cured product, require several 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 than a thermosetting optical resin represented by polythiourethane and has high productivity. Furthermore, the cured product and the optical component of the present invention have excellent optical, mechanical, and thermal characteristics and 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.

[0135]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples and Examples, but the present invention is not limited to these Examples. The physical properties of the cured product or optical component (lens) produced in each of the following examples were evaluated by the following methods. -Appearance: Color and transparency were visually observed. -Refractive index, Abbe number: 2 using Pulfrich refractometer
It was measured at 0 ° 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. ：: No crack on lens ×: Crack on lens

Example 1 [Production of sulfur-containing dimercapto compound represented by formula (2) of the present invention] 220.4 g (2.00 mol) of benzenethiol, 3.0 g (0.075 mol) of sodium hydroxide, A dimethylbiphenylbis (epithiopropyl) ether 3 of the following formula (3-1) was added to a raw material mixture of 300 g of methanol.
A solution of 86.6 g (1.00 mol) dissolved in 400 g of methanol was added dropwise at 10 ° C. for 1 hour. After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 3 hours,
After confirming that there was no remaining raw material by (high performance liquid chromatography), the reaction solution was discharged into ice water. The oily product was extracted with 300 g of toluene, washed repeatedly with water until the drainage layer became neutral, and then separated to remove the organic layer. The toluene was distilled off at 40 ° C. under reduced pressure to obtain 549.1 g of a viscous slightly yellow transparent liquid sulfur-containing dimercapto compound of the formula (2-1).

[0137]

Embedded image

The results of mass spectrometry of the product are shown below. FD-MS: 606 (M +)

Example 2 [Production of sulfur-containing dimercapto compound represented by formula (2) of the present invention] In Example 1, instead of using benzenethiol, 2-mercaptomethyl-1,3-dithiolane, In the same manner as in Example 1, except that bisphenol A bisepithiopropyl ether of the following formula (3-2) is used instead of using dimethylbiphenylbis (epithiopropyl) ether of (3-1). As a result, a colorless transparent liquid sulfur-containing dimercapto compound represented by the following formula (2-2) was obtained.

[0140]

Embedded image

The measurement results of the product by mass spectrometry are shown below. FD-MS: 676 (M +)

Example 3 [Production of a sulfur-containing dimercapto compound represented by the formula (2) of the present invention] In Example 1, instead of using benzenethiol, 1,3-dithiolan-2-carboxylic acid was used. (3
-1) Dimethylbiphenylbis (epithiopropyl)
A colorless transparent liquid represented by the following formula (2-3) was prepared in the same manner as in Example 1 except that diphenyl sulfide bisepithiopropyl ether of the following formula (3-3) was used instead of using ether. The sulfur-containing dimercapto compound represented was obtained.

[0143]

Embedded image

The measurement results of the product by mass spectrometry are shown below. FD-MS: 662 (M +)

Examples 4 to 23 By the same method as described in Examples 1 to 3 above, the reaction between the bisepithiopropyl compound and the sulfur-containing compound was carried out to obtain the general formula of the present invention shown in Table 3 below. A sulfur-containing dimercapto compound represented by (2) was produced.

[0146]

[Table 67]

[0147]

[Table 68]

Example 24 72.8 g (0.12 mol) of the sulfur-containing dimercapto compound represented by the formula (2-1) produced in Example 1 and pyridine 1
To a mixed solution of 9.0 g (0.24 mol) and 200 g of chloroform, 23.5 g (0.26 mol) of acrylic acid chloride was added dropwise 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. After the chloroform solution of the filtrate was further washed with 200 g of dilute hydrochloric acid, water was washed until the drainage phase became neutral, followed by liquid separation, and the organic phase was taken out. Chloroform under reduced pressure
The residue was distilled at ℃ to obtain a crude product as a pale yellow transparent liquid. The crude product was purified by silica gel chromatography to obtain 68.6 g of a sulfur-containing acrylic acid thioester compound represented by the following formula (1-1) as a viscous colorless transparent liquid.

[0149]

Embedded image

The results of mass spectrometry of the product are shown below. FD-MS: 714 (M +)

Example 25 The procedure of Example 24 was repeated, except that the dimercapto compound represented by the formula (2-2) produced in Example 2 was used instead of using the dimercapto compound represented by the formula (2-1). In the same manner as in Example 4, a sulfur-containing acrylic acid thioester compound represented by the following formula (1-2) was obtained as a colorless transparent liquid.

[0152]

Embedded image

The results of mass spectrometry of the product are shown below. FD-MS: 784 (M +)

Example 26 In Example 24, a dimercapto compound represented by the formula (2-3) produced in Example 3 was used instead of using the dimercapto compound represented by the formula (2-1). In the same manner as in the method described in Example 24, a sulfur-containing acrylic acid thioester compound represented by the following formula (1-3) was obtained as a colorless transparent liquid.

[0155]

Embedded image

The measurement results of the product by mass spectrometry are shown below. FD-MS: 770 (M +)

Example 27 A colorless transparent liquid was prepared in the same manner as in Example 24 except that methacrylic acid chloride was used instead of acrylic acid chloride. The sulfur-containing methacrylic acid thioester compound represented by 4) was obtained.

[0158]

Embedded image

The measurement results of the product by mass spectrometry are shown below. FD-MS: 742 (M +)

Examples 28 to 47 The sulfur-containing (meth) acrylic acid thioesters represented by the general formula (1) of the present invention shown in Table 4 below were prepared in the same manner as described in the above Examples 24 to 27. The compound was obtained.

[0161]

[Table 69]

[0162]

[Table 70]

Example 48 To 30 g of the sulfur-containing acrylic acid thioester compound of the formula (1-1) obtained in Example 24 was added 2-hydroxy-2-methyl-1-phenylpropane- as a photopolymerization initiator.
30 mg of 1-one (Darocur-1173, Ciba-Geigy) was added, 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. Use a metal halide lamp (80 W / cm) to emit 60 UV rays.
The polymerization was performed by irradiation for 2 seconds. 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 1.633 and the Abbe number (νd) was 30.3.

Examples 42 to 74 In Example 41, the sulfur-containing acrylic acid thioester compounds produced in Examples 25 to 47 were used instead of using the acrylic acid thioester compound of the formula (1-1). In the same manner as described in Example 48,
A cured product was obtained. Table 5 shows the physical properties of the obtained cured product after polymerization.

[0165]

[Table 71]

Example 75 To a mixture of 20 g of the acrylic acid thioester compound of the formula (1-2) obtained in Example 25, 5 g of an epoxy acrylate of resorcin diglycidyl ether represented by the following formula (d) and 5 g of divinylbenzene was added. , 2-hydroxy-2-methyl-1-phenylpropan-1-one 60 m
g (0.2% by mass relative to the polymerizable monomer) was added and mixed and dissolved well. After sufficiently defoaming the obtained liquid, it was poured into a mold composed of a glass mold and a tape.
After irradiating with a metal halide lamp for 60 seconds, ultraviolet rays were heated at 80 ° C. for 1 hour to perform polymerization. After completion of the polymerization, the mixture is allowed to cool to room temperature, and has a diameter of 30 mm and a center thickness of 1.5 mm.
I got a minus lens. The lens is colorless and transparent,
Refractive index (nd) is 1.628, Abbe number (νd) is 3
4.7. Glass transition temperature (T
g) was 70 ° C. or higher. Further, as a result of the impact resistance test by the above method, there was no crack of the lens.

[0167]

Embedded image

Examples 76 to 81 In the same manner as in Example 75, a polymerizable composition having the composition shown in Table 6 was prepared to prepare a lens. Table 6 shows the results of evaluating the physical properties of the lens.

[0169]

[Table 72]

The cured product and the optical component obtained by polymerizing the polymerizable composition containing the sulfur-containing (meth) acrylic acid thioester 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.

[0171]

The sulfur-containing (meth) acrylic acid thioester compound of the present invention is useful as a monomer for a photocurable polymerizable composition. 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.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 1/04 G02B 1/04 (72) Inventor Atsushi Ohtsuji 580-2, Takuji Nagaura, Takuji Nagaura, Sodegaura-shi, Chiba 32 F-term (reference) in Mitsui Chemicals, Inc. 4H006 AA01 AB46 TA04 TB14 TB31 TB35 TB74 TB76 TC23 TN10 TN30 TN60 4J100 AL65P AL71P AP02P BA04P BA41P BA51P BB00P BC43P CA01 DA63 JA33

Claims (13)

[Claims] 1. A sulfur-containing (meth) acrylic acid thioester compound represented by the following general formula (1). Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a substituent containing a sulfur atom, R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a methyl group, Y ¹ represents a single bond, —C (R ¹⁵ ) (R ¹⁶ )-
Groups (R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and in the case of an alkyl group or an aryl group, may combine to form a ring), an oxygen atom, a sulfur atom,- Represents an SO ₂ — group, and Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom] 2. A sulfur-containing (meth) acrylic acid thioester compound represented by the following general formula (1-A). Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a sulfur atom-containing substituent; R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a methyl group; Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom Represents 3. A sulfur-containing (meth) acrylic acid thioester compound represented by the following general formula (1-B). Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a substituent containing a sulfur atom, R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a methyl group, and R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group. And Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom] 4. A sulfur-containing (meth) acrylic acid thioester compound represented by the following general formula (1-C). Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a sulfur atom-containing substituent; R ¹¹ and R ¹⁴ each independently represent a hydrogen atom or a methyl group; Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom Represents 5. A sulfur-containing (meth) acrylic acid thioester compound represented by the following general formula (1-D). Embedded image [Wherein, R ⁹ and R ¹² each independently represent a hydrogen atom or an alkyl group, R ¹⁰ and R ¹³ each independently represent a substituent containing a sulfur atom, and R ¹¹ and R ¹⁴ each independently represent Represents a hydrogen atom or a methyl group, and Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom. 6. A polymerizable composition containing the sulfur-containing (meth) acrylic acid thioester compound according to claim 1. 7. A cured product obtained by polymerizing the polymerizable composition according to claim 6. 8. An optical component comprising the cured product according to claim 7. 9. A sulfur-containing dimercapto compound represented by the following general formula (2). Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a substituent containing a sulfur atom, Y ¹ is a single bond, a —C (R ¹⁵ ) (R ¹⁶ ) — group (R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, Represents an alkyl group or an aryl group, and in the case of an alkyl group or an aryl group, may combine to form a ring.), An oxygen atom, a sulfur atom, a —SO ₂ — group, and Z ¹ and Z ² represent Each independently represents an oxygen atom or a sulfur atom] 10. A sulfur-containing dimercapto compound represented by the following general formula (2-A). Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a substituent containing a sulfur atom, and Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom.] 11. A sulfur-containing dimercapto compound represented by the following general formula (2-B). Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a substituent containing a sulfur atom, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group, and Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom. Represents) 12. A sulfur-containing dimercapto compound represented by the following general formula (2-C). Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group,
A nitro group or a halogen atom, a R ^9, R ¹² each independently represent a hydrogen atom or an alkyl group, R ^10,
R ¹³ each independently represents a substituent containing a sulfur atom, and Z ¹ and Z ² each independently represent an oxygen atom or a sulfur atom.] 13. A sulfur-containing dimercapto compound represented by the following general formula (2-D). Embedded image [Wherein, R ⁹ and R ¹² each independently represent a hydrogen atom or an alkyl group, R ¹⁰ and R ¹³ each independently represent a substituent containing a sulfur atom, and Z ¹ and Z ² each represent Independently represents an oxygen atom or a sulfur atom)