JP2002275216A - Acrylic ester compound and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical resin having a high refractive index, good transparency, thermal characteristics and mechanical properties and excellent in workability and productivity. SOLUTION: The objective acrylic ester compound is represented by the general formula (1) [wherein, R1 and R2 are each independently H, a (substituted) alkyl, a (substituted) aromatic alkyl or a (substituted) aromatic residue; R3 is H or an alkyl; A is a bivalent organic group; X is S or O; and if X is O, R1 is a (substituted) aromatic residue], and a polymerizable composition containing the compound, a cured product obtained by polymerizing the polymerizable composition and optical components are also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an acrylate compound, a method for producing the same, and a sulfur-containing compound as an intermediate for the synthesis thereof. Further, the present invention relates to a polymerizable composition containing the acrylate compound, a cured product obtained by polymerizing the polymerizable composition, and an optical component.

The acrylate compound of the present invention is a novel compound having a specific dithiolane ring structure in the molecule, and is useful as a monomer for a photocurable polymerizable composition. An optical component obtained by curing the polymerizable composition has good optical properties, thermal properties, and mechanical properties, and is excellent in productivity, has 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, transparent coating materials such as antireflection films and optical fiber coating materials, LED sealing materials, dental 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 (organic optical materials) in place of inorganic glass has been actively conducted.

A fundamentally important property as an optical resin is transparency. Up to 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 (CO
P), polydiethylene glycol bisallyl carbonate (EGAC), 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.

Although PS and MS are excellent in moldability, transparency, low water absorption and high refraction, they are inferior 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 used.

TPX and COP are transparent, have low water absorption,
Although having excellent heat resistance, it has 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.

An optical lens is obtained by photopolymerization using an acrylate compound containing a bromine atom or a sulfur atom as a polymerizable compound for the purpose of performing polymerization and curing in a short time to enhance the productivity. Method (for example, JP-A-63-248811, JP-A-3-21
No. 7412), having a sulfur-containing alicyclic structure (meth)
A method of obtaining an optical lens using an acrylate compound (for example, Japanese Patent Application Laid-Open No. Hei 3-215081) has been proposed.

However, according to these methods, the obtained resin has never been satisfactory when used as an optical material. That is, for example,
Although the viscosity of the polymerizable compound (monomer) is high and the fluidity is low, there is a problem that the operation efficiency is reduced during operations such as filtration and injection into a mold, or polymerization can be performed in a short time. If the refractive index or Abbe number is not sufficiently high, or if used as a spectacle lens, high refractive index ones are fragile and easily cracked, and have a large specific gravity. Development was strongly desired.

As described above, conventional optical resins have excellent characteristics, but at present, each has its own disadvantages to be overcome. Under such circumstances, the development of a high-refractive-index optical resin having excellent transparency, thermal properties, and mechanical properties, and excellent workability and productivity has been desired. It is the current situation.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the conventional optical resin, and to improve transparency,
An object of the present invention is to provide a high-refractive-index optical resin which has good thermal characteristics and mechanical characteristics, and is excellent in workability and productivity.

[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 an acrylate compound represented by the general formula (1).

[0017]

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(Wherein R ₁ and R ₂ are each independently
A hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or an aromatic residue which may have a substituent, and R ₃ is a hydrogen atom Or an alkyl group, A represents a divalent organic group, and X represents a sulfur atom or an oxygen atom. However, when X is an oxygen atom, R ₁ represents an aromatic residue which may have a substituent.

Further, a polymerizable composition containing the acrylate compound represented by the above general formula (1), a cured product obtained by polymerizing the polymerizable composition, and an optical composition comprising the cured product Related to parts.

Further, the present invention provides a method for producing an acrylate compound represented by the above general formula (1), wherein the sulfur-containing compound represented by the following general formula (2) is acrylated. In particular, the compound of the general formula (2) is reacted with a halopropionic acid or an acid halide thereof to form a halopropionate compound, and then dehydrohalogenated to form an acrylate. About the method.

Furthermore, the present invention relates to a sulfur-containing compound represented by the general formula (2), which is useful as a raw material of the acrylate compound.

[0022]

Embedded image

Wherein R ₁ and R ₂ are each independently
A represents a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or an aromatic residue which may have a substituent; X represents an organic group, and X represents a sulfur atom or an oxygen atom. Where X
When is an oxygen atom, R ₁ represents an aromatic residue which may have a substituent)

[0024]

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

The acrylate compound represented by the general formula (1) of the present invention is a novel compound characterized by having a specific dithiolane ring structure.

In the general formula (1), R ₁ and R ₂ are
Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent, or an aromatic residue which may have a substituent.
Here, “aromatic alkyl group” and “aromatic residue” mean that the former is directly bonded to a constituent atom of the aromatic ring while the latter is bonded via an alkyl group. Which means that the aromatic ring in these groups may be a heterocyclic ring containing a hetero atom and having aromaticity.

However, when X in the general formula (1) is an oxygen atom, R ₁ represents an aromatic residue which may have a substituent.

When R ₁ and / or R ₂ is an alkyl group which may have a substituent, the substituent contained in the alkyl group may be an alkoxy group, an alkoxyalkoxy group, an aromatic alkyloxy group, Examples include an aryloxy group, an aryloxyalkyloxy group, an alkylthio group, an alkylthioalkylthio group, an aromatic alkylthio group, an arylthio group, and an arylthioalkylthio group.

When R ₁ and / or R ₂ is an aromatic alkyl group or an aromatic residue which may have a substituent, the aromatic ring in the aromatic alkyl group or the aromatic residue may be substituted. Is preferably performed. Examples of such a substituent include an alkyl group, an alkoxy group, an alkoxyalkoxy group, an aralkyloxy group, an aryl group, an aryloxy group, an aryloxyalkyloxy group, an alkylthio group, an alkylthioalkylthio group, an aralkylthio group, an arylthio group, and an arylthioalkylthio group. Or a halogen atom.

The aromatic ring in the aromatic alkyl group or aromatic residue in which R ₁ and / or R ₂ may have a substituent includes aromatic hydrocarbons such as benzene, naphthalene, anthracene and phenanthrene; Or thiophene, pyridine, pyrrole, furan, γ-pyran, γ-thiopyran, thiazole, imidazole, pyrimidine, 1,3,
Rings such as heterocyclic rings having aromaticity such as 5-triazine, indole, quinoline, and purine are exemplified.

The substituents R ₁ and R ₂ in the general formula (1)
Are each independently preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkyl group formed by combining these, or a combination thereof, and a carbon atom which may have a substituent. An aromatic alkyl group having 5 to 20 carbon atoms, an aromatic residue having 4 to 20 carbon atoms which may have a substituent,
More preferably, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, a cyclic or cyclic or a combination thereof, and 5 to 5 carbon atoms which may have a substituent
It is an aromatic alkyl group having 12 and an aromatic residue having 4 to 12 carbon atoms which may have a substituent.

Specific examples of such substituents R ₁ and R ₂ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, ter
t-butyl group, n-pentyl group, isopentyl group, n-
Hexyl group, heptyl group, octyl group, cyclohexyl group, cyclohexylmethyl group, etc., straight-chain, branched or cyclic alkyl group, benzyl group, 4-methylbenzyl group,
Substituted or unsubstituted aromatic alkyl group such as 4-chlorobenzyl group, 4-bromobenzyl group, β-phenylethyl group, etc., phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-phenylphenyl group, 4-phenoxyphenyl group, 3-phenoxyphenyl group, 2-phenoxyphenyl group, 4-methylthiophenyl group, 3 -Methylthiophenyl group, 2-methylthiophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 3-bromophenyl group, 2
Substituted or unsubstituted aromatic residues such as -bromophenyl group, α-naphthyl group, β-naphthyl group, 2-furyl group, 3-furyl group, thiophen-2-yl group, thiophen-3-yl group, etc. And the like.

The substituent R ₁ and / or R ₂ is more preferably a hydrogen atom, a methyl group, a benzyl group, a β
-Phenylethyl group, phenyl group, thiophen-2-yl group, thiophen-3-yl group, 4-phenylphenyl group, α-naphthyl group or β-naphthyl group.

Considering the effects of the present invention, the substituent R ₁
Are particularly preferably phenyl, thiophen-2-yl, thiophen-3-yl, 4-phenylphenyl, α-naphthyl or β-naphthyl.

In the general formula (1), R ₃ represents a hydrogen atom or an alkyl group. The substituent R ₃ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the general formula (1), A represents a divalent organic group. The organic group A is preferably an alkylene group optionally containing an oxygen atom or a sulfur atom, and more preferably an alkylene group optionally containing an oxygen atom or a sulfur atom having 1 to 10 carbon atoms. And more preferably a group represented by the following formula (a).

[0037]

Embedded image

In the above formula (a), B has 1 to 3 carbon atoms.
Represents an alkylene group, preferably a methylene group,
2-ethylene group, trimethylene group, propylene group (1-
Methyl-1,2-ethylene group).

In the above formula (a), Y is an oxygen atom or a sulfur atom, preferably a sulfur atom.

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

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

In the general formula (1), X represents an oxygen atom or a sulfur atom, and is preferably a sulfur atom.

To obtain various desired effects of the present invention,
In the general formula (1), one of R _{1 and} R ₂ is preferably an aromatic residue which may have a substituent,
More preferably, X is a sulfur atom, R ₁ is an aromatic residue which may have a substituent, and R ₂ is a hydrogen atom.

Examples of the acrylate compound represented by the general formula (1) of the present invention include, for example, 4-acryloylthiomethyl-1,3-dithiolane and 2-methyl-4-acryloylthiomethyl-1,3- Dithiolane, 2-ethyl-4-acryloylthiomethyl-1,3-dithiolane, 2-n-propyl-4-acryloylthiomethyl-
1,3-dithiolane, 2-n-butyl-4-acryloylthiomethyl-1,3-dithiolane, 2-phenyl-4
-Acryloylthiomethyl-1,3-dithiolane, 2-
(4′-methylphenyl) -4-acryloylthiomethyl-1,3-dithiolane, 2- (3′-methylphenyl) -4-acryloylthiomethyl-1,3-dithiolane, 2- (2′-methylphenyl) ) -4-Acryloylthiomethyl-1,3-dithiolane, 2- (4′-ter
t-butylphenyl) -4-acryloylthiomethyl-
1,3-dithiolane, 2- (4′-methoxyphenyl)
-4-acryloylthiomethyl-1,3-dithiolane,
2- (4'-phenylphenyl) -4-acryloylthiomethyl-1,3-dithiolane, 2- (4'-phenoxyphenyl) -4-acryloylthiomethyl-1,3-
Dithiolane, 2- (4'-methylthiophenyl) -4-
Acryloylthiomethyl-1,3-dithiolane, 2-
(2,4,6-trimethylthiophenyl) -4-acryloylthiomethyl-1,3-dithiolane, 2- (4′-
(Chlorophenyl) -4-acryloylthiomethyl-1,
3-dithiolane, 2- (4'-bromophenyl) -4-
Acryloylthiomethyl-1,3-dithiolane, 2-
(Α-naphthyl) -4-acryloylthiomethyl-1,
3-dithiolane, 2- (β-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane, 2,2-dimethyl-4-acryloylthiomethyl-1,3-dithiolane, 2-methyl-2-phenyl- 4-acryloylthiomethyl-1,3-dithiolane, 2,2-diphenyl-4
-Acryloylthiomethyl-1,3-dithiolane,

4- (2-acryloylthioethyl)-
1,3-dithiolane, 4- (3-acryloylthiopropyl) -1,3-dithiolane, 4- (2-methyl-2-
Acryloylthioethyl) -1,3-dithiolane, 4-
Acryloylthiomethylthiomethyl-1,3-dithiolane, 4- (2-acryloylthioethylthio) methyl-
1,3-dithiolane, 4- (3-acryloylthiopropylthio) methyl-1,3-dithiolane, 4- (2-methyl-2-acryloylthioethylthio) methyl-1,
3-dithiolane, 4- [2- (acryloylthiomethylthio) ethyl] -1,3-dithiolane, 4- [2- (2
-Acryloylthioethylthio) ethyl] -1,3-dithiolane, 4- [2- (3-acryloylthiopropylthio) ethyl] -1,3-dithiolane, 4- [2- (2
-Methyl-2-acryloylthioethylthio) ethyl]
-1,3-dithiolane, 4- [3- (acryloylthiomethylthio) propyl] -1,3-dithiolane, 4-
[3- (2-acryloylthioethylthio) propyl]
-1,3-dithiolane, 4- [3- (3-acryloylthiopropylthio) propyl] -1,3-dithiolane,
4- [3- (2-methyl-2-acryloylthioethylthio) propyl] -1,3-dithiolane, 4- [2-methyl-2- (acryloylthiomethylthio) ethyl]-
1,3-dithiolane, 4- [2-methyl-2- (2-acryloylthioethylthio) ethyl] -1,3-dithiolane, 4- [2-methyl-2- (3-acryloylthiopropylthio) ethyl -1,3-dithiolane, 4-
[2-methyl-2- (2-methyl-2-acryloylthioethylthio) ethyl] -1,3-dithiolane,

2- (4-methylphenyl) -4- (2-
Acryloylthioethyl) -1,3-dithiolane, 2-
α-naphthyl-4- (3-acryloylthiopropyl)
-1,3-dithiolane, 2-phenyl-4- (acryloylthiomethylthio) methyl-1,3-dithiolane,
-(4-methoxyphenyl) -4- (2-acryloylthioethylthio) methyl-1,3-dithiolane, 2-
(4-bromophenyl) -4- (2-acryloylthiopropylthio) methyl-1,3-dithiolane, 2- (thiophen-2-yl) -4- (2-methyl-2-acryloylthioethylthio) methyl -1,3-dithiolane,
2-freel-4- [2- (2-acryloylthioethylthio) ethyl] -1,3-dithiolane, 2- (4-methylthiophenyl) -4- [3- (acryloylthiomethylthio) propyl] -1, 3-dithiolane, 2-β-
Naphthyl-4- [2-methyl-2- (acryloylthiomethylthio) ethyl] -1,3-dithiolane,

2-methyl-4-acryloyloxymethyl-1,3-dithiolane, 2-phenyl-4-acryloyloxymethyl-1,3-dithiolane, 2- (4'-
Methylphenyl) -4-acryloyloxymethyl-
1,3-dithiolane, 2- (4′-methoxyphenyl)
-4-acryloyloxymethyl-1,3-dithiolane, 2- (4'-phenylphenyl) -4-acryloyloxymethyl-1,3-dithiolane, 2- (4'-phenoxyphenyl) -4-acryloyloxymethyl −
1,3-dithiolane, 2- (4'-methylthiophenyl) -4-acryloyloxymethyl-1,3-dithiolane, 2- (2,4,6-trimethylthiophenyl)-
4-acryloyloxymethyl-1,3-dithiolane,
2- (4'-chlorophenyl) -4-acryloyloxymethyl-1,3-dithiolane, 2- (4'-bromophenyl) -4-acryloyloxymethyl-1,3-dithiolane, 2- (α-naphthyl) -4-acryloyloxymethyl-1,3-dithiolane, 2- (β-naphthyl) -4-acryloyloxymethyl-1,3-dithiolane, 2-methyl-2-phenyl-4-acryloyloxymethyl-1,3 -Dithiolane, 2,2-diphenyl-4-acryloyloxymethyl-1,3-dithiolane,

2- (4-methylphenyl) -4- (2-
Acryloyloxyethyl) -1,3-dithiolane, 2
-Α-naphthyl-4- (3-acryloyloxypropyl) -1,3-dithiolane, 2-phenyl-4- (2-
Acryloyloxymethylthio) methyl-1,3-dithiolane, 2- (4-methoxyphenyl) -4- (2-acryloyloxyethylthio) methyl-1,3-dithiolane, 2- (4-bromophenyl) -4- (2-acryloyloxypropylthio) methyl-1,3-dithiolane, 2- (thiophen-2-yl) -4- (2-methyl-2-acryloyloxyethylthio) methyl-1,3
-Dithiolane, 2-freel-4- [2- (2-acryloyloxyethylthio) ethyl] -1,3-dithiolane, 2- (4-methylthiophenyl) -4- [3- (2
-Acryloyloxymethylthio) propyl] -1,3
-Dithiolane, 2-β-naphthyl-4- [2-methyl-
2- (2-acryloyloxymethylthio) ethyl]-
1,3-dithiolane,

4-methacryloylthiomethyl-1,3
-Dithiolane,

2-methyl-4-methacryloylthiomethyl-1,3-dithiolane, 2-ethyl-4-methacryloylthiomethyl-1,3-dithiolane, 2-n-propyl-4-methacryloylthiomethyl- 1,3-dithiolane, 2-n-butyl-4-methacryloylthiomethyl-1,3-dithiolane, 2-phenyl-4-methacryloylthiomethyl-1,3-dithiolane, 2-
(4′-methylphenyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2- (3′-methylphenyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2- (2′- Methylphenyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2-
(4′-tert-butylphenyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2- (4′-
Methoxyphenyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2- (4-phenylphenyl)
-4-methacryloylthiomethyl-1,3-dithiolane, 2- (4'-phenoxyphenyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2- (4 '
-Methylthiophenyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2- (2,4,6-trimethylthiophenyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2- (4 ' -Chlorophenyl)
-4-methacryloylthiomethyl-1,3-dithiolane, 2- (4′-bromophenyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2- (α-naphthyl) -4-methacryloylthio Methyl-1,3-dithiolane, 2- (β-naphthyl) -4-methacryloylthiomethyl-1,3-dithiolane, 2,2-dimethyl-4-methacryloylthiomethyl-1,3-dithiolane, 2- Methyl-2-phenyl-4-methacryloylthiomethyl-1,3-dithiolane, 2,2-diphenyl-4-methacryloylthiomethyl-1,3-dithiolane,

4- (2-methacryloylthioethyl)
-1,3-dithiolane, 4- (3-methacryloylthiopropyl) -1,3-dithiolane, 4- (2-methyl-2-methacryloylthioethyl) -1,3-dithiolane, 4-methacryloylthio Methylthiomethyl-
1,3-dithiolane, 4- (2-methacryloylthioethylthio) methyl-1,3-dithiolane, 4- (3-
(Methacryloylthiopropylthio) methyl-1,3-
Dithiolane, 4- (2-methyl-2-methacryloylthioethylthio) methyl-1,3-dithiolane, 4-
[2- (2-methacryloylthiomethylthio) ethyl] -1,3-dithiolane, 4- [2- (2-methacryloylthioethylthio) ethyl] -1,3-dithiolane, 4- [2- (3 -Methacryloylthiopropylthio) ethyl] -1,3-dithiolane, 4- [2- (2-
Methyl-2-methacryloylthioethylthio) ethyl] -1,3-dithiolane, 4- [3- (2-methacryloylthiomethylthio) propyl] -1,3-dithiolane, 4- [3- (2-meta) Acryloylthioethylthio) propyl] -1,3-dithiolane, 4- [3- (3
-Methacryloylthiopropylthio) propyl]-
1,3-dithiolane, 4- [3- (2-methyl-2-methacryloylthioethylthio) propyl] -1,3-
Dithiolane, 4- [2-methyl-2- (2-methacryloylthiomethylthio) ethyl] -1,3-dithiolane, 4- [2-methyl-2- (2-methacryloylthioethylthio) ethyl] -1 , 3-dithiolane, 4-
[2-methyl-2- (3-methacryloylthiopropylthio) ethyl] -1,3-dithiolane, 4- [2-methyl-2- (2-methyl-2-methacryloylthioethylthio) ethyl]- 1,3-dithiolane,

2- (4-methylphenyl) -4- (2-
(Methacryloylthioethyl) -1,3-dithiolane,
2-α-naphthyl-4- (3-methacryloylthiopropyl) -1,3-dithiolane, 2-phenyl-4-
(2-methacryloylthiomethylthio) methyl-1,
3-dithiolane, 2- (4-methoxyphenyl) -4-
(2-methacryloylthioethylthio) methyl-1,
3-dithiolane, 2- (4-bromophenyl) -4-
(2-methacryloylthiopropylthio) methyl-
1,3-dithiolane, 2- (thiophen-2-yl)-
4- (2-methyl-2-methacryloylthioethylthio) methyl-1,3-dithiolane, 2-freel-4-
[2- (2-methacryloylthioethylthio) ethyl] -1,3-dithiolane, 2- (4-methylthiophenyl) -4- [3- (2-methacryloylthiomethylthio) propyl] -1,3- Dithiolane, 2-β-naphthyl-4- [2-methyl-2- (2-methacryloylthiomethylthio) ethyl] -1,3-dithiolane,

2-methyl-4-methacryloyloxymethyl-1,3-dithiolane, 2-phenyl-4-methacryloyloxymethyl-1,3-dithiolane, 2-
(4′-methylphenyl) -4-methacryloyloxymethyl-1,3-dithiolane, 2- (4′-methoxyphenyl) -4-methacryloyloxymethyl-1,
3-dithiolane, 2- (4-phenylphenyl) -4-
Methacryloyloxymethyl-1,3-dithiolane,
2- (4'-phenoxyphenyl) -4-methacryloyloxymethyl-1,3-dithiolane, 2- (4'-
Methylthiophenyl) -4-methacryloyloxymethyl-1,3-dithiolane, 2- (2,4,6-trimethylthiophenyl) -4-methacryloyloxymethyl-1,3-dithiolane, 2- (4′- (Chlorophenyl) -4-methacryloyloxymethyl-1,3-dithiolane, 2- (4′-bromophenyl) -4-methacryloyloxymethyl-1,3-dithiolane, 2-
(Α-naphthyl) -4-methacryloyloxymethyl-1,3-dithiolane, 2- (β-naphthyl) -4-methacryloyloxymethyl-1,3-dithiolane,
-Methyl-2-phenyl-4-methacryloyloxymethyl-1,3-dithiolane, 2,2-diphenyl-4
-Methacryloyloxymethyl-1,3-dithiolane,

2- (4-methylphenyl) -4- (2-
(Methacryloyloxyethyl) -1,3-dithiolane, 2-α-naphthyl-4- (3-methacryloyloxypropyl) -1,3-dithiolane, 2-phenyl-
4- (2-methacryloyloxymethylthio) methyl-1,3-dithiolane, 2- (4-methoxyphenyl)
-4- (2-methacryloyloxyethylthio) methyl-1,3-dithiolane, 2- (4-bromophenyl)
-4- (2-methacryloyloxypropylthio) methyl-1,3-dithiolane, 2- (thiophen-2-yl) -4- (2-methyl-2-methacryloyloxyethylthio) methyl-1,3 -Dithiolane, 2-freel-4- [2- (2-methacryloyloxyethylthio) ethyl] -1,3-dithiolane, 2- (4-methylthiophenyl) -4- [3- (2-methacryloyloxy Methylthio) propyl] -1,3-dithiolane, 2
Examples include-[beta] -naphthyl-4- [2-methyl-2- (2-methacryloyloxymethylthio) ethyl] -1,3-dithiolane, but the present invention is not limited thereto.

The acrylate compound represented by the general formula (1) of the present invention is preferably prepared by using the sulfur-containing compound represented by the general formula (2) as a raw material by various esterification methods known per se. It is manufactured in. That is, a (meth) acrylic acid (for example, (meth) acrylic acid, an acid halide thereof, or an ester derivative thereof) is reacted with a sulfur-containing compound represented by the following general formula (2) to obtain (meth) acrylic acid. ) Acrylic esterification method (for example, the method described in JP-A-64-26613, JP-A-64-31759, JP-A-63-188660, etc.); Halopropionic acids (for example, 3 -Chloropropionic acid, 3-bromopropionic acid, 3-chloro-2-methylpropionic acid, 3-bromo-2-methylpropionic acid) or an acid halide thereof to give a halopropionic ester compound. A method of dehydrohalogenating and converting to an acrylate (for example,
0-204056, JP-A-2-172968, JP-A-2-172969, JP-A-4-299
The acrylic acid ester compound represented by the general formula (1) is produced by various known esterification methods, such as those described in, for example, JP-A-67-167).

[0056]

Embedded image (Wherein R ₁ , R ₂ , A and X are as defined above)

Among the above methods, the general formula (1) of the present invention
As the method for producing the acrylate compound represented by the formula, the latter method is more preferable.

Among these methods, the method shown in the following reaction route, that is, the reaction of the sulfur-containing compound represented by the general formula (2) with an acid halide of a halopropionic acid,
After obtaining the halopropionate compound (3), the halopropionate compound (3) is dehydrohalogenated in the presence of a base to produce an acrylate compound represented by the general formula (1). Is more preferred.

[0059]

Embedded image (In the above formula, R ₁ , R ₂ , R ₃ , A and X are the same as described above, and Z ₁ and Z ₂ each represent a chlorine atom or a bromine atom.)

Hereinafter, the present method will be described in more detail. First, a method for producing a halopropionic acid ester compound (3) by reacting a sulfur-containing compound represented by the general formula (2) with an acid halide of a halopropionic acid will be described in detail.

At the time of such a reaction, halopropionic acids (eg, 3-chloropropionic acid, 3-bromopropionic acid, 3-chloro-2-acid) which act on the sulfur-containing compound represented by the above general formula (2) The amount of the acid halide such as methylpropionic acid and 3-bromo-2-methylpropionic acid is not particularly limited, but is usually 0.1 to 5 mol per 1 mol of the sulfur-containing compound. , Preferably 0.2 to 3 mol, more preferably 0.1 to 3 mol.
There are 5 to 2 moles. It is particularly preferable that the use amount of the acid halide of halopropionic acids is 0.8 to 1.5 mol.

The reaction may be carried out without solvent or in an inert solvent for the reaction. The solvent is not particularly limited as long as it is a reaction-inert solvent. For example, water, an organic solvent, or a mixture thereof may be used. As the organic solvent, n-hexane, hydrocarbon solvents such as benzene or toluene, acetone, ketone solvents such as methyl ethyl ketone or methyl isobutyl ketone, ester solvents such as ethyl acetate or butyl acetate, diethyl ether, diethylene glycol dimethyl ether, Ether solvents such as tetrahydrofuran or dioxane, halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, chlorobenzene, orthochlorobenzene, acetonitrile, N, N-dimethylformamide, N, N-dimethyl Imidazolidinones,
Examples thereof include polar solvents such as dimethyl sulfoxide and sulfolane. These solvents may be used alone or in combination of two or more.

The reaction temperature is not particularly limited and is usually -78.
To 150 ° C, preferably from -20 to 120 ° C.
° C, more preferably 0 to 100 ° C.

The reaction time depends on the reaction temperature, but is usually several minutes to 100 hours, preferably 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 checking the reaction rate by a known analysis means (for example, liquid chromatography, gas chromatography, thin-layer chromatography, IR, etc.).

Such a reaction may be carried out in the absence of a catalyst while removing by-produced hydrogen halide (for example, hydrogen chloride) out of the reaction system, or by using a dehydrohalogenating agent. Is also good.

As the dehydrohalogenating agent, for example,
Triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DB
Examples thereof include organic bases such as U) and inorganic bases such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium oxide.

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

Next, a method for producing the acrylate compound represented by the general formula (1) of the present invention by dehydrohalogenating the halopropionate compound (3) in the presence of a base will be described in detail. State.

As the base used in this reaction, for example,
Methylamine, dimethylamine, triethylamine, pyridine, picoline, aniline, dimethylaniline, diethylaniline, toluidine, anisidine, 1,4-diazabicyclo [2.2.2] octane (DABCO),
1,8-diazabicyclo [5.4.0] undec-7-
Examples thereof include organic bases such as ene (DBU), and inorganic bases such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium oxide.

The amount of the base to be used is not particularly limited, but is 0.05 to 10 mol, preferably 1 to 10 mol, per mol of the halopropionate compound (3).
It is 0.1 to 5 mol, and more preferably 0.5 to 3 mol.

The reaction may be carried out without a solvent or in an inert solvent for the reaction. The solvent is not particularly limited as long as it is a reaction-inert solvent. For example, water, an organic solvent, or a mixture thereof may be used.

Examples of the organic solvent include hydrocarbon solvents such as n-hexane, benzene, toluene and xylene, methanol, ethanol, isopropanol, n-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. Alcohol solvents such as ethyl ether and diethylene glycol monobutyl ether; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane , Dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethyl Emissions, chlorobenzene, halogenated solvents such as o- dichlorobenzene, acetonitrile,
Examples thereof include polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethylsulfoxide, and sulfolane. These solvents may be used alone or in combination of two or more.

The reaction temperature is not particularly limited and is usually -78.
To 150 ° C, preferably from -20 to 120 ° C.
° 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 checking the reaction rate by a known analysis means (for example, liquid chromatography, gas chromatography, thin-layer chromatography, IR, etc.).

In the above-described reaction route, after the halopropionate esterification reaction in the first step, the halopropionate compound represented by the general formula (3), which is an intermediate, is once taken out, and then the second step is carried out. May be a stepwise method of dehydrohalogenation, or without removing the halopropionate compound in the middle,
Any of the methods for performing the next dehydrohalogenation reaction in one step (one-pot) may be used.

In the production of the acrylate compound represented by the general formula (1) of the present invention, it is preferable to use a polymerization inhibitor in order to prevent polymerization of the product during or after the reaction. That is.

As such a polymerization inhibitor, for example, 4-
Various known compounds such as methoxyphenol, 2,6-di-tert-butylcresol, hydroquinone, and phenothiazine can be exemplified.

The amount of the polymerization inhibitor used is not particularly limited.
It is usually 0.001 to 5% by mass relative to the raw material mixture or the reaction product in the reaction system, and preferably 0.0
It is 5 to 3% by mass, more preferably 0.01 to 1% by mass.

After completion of the reaction, the product, the acrylate compound represented by the general formula (1) of the present invention, is subjected to known procedures and treatment methods (eg, neutralization, solvent extraction, water washing, liquid separation, solvent separation). And then isolated. The acrylate compound represented by the general formula (1) obtained by the above-mentioned method may be further separated and purified by a known method (for example, distillation, recrystallization, chromatography or activated carbon treatment), if necessary. And is isolated as a higher purity compound.

The sulfur-containing compound of the present invention represented by the general formula (2) is a novel compound and, as described above, is a synthetic intermediate of the acrylate compound represented by the general formula (1).

[0081] In the general formula _{(2), R 1, R} 2, A and X are, R ₁ in the general formula described above (1), R _2,
Represents the same meaning as A and X.

The sulfur-containing compound represented by the general formula (2) of the present invention includes, for example, 4-mercaptomethyl-1,3-
Dithiolane, 2-methyl-4-mercaptomethyl-1,
3-dithiolane, 2-ethyl-4-mercaptomethyl-
1,3-dithiolan, 2-n-propyl-4-mercaptomethyl-1,3-dithiolan, 2-n-butyl-4-
Mercaptomethyl-1,3-dithiolane, 2-phenyl-4-mercaptomethyl-1,3-dithiolane, 2-
(4′-methylphenyl) -4-mercaptomethyl-
1,3-dithiolane, 2- (3'-methylphenyl)-
4-mercaptomethyl-1,3-dithiolane, 2-
(2′-methylphenyl) -4-mercaptomethyl-
1,3-dithiolane, 2- (4′-tert-butylphenyl) -4-mercaptomethyl-1,3-dithiolane, 2- (4′-methoxyphenyl) -4-mercaptomethyl-1,3-dithiolane, 2- (4'-phenylphenyl) -4-mercaptomethyl-1,3-dithiolane, 2- (4'-phenoxyphenyl) -4-mercaptomethyl-1,3-dithiolane, 2- (4'-methylthiophenyl ) -4-Mercaptomethyl-1,3-dithiolane, 2- (2,4,6-trimethylthiophenyl)-
4-mercaptomethyl-1,3-dithiolane, 2-
(4'-chlorophenyl) -4-mercaptomethyl-
1,3-dithiolane, 2- (4'-bromophenyl)-
4-mercaptomethyl-1,3-dithiolane, 2- (α
-Naphthyl) -4-mercaptomethyl-1,3-dithiolane, 2- (β-naphthyl) -4-mercaptomethyl-
1,3-dithiolane, 2,2-dimethyl-4-mercaptomethyl-1,3-dithiolane, 2-methyl-2-phenyl-4-mercaptomethyl-1,3-dithiolane,
2,2-diphenyl-4-mercaptomethyl-1,3-
Dithiolane,

4- (2-mercaptoethyl) -1,3-
Dithiolane, 4- (3-mercaptopropyl) -1,3
-Dithiolane, 4- (2-methyl-2-mercaptoethyl) -1,3-dithiolane, 4-mercaptomethylthiomethyl-1,3-dithiolane, 4- (2-mercaptoethylthio) methyl-1,3-dithiolane , 4- (3-mercaptopropylthio) methyl-1,3-dithiolane,
4- (2-methyl-2-mercaptoethylthio) methyl-1,3-dithiolane, 4- [2- (mercaptomethylthio) ethyl] -1,3-dithiolane, 4- [2- (2
-Mercaptoethylthio) ethyl] -1,3-dithiolane, 4- [2- (3-mercaptopropylthio) ethyl] -1,3-dithiolane, 4- [2- (2-methyl-
2-mercaptoethylthio) ethyl] -1,3-dithiolane, 4- [3- (mercaptomethylthio) propyl]
-1,3-dithiolane, 4- [3- (2-mercaptoethylthio) propyl] -1,3-dithiolane, 4- [3
-(3-mercaptopropylthio) propyl] -1,3
-Dithiolane, 4- [3- (2-methyl-2-mercaptoethylthio) propyl] -1,3-dithiolane, 4-
[2-methyl-2- (mercaptomethylthio) ethyl]
-1,3-dithiolane, 4- [2-methyl-2- (2-
Mercaptoethylthio) ethyl] -1,3-dithiolane, 4- [2-methyl-2- (3-mercaptopropylthio) ethyl] -1,3-dithiolane, 4- [2-methyl-2- (2- Methyl-2-mercaptoethylthio) ethyl] -1,3-dithiolane,

2- (4-methylphenyl) -4- (2-
(Mercaptoethyl) -1,3-dithiolane, 2-α-naphthyl-4- (3-mercaptopropyl) -1,3-dithiolane, 2-phenyl-4- (mercaptomethylthio) methyl-1,3-dithiolane, -(4-methoxyphenyl) -4- (2-mercaptoethylthio) methyl-1,3-dithiolane, 2- (4-bromophenyl)-
4- (2-mercaptopropylthio) methyl-1,3-
Dithiolane, 2- (thiophen-2-yl) -4- (2
-Methyl-2-mercaptoethylthio) methyl-1,3
-Dithiolane,

2-Freel-4- [2- (2-mercaptoethylthio) ethyl] -1,3-dithiolane, 2-
(4-methylthiophenyl) -4- [3- (mercaptomethylthio) propyl] -1,3-dithiolane, 2-β
-Naphthyl-4- [2-methyl-2- (mercaptomethylthio) ethyl] -1,3-dithiolane,

2-methyl-4-hydroxymethyl-1,
3-dithiolane, 2-phenyl-4-hydroxymethyl-1,3-dithiolane, 2- (4′-methylphenyl)
-4-hydroxymethyl-1,3-dithiolane, 2-
(4'-methoxyphenyl) -4-hydroxymethyl-
1,3-dithiolane, 2- (4′-phenylphenyl)
-4-hydroxymethyl-1,3-dithiolane, 2-
(4'-phenoxyphenyl) -4-hydroxymethyl-1,3-dithiolane, 2- (4'-methylthiophenyl) -4-hydroxymethyl-1,3-dithiolane,
-(2,4,6-trimethylthiophenyl) -4-hydroxymethyl-1,3-dithiolane, 2- (4'-chlorophenyl) -4-hydroxymethyl-1,3-dithiolane, 2- (4'- Bromophenyl) -4-hydroxymethyl-1,3-dithiolane, 2- (α-naphthyl)-
4-hydroxymethyl-1,3-dithiolane, 2- (β
-Naphthyl) -4-hydroxymethyl-1,3-dithiolane, 2-methyl-2-phenyl-4-hydroxymethyl-1,3-dithiolane, 2,2-diphenyl-4-hydroxymethyl-1,3-dithiolane ,

2- (4-methylphenyl) -4- (2-
(Hydroxyethyl) -1,3-dithiolane, 2-α-naphthyl-4- (3-hydroxypropyl) -1,3-dithiolane, 2-phenyl-4- (hydroxymethylthio) methyl-1,3-dithiolane, -(4-methoxyphenyl) -4- (2-hydroxyethylthio) methyl-1,3-dithiolane, 2- (4-bromophenyl)-
4- (2-hydroxypropylthio) methyl-1,3-
Dithiolane, 2- (thiophen-2-yl) -4- (2
-Methyl-2-hydroxyethylthio) methyl-1,3
-Dithiolane, 2-freel-4- [2- (2-hydroxyethylthio) ethyl] -1,3-dithiolane, 2-
(4-methylthiophenyl) -4- [3- (hydroxymethylthio) propyl] -1,3-dithiolane, 2-β
-Naphthyl-4- [2-methyl-2- (hydroxymethylthio) ethyl] -1,3-dithiolane and the like are shown, but the present invention is not limited to these exemplified compounds.

Compounds in which X is an oxygen atom in the above general formula (2) can be prepared by a known method per se [for example, Jo
urnal of Chemical Society (C), pp. 415-419 (1
966)).

That is, for example, the known compound 2,
According to a method in which an aqueous formaldehyde solution (formalin) is allowed to act on 3-dimercaptopropanol in the presence of an acid catalyst, in the general formula (2), R ₁ = hydrogen atom, R ₂ = hydrogen atom, and A is- A CH ₂ — group, X
Is a compound where is an oxygen atom.

As shown below, a dimercapto compound represented by the following formula (4) is reacted in the same manner with a dimercapto compound represented by the following formula (5) in the presence of an acid catalyst (eg, a protonic acid or a Lewis acid). By reacting the represented carbonyl group-containing compound, a sulfur-containing hydroxy compound in which X is an oxygen atom in the general formula (2) is produced.

[0091]

Embedded image (Wherein R ₁ , R ₂ , A and X are the same as described above)

The sulfur-containing thiol compound of the general formula (2) in which X is a sulfur atom can be obtained by using a sulfur-containing hydroxy compound in which X is an oxygen atom in the general formula (2) as a raw material. It is suitably produced by converting a hydroxy group in a molecule into a thiol group according to a known method.

That is, for example, in order to convert a hydroxy compound in which X is an oxygen atom in the general formula (2) into a thiol (mercapto) compound in which X is a sulfur atom, a known method, for example, Journal of American Chemic
al Society, 68, pp. 2103-2104 (1946)
Year), Journal of Organic Chemistry, vol. 27, p. 93
-95 (1962), Organic Synthesis, V, p. 40
1 to 403 (1963),
It is preferably implemented.

That is, a hydroxy compound in which X in formula (2) is an oxygen atom is allowed to react with, for example, hydrogen chloride, hydrogen bromide, etc. to derive the hydroxy compound into a halogen compound. A thiol compound in which X is a sulfur atom in the general formula (2) of the present invention is preferably produced by a method of reacting urea to form a thiolonium salt and then hydrolyzing with a base such as aqueous ammonia or sodium hydroxide. Is done.

Next, the polymerizable composition containing the acrylate compound 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, the acrylate compound represented by the general formula (1) of the present invention and a polymerization initiator. The polymerization initiator is a compound that initiates polymerization of the polymerizable compound by light, heat, or the like, and various known polymerization initiators as described below are used.

In the polymerizable composition of the present invention, the acrylate compound may be used alone, or two or more different acrylate compounds included in the general formula (1) may be used in combination. Absent.

Further, the polymerizable composition of the present invention may contain, if necessary, an acrylate compound represented by the general formula (1) as long as the desired effect is not impaired.
It may contain a known polymerizable compound (light or / and heat polymerizable monomer or oligomer, etc.).

The amount of the acrylate compound represented by the general formula (1) contained in the polymerizable composition is not particularly limited, but is usually 10% by mass based on the total mass of the polymerizable composition. Or more, preferably 20% 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 is a known compound that initiates polymerization by heat (thermal polymerization initiator) or a compound that initiates polymerization by light (light polymerization initiator). Polymerization initiator).

Examples of the photopolymerization initiator include benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 2,4,6-trimethylbenzophenone, o-benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, -(4-methylphenylthio) benzophenone, 3,3-dimethyl-4-methylbenzophenone, 4- (1,3-acryloyl-1,4,
7,10,13-pentaoxatridecyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-methylbenzenemethananium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propanaminium chloride, 4-benzoyl-N, N-dimethyl-N-
[(2- (1-oxo-2-propenoxy) ethyl) benzenemethaminium bromide, 4-benzoyl-N,
N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethanaminium bromide,
2-isopropylthioxatone, 4-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-
Diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo 9H-thioxanthone-2-yloxy) Carbonyl compounds such as -N, N, N-trimethyl-1-propanaminium chloride, 2-benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline;

Benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione (commonly referred to as
Camphorquinone), 2-methylanthraquinone, 2-
Dicarbonyl compounds such as ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 9,10-phenanthrenequinone, and α-oxobenzeneacetic acid methyl ester; acetophenone, 2-hydroxy-2- Methyl-1
-Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, dimethoxyacetophenone, diethoxyacetophenone,
2,2-dimethoxy-1,2-diphenylethane-1-
On, 2,2-diethoxy-1,2-diphenylethan-1-one, 1,1-dichloroacetophenone, N, N
-Dimethylaminoacetophenone, 2-methyl-1-
(4-methylthiophenyl) -2-morpholinolpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-phenyl-1,2-propane Zeon-2- (o
-Ethoxycarbonyl) oxime, 3,6-bis (2-
Acetophenone-based compounds such as methyl-2-morpholinopropanoyl) -9-butylcarbazole; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-
Benzoin ether compounds such as n-butyl ether and benzoin isobutyl ether; allyls such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dichlorobenzoyl)-(4-n-propylphenyl) phosphine oxide Phosphine oxide compounds; 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid-n-butoxyethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, benzoic acid-2- Dimethylaminoethyl ester,
Aminocarbonyl compounds such as 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4,4'-bisdiethylaminobenzophenone, and 2,5'-bis (4-dimethylaminobenzal) cyclopentanone;

2,2,2-Trichloro-1- (4'-t
tert-butylphenyl) ethan-1-one, 2,2-
Dichloro-1- (4-phenoxyphenyl) ethane-1
-One, α, α, α-tribromomethylphenylsulfone, 2,4,6-tris (trichloromethyl) triazine, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) triazine, 4-bis (trichloromethyl) -6- (4-methoxystyryl) triazine, 2,4-bis (trichloromethyl) -6- (3,4
-Methylenedioxyphenyl) triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) triazine, 2,4-bis (trichloromethyl)-
6- [2- (5-methylfuryl) ethylidine] triazine, 2,4-bis (trichloromethyl) -6- [2-
Freeethylethiridine] halogen compounds such as triazine; 9-phenylacridine, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole, 2-azobis (2-aminopropane) dihydrochloride, 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride, η-5-2-4- (cyclopentadienyl)
(1,2,3,4,5,6, η)-(methylethyl)-
Examples of known compounds such as benzene] iron (II) hexafluorophosphate, bis (5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-pyr-1-yl) phenyl] titanium and the like. Can be. These may 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 with respect to 100 parts by mass of the acrylate compound represented by, preferably,
0.01 to 30 parts by mass, more preferably 0.1 to 30 parts by mass.
10 to 10 parts by mass, and more preferably 0.2 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 used is determined by the general formula (1)
With respect to 100 parts by mass of the acrylate compound represented by the formula, 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, more preferably 0.2 to 10 parts by mass.
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 acrylate compound represented by the general formula (1) includes, for example, 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,
Monofunctional acrylates such as 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 (2-acryloyloxy) phenyl sulfide, 4,4'-bis (2-methacryloyloxy) phenyl sulfide, 2,2-bis (4-acryloyloxyethoxyphenyl) propane, 2,2- Bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis [4- (2-acryloyloxypropoxy) phenyl] propane, 2,
2-bis [4- (2-methacryloyloxypropoxy) phenyl] propane, bis (4-acryloyloxyethoxyphenyl) methane, bis (4-methacryloyloxyethoxyphenyl) methane, bis [4- (2
-Acryloyloxypropoxy) phenyl] methane,
[4- (2-methacryloyloxypropoxy) phenyl] methane, 4,4′-bis (2-acryloyloxyethoxy) phenyl sulfide, 4,4′-bis (2
-Methacryloyloxyethoxy) phenyl sulfide, 4,4′-bis (2-acryloyloxypropoxy) phenyl sulfide, 4,4′-bis (2-methacryloyloxypropoxy) phenyl sulfide,
4,4'-bis (2-acryloyloxyethoxy) phenylsulfone, 4,4'-bis (2-methacryloyloxyethoxy) phenylsulfone, 4,4'-
Bifunctional (meth) acrylates such as bis (2-acryloyloxypropoxy) phenylsulfone and 4,4′-bis (2-methacryloyloxypropoxy) phenylsulfone;

Trimethylolpropane tri (meth) acrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylol tetraacrylate, dipentaerythritol hexaacrylate, 2- (meth) acryloyloxyethyl tris isocyanurate Polyfunctional (meth) acrylates such as, (meth) acryloxypropyltris (methoxy) silane;

Phenyl 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'-Bishydroxyphenyl sulfone (commonly known as bisphenol S)
Diglycidyl ether, 4,4'-biphenol diglycidyl ether, 3,3 ', 5,5'-tetramethyl-
Epoxy obtained by reacting a (meth) acrylic acid compound with a monovalent or divalent or higher valent epoxy compound such as 4,4′-biphenol diglycidyl ether and tris (2,3-epoxypropyl) isocyanurate (Meth) acrylates; epoxy (meth) acrylates obtained by reacting a (meth) acrylic acid compound with an epoxy resin such as a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol ziroc type epoxy resin, and a bisphenol type epoxy resin. ) Acrylates and the like;

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.

The amount of these is usually 300 parts by mass or less based on 100 parts by mass of the acrylate compound represented by the general formula (1) in order to further achieve the effects of the present invention. Is 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, using the acrylate compound represented by the general formula (1) of the present invention, optionally using the above-mentioned various polymerizable compounds in combination, further adding the above-mentioned polymerization initiator, and then mixing -Obtained by dissolving. 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.

In 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 the optical component made of 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 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 the thermal polymerization, the polymerization temperature is affected by the polymerization conditions such as the type of the polymerization initiator, and is not limited, but is usually 25 to 200 ° 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 with 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 acrylate compound represented by the general formula (1) of the present invention produced by the above-described method is defoamed by an appropriate method, if necessary. After that, it is preferably carried out by a method of injecting into a mold and usually performing polymerization by irradiation with 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 of molding a substrate of an optical disk or a magneto-optical disk, for example, a polymerizable composition containing an acrylate compound represented by the general formula (1) obtained by the above method is molded by using a mold for a disk substrate. Inject into
This is polymerized by a radical polymerization method or the like, and post-heat treated as necessary (Japanese Patent Application Laid-Open Nos. 58-130450, 58-137150, 62-280008, etc.). Polymerization method (JP-A-6
No. 0-202557), a method of thermally polymerizing a liquid resin by pressurizing after completion of vacuum casting or liquid injection (Japanese Patent Application Laid-Open No. 60-1985).
-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 polymerization and molding can be performed in a short time as compared with thermosetting optical resins represented by polythiourethane, and the productivity is high.

Further, the cured product and the optical component of the present invention are characterized by having good transparency, mechanical properties, and thermal properties, and having a higher refractive index than known photopolymerizable monomers. Have. 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 (meta) represented by the general formula (1) of the present invention
The acrylate compound is a novel compound having a cyclic thioacetal structure in the molecule, and is a very useful compound as a resin material monomer for optical components such as corrective spectacle lenses.

[0127]

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 of Sulfur-Containing Compound Represented by General Formula (2) Production Example 1 [Synthesis of 4-hydroxymethyl-1,3-dithiolane] Journal of Chemical Society (C), 415-419 (1966) Was performed according to the method described in (1). That is, 250 ml of a 30% aqueous solution of formaldehyde and 250 ml of dioxane were weighed into a 1-liter glass reactor equipped with a stirrer and a cooling tube, and the mixture was stirred with 2,3-dimercaptopropanol 1
86 g (1.5 mol) were added. After further adding 1 g of sulfuric acid, the mixture was reacted by heating and stirring at 90 to 100 ° C. for 6 hours under a nitrogen atmosphere. After confirming that the raw materials had disappeared and the reaction was completed by gas chromatography, the solvent was distilled off under reduced pressure. The solvent was distilled off from the organic layer obtained by extracting with chloroform and further washing with water, and 133 g of the desired product, 4-hydroxymethyl-1,3-dithiolane (0.98 g) was obtained.
Mol). Yield 65% Purity> 99% (Area method by gas chromatography analysis) Boiling point: 124 to 125 ° C / 266 kPa (2 mmHg) EI-MS: 136 (M)

Example 1 [4-mercaptomethyl-1,3
-Synthesis of dithiolane; compound of the formula (2) in which R ₁ = hydrogen atom, R ₂ = hydrogen atom, A = —CH ₂ — group, X = sulfur atom] 500 ml of glass equipped with a stirrer and a condenser Thiourea, 38.0 g (0.50 mol), 4
88 g of 8% hydrobromic acid (corresponding to 0.5 mol of hydrogen bromide) was added. 68 g of the 4-hydroxymethyl-1,3-dithiolane synthesized in Production Example 1 (0.50
Mol) was added dropwise at 60 ° C. over 35 minutes. In addition, 80
The reaction was carried out at 4 ° C. for 4 hours to thiuronium chloride. The reaction solution was analyzed by high performance liquid chromatography to confirm that the starting hydroxy compound had disappeared, and 300 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. 200g of toluene
After adding and separating and extracting, the toluene phase is washed with water until the waste water phase becomes neutral, and then the toluene phase is taken out and the toluene is distilled off at 40 ° C. under reduced pressure to obtain a yellow transparent liquid crude product. I got The crude product was purified by silica gel column chromatography (using toluene as a solvent) to obtain 61 g (0.40 mol) of a colorless liquid of 4-mercaptomethyl-1,3-dithiolane represented by the following formula (2-1). ) Got. Yield = 80%, purity> 99% (area method by gas chromatography analysis) EI-MS: 152 (M)

[0130]

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Example 2 [Synthesis of 2-phenyl-4-hydroxymethyl-1,3-dithiolane; In the general formula (2), R ₁ = phenyl group, R ₂ = hydrogen atom, A = —CH ₂
-Group, compound in which X = sulfur atom] 50.0 g of 2,3-dimercaptopropanol in a 1-liter glass reactor equipped with a stirrer and a condenser
(0.40 mol), 98% sulfuric acid 0.44 g (0.00
4 mol) and 80 g of dioxane were weighed, and 46.8 g (0.44 g) of benzaldehyde was added to the mixed solution.
2 mol) was added dropwise at 25 ° C. over 30 minutes. After the reaction was completed by stirring at 70 ° C. for 5 hours, the reaction product was discharged into 500 g of water and extracted with toluene. The organic layer (toluene solution) was washed with water until the aqueous layer became neutral, liquid separation was repeated, and the organic layer was taken out. Toluene was distilled off under reduced pressure and concentrated, whereupon n-hexane was added and allowed to stand, and the precipitated crystals were filtered out. The solid was further washed with toluene / hexane (weight ratio = 60/40) to give 2-phenyl- represented by the following formula (2-2) as white crystals.
4-hydroxymethyl-1,3-dithiolane 72.2
g was obtained. Yield 85% Purity 99% (calculated by gas chromatography area percentage method) 270 MHz ¹ H-NMR δ (CDCl ₃ ): 2.
25 (t, 1H), 3.40 to 4.20 (m, 5H),
5.65 (d, 1H), 7.20 to 7.55 (5H) E
I-MS: 212 (M)

[0132]

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Example 3 [2- (α-naphthyl) -4-
Synthesis of hydroxymethyl-1,3-dithiolane; compound of the formula (2) in which R ₁ = α-naphthyl group, R ₂ = hydrogen atom, A = —CH ₂ — group, and X = oxygen atom] Example 2 was repeated except that α-formylnaphthalene was used instead of using benzaldehyde.
The method was performed in the same manner as described in 2- (α-naphthyl) -4-hydroxymethyl-
1,3-Dithiolane was obtained. EI-MS: 262 (M)

[0134]

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Example 4 [2- (β-naphthyl) -4-
Synthesis of hydroxymethyl-1,3-dithiolane; compound of the formula (2) in which R ₁ = β-naphthyl group, R ₂ = hydrogen atom, A = —CH ₂ — group, and X = oxygen atom] Example 2 was repeated except that β-formylnaphthalene was used instead of using benzaldehyde.
In the same manner as described in 2- (β-naphthyl) -4-hydroxymethyl- represented by the following formula (2-4).
1,3-Dithiolane was obtained. EI-MS: 262 (M)

[0136]

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Example 5 [2- (thiophen-2-i
L) 4-Hydroxymethyl-1,3-dithiolane
In the general formula (2), R₁= Thiophene-2-a
R group, R _Two= Hydrogen atom, A = -CH2- group, X = oxygen atom
In Example 2, instead of using benzaldehyde,
Example 2 except that 2-formylthiophene was used.
Performed in the same manner as described in
2- (thiophen-2-yl) -4-hydroxy
Methyl-1,3-dithiolane was obtained. EI-MS: 218 (M)

[0138]

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Example 6 [Synthesis of 2-phenyl-4-mercaptomethyl-1,3-dithiolane; In formula (2), R ₁ = phenyl group, R ₂ = hydrogen atom, A = -CH _2-
Group, compound in which X = sulfur atom] In Example 1, 2-phenyl-4-hydroxy produced in Example 2 is used instead of using 4-hydroxymethyl-1,3-dithiolan synthesized in Production Example 1 Methyl-
Except for using 1,3-dithiolane, the same procedure as in Example 1 was carried out to obtain 2-phenyl-4-mercaptomethyl-1,3-dithiolane represented by the following formula (2-6). Was.・ 270 MHz ¹ H-NMR δ (CDC
l ₃ ): 1.68 (dt, 1H), 2.80 to 3.58
(M, 4H), 3.97 (dm, 1H), 5.65
(D, 1H), 7.20 to 7.53 (5H) EI-MS
: 228 (M)

[0140]

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Example 7 [Synthesis of 2- (α-naphthyl) -4-mercaptomethyl-1,3-dithiolane; In the general formula (2), R ₁ = α-naphthyl group, R ₂ = hydrogen atom,
A = —CH ₂ —Group, X = Sulfur Atom] In Example 1, instead of using 4-hydroxymethyl-1,3-dithiolane synthesized in Production Example 1, 2 prepared in Example 3 Example 1 except that-(α-naphthyl) -4-hydroxymethyl-1,3-dithiolane was used.
2- (α-naphthyl) -4-mercaptomethyl- represented by the following formula (2-7):
1,3-Dithiolane was obtained. EI-MS: 278 (M)

[0142]

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Example 8 [2- (β-naphthyl) -4-
Synthesis of mercaptomethyl-1,3-dithiolane; compound of the formula (2) in which R ₁ = β-naphthyl group, R ₂ = hydrogen atom, A = —CH ₂ — group, and X = sulfur atom] In place of 4-hydroxymethyl-1,3-dithiolane synthesized in Production Example 1 in Example 1, 2- (β-naphthyl) -4-hydroxymethyl-1,3-dithiolane produced in Example 4 was replaced with Example 1 except for use
2- (β-naphthyl) -4-mercaptomethyl- represented by the following formula (2-8):
1,3-Dithiolane was obtained. EI-MS: 278 (M)

[0144]

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Example 9 [2- (thiophen-2-i
L) 4-mercaptomethyl-1,3-dithiolane
In the general formula (2), R₁= Thiophene-2-a
R group, R _Two= Hydrogen atom, A = -CH_Two-Group, X = sulfur atom
In Example 1, 4-hydroxy synthesized in Production Example 1
Instead of using methyl-1,3-dithiolane,
2- (thiophen-2-yl) -4-hydr prepared in 5
Except for using roxymethyl-1,3-dithiolane,
Performed in the same manner as in the method described in Example 1, the following formula (2-
2- (thiophen-2-yl) -4-me shown in 9)
Lucatomethyl-1,3-dithiolane was obtained. EI-MS: 234 (M)

[0146]

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Synthesis of acrylate compound represented by general formula (1) Example 10 Synthesis of 4-acryloylthiomethyl-1,3-dithiolane; In general formula (1), R ₁ = hydrogen atom, R ₂ = hydrogen atom, R ₃ = hydrogen, A = -CH ₂ -
Group, compound in which X = sulfur atom] The 4-mercaptomethyl-1,3 produced in Example 1 was placed in a glass 500 ml reaction vessel equipped with a stirrer and a condenser.
91.2 g (0.60 mol) of dithiolane (2-1) was weighed, and 80.0 g (0.63 mol) of 3-chloropropionic chloride was added dropwise at 40 ° C. over 15 minutes. did. After further reacting with stirring at 40 ° C. for 8 hours, 200 g of toluene was added to and dissolved in the reaction mixture solution, and the solution was transferred to a separating funnel and washed three times with 300 g of a 3 mass% aqueous sodium hydrogen carbonate solution. . Then, pure water 30
After washing the aqueous layer with 0 g until the aqueous layer became neutral, the organic layer (toluene solution) was taken out, and toluene was distilled off under reduced pressure to remove colorless and transparent liquid 4- (3-chloropropionylthio) methyl-1,3. 119 g of dithiolane were obtained.

Next, in a 1-liter glass reaction vessel,
119 g of 4- (3-chloropropionylthiomethyl) -1,3-dithiolane obtained as above (0.
49 mol) was dissolved in 200 g of acetone, and 74 g (0.73 mol) of triethylamine was added at 25 ° C.
For 1 hour. Thereafter, the mixture was stirred and reacted at 25 ° C. for 6 hours, and then 400 g of toluene and 400 g of water were added to the reaction mixture, and the toluene phase was separated and extracted. After washing the toluene solution with a 5% by mass aqueous hydrochloric acid solution and further washing with water until the aqueous phase becomes neutral, the toluene is distilled off under reduced pressure to obtain a viscous colorless transparent liquid represented by the following formula (1-1). 99 g of the target compound 4-acryloylthiomethyl-1,3-dithiolane (0.
48 mol).

Yield = 80% Purity> 99% (Area method by liquid chromatography analysis) EI-MS; 206 (M)

[0150]

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Example 11 [Synthesis of 2-phenyl-4-acryloylthiomethyl-1,3-dithiolane; R ₁ = phenyl group, R ₂ = hydrogen atom, R _{3 in} formula (1)
= Hydrogen atom, A = —CH ₂ — group, X = Sulfur atom] In Example 10 above, 4-mercaptomethyl-1,3-dithiolane (2
Instead of using -1), 2-phenyl-4-mercaptomethyl-1,3-dithiolane (2
Except for using -6), the same procedure as described in Example 10 was carried out, and the target compound 2-phenyl-4-acryloylthiomethyl-1,3 represented by the following formula (1-2) was obtained.
-Dithiolane is obtained. 270 MHz ¹ H-NMR δ (CDCl ₃ ): 3.
22-3.55 (m, 4H), 4.08 (dm, 1
H) 5.68-5.77 (m, 2H), 6.35-
6.40 (d, 2H), 7.25 to 7.55 (5H) EI-MS: 282 (M)

[0152]

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When the viscosity of the compound was measured, it was found to be 200
mPa · s (200 cPoise) or less, relatively low viscosity, easy to flow, and easy handling during operations such as filtration and liquid transfer.

Example 12 [2- (α-naphthyl) -4
Synthesis of -acryloylthiomethyl-1,3-dithiolane; R ₁ = α-naphthyl group, R ₂ =
Compound in which hydrogen atom, R ₃ = hydrogen atom, A = —CH ₂ — group, and X = sulfur atom] In Example 10 above, 4-mercaptomethyl-1,3-dithiolane produced in Example 1 as a reaction raw material (2
Instead of using -1), 2- (α) produced in Example 7 was used.
-Naphthyl) -4-mercaptomethyl-1,3-dithiolane (2-7), except that the target compound represented by the following formula (1-3) was prepared in the same manner as in Example 10. Of 2- (α-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane was obtained. EI-MS: 332 (M)

[0155]

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Example 13 [2- (β-naphthyl) -4
Synthesis of -acryloylthiomethyl-1,3-dithiolane; R ₁ = β-naphthyl group, R ₂ =
Compound in which hydrogen atom, R ₃ = hydrogen atom, A = —CH ₂ — group, and X = sulfur atom] In Example 10 above, 4-mercaptomethyl-1,3-dithiolane produced in Example 1 as a reaction raw material (2
Instead of using -1), 2- (β
-Naphthyl) -4-mercaptomethyl-1,3-dithiolane (2-8), except that the target compound represented by the following formula (1-4) was prepared in the same manner as in Example 10. Of 2- (β-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane was obtained. EI-MS: 332 (M)

[0157]

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Example 14 [Synthesis of 2- (thiophen-2-yl) -4-acryloylthiomethyl-1,3-dithiolane; R ₁ = thiophen-2 in the general formula (1)
-Yl group, R ₂ = hydrogen atom, R ₃ = hydrogen atom, A = -CH
_2- Compound wherein X = sulfur atom] In Example 10 described above, 4-mercaptomethyl-1,3-dithiolane (2
Instead of using -1), 2- (thiophen-2-yl) -4-mercaptomethyl-1,3 prepared in Example 9
Example 10 except that -dithiolane (2-9) was used
And the target compound represented by the following formula (1-5): 2- (thiophen-2-yl) -4
-Acryloylthiomethyl-1,3-dithiolane was obtained. EI-MS: 288 (M)

[0159]

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Example 15 [Synthesis of 2-phenyl-4-acryloyloxymethyl-1,3-dithiolane; R ₁ = phenyl group, R ₂ = hydrogen atom, R 1
₃ = hydrogen atom, A = —CH ₂ — group, X = oxygen atom] In Example 10 above, the 4-mercaptomethyl-1,3-dithiolane (2
Instead of using -1), 2-phenyl-4-hydroxymethyl-1,3-dithiolane (2
Except for using -2), the same procedure as in Example 10 was carried out, and the target compound represented by the following formula (1-6), 2-phenyl-4-acryloyloxymethyl-1,2
3-Dithiolane was obtained. 270 MHz ¹ H-NMR δ (CDCl ₃ ): 3.
30-3.55 (m, 2H), 4.00-4.55
(M, 3H), 5.75 (s, 1H), 5.85-5.
90 (dd, 1H), 6.10 to 6.20 (dd, 1
H), 6.40-6.50 (d, 1H), 7.20-
7.60 (5H) EI-MS: 266 (M)

[0161]

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Production of Polymerizable Composition Using Acrylic Ester Compound Represented by General Formula (1) and Production of Cured Product by Curing The cured product or optical component (lens) produced in the following Examples and Comparative Examples ) Physical properties evaluation (transparency, thermal properties,
Mechanical properties) were performed by the following method. -Appearance: Color and transparency were visually confirmed. -Refractive index, Abbe number: 20 using a Pulfrich refractometer
Measured in ° C. Heat resistance: The glass transition temperature of the cured product was measured using TMA (needle penetration method). 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 16 Acrylic ester compound (4-acryloylthiomethyl-1,3-dithiolane) obtained in Example 10 above
For 30 g, 2-hydroxy- as a photopolymerization initiator was used.
2-methyl-1-phenylpropan-1-one ("Da
rocur-1173 ", a registered trademark of Ciba Corporation) 150 m
g 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. 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 1.660 and Abbe number was 36 (νd).

Examples 17 to 21 Hereinafter, the procedure of Example 11 was repeated, except that the acrylate compound (4-acryloylthiomethyl-1,3-dithiolane) obtained in Example 10 was used. Instead of using the acrylate compound prepared in the above-mentioned (1) to (15) and using 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photopolymerization initiator,
A polymerization composition was prepared, and polymerization and curing were performed in the same manner as in Example 16 except that 2,4,6-trimethoxybenzoyldiphenylphosphine oxide (manufactured by BASF) was used.

The results of measuring the refractive index and Abbe number of the cured product are shown in Table 1 below.

[0167]

[Table 1]

The polymerizable composition containing the acrylate compound of the present invention can be polymerized and cured in a short time by a polymerization reaction initiated by light irradiation, and the cured product obtained has a very high refractive index.

Example 22 The acrylic acid ester compound (2-phenyl-4-acryloylthiomethyl-1,3) obtained in Example 11 was obtained.
-Dithiolane) A mixture obtained by mixing 24 g of trimethylolpropane trimethacrylate 3 g and bisphenol A diglycidyl ether dimethacrylate 3 g was mixed with 2,4,4 as a photopolymerization initiator.
30 mg of 6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF) was added, mixed well and dissolved to prepare a liquid polymerizable composition having a low viscosity. After defoaming the obtained composition under sufficiently reduced pressure, it was poured into a mold composed of a glass mold and a gasket. Ultraviolet rays were irradiated for 60 seconds using a metal halide lamp (120 W / cm) to perform polymerization. afterwards,
After gradually cooling to room temperature, the cured product was removed from the mold, and then further heated to 130 ° C. in an inert oven.
For 2 hours to perform annealing.

The obtained cured product was colorless and transparent, and no optical distortion was observed. The refractive index (nd) was 1.655 and Abbe number was 33 (νd).

The glass transition temperature of the cured product was practically acceptable when used as a spectacle lens for correcting vision, and the impact resistance was good.

Comparative Example 1 In Example 22, instead of using the acrylate compound represented by the general formula (1) of the present invention as the polymerizable compound, a known compound (described in JP-A-3-217412) was used. 1,4-bis (2-methacryloyloxyethylthio) xylylene 2, which is an acrylate compound
A polymerizable composition was prepared and a lens was prepared in the same manner as in Example 22, except that 4 g and 6,2-bis (4-methacryloyloxyethoxyphenyl) propane 6 g were used.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.588 and Abbe number (νd) was 39.

Comparative Example 2 Instead of using the acrylate compound represented by the general formula (1) of the present invention as the polymerizable compound in Example 22, a known compound (Example of JP-A-3-215801) was used. Except for using 2-methacryloyloxymethyl-1,4-dithiane which is a compound used in Example 1, a polymerizable composition was prepared in the same manner as in Example 22, and a cured product was prepared. Was prepared. The cured product was colorless and transparent, and had a refractive index (nd) of 1.590 and an Abbe number (νd) of 43.

Comparative Example 3 In Example 22, instead of using the acrylate compound represented by the general formula (1) of the present invention as the polymerizable compound, a known compound (Japanese Patent Application Laid-Open No. 12-509075) was used. The polymerizable composition was prepared in the same manner as in Example 22 except that 6-methacryloyloxy-1,4-dithiacycloheptane, which is the compound described on page 61 in the specification, was used. A cured product was prepared.
The cured product is colorless and transparent, and has a refractive index (nd) of 1.54.
5, Abbe number (νd) was 43.5.

Since the acrylic ester compound of the present invention has a lower viscosity than conventionally known monomers, it can be used when preparing a polymerizable composition or preparing an optical component using the polymerizable composition. Easy to flow and excellent workability during handling.

The polymerizable composition containing the acrylate compound of the present invention can be polymerized and cured in a short time by a compound (polymerization initiator) which initiates polymerization by light irradiation, and the cured product can be produced with high production efficiency. Alternatively, an optical component such as a lens is obtained. The resulting cured product or lens has practically no problem in physical properties such as heat resistance and impact resistance, and has a higher refractive index than known acrylate compounds.

[0178]

The acrylate compound of the present invention is
As a monomer for a photocurable polymerizable composition, it is very useful in applications such as optical materials and dental materials. An optical component obtained by curing the polymerizable composition can be polymerized, cured and molded in a short time (high productivity), has good thermal and mechanical properties, and has a high refractive index. The present invention is useful as various plastic lenses represented by corrective spectacle 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 general formula (2), which is very useful as a raw material of the acrylate compound.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Atsushi Ohtsuji 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Mitsuo Nakamura 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals F Terms (reference) 4C023 NA01 4C063 AA01 BB01 CC97 DD92 EE10 4J100 AL08P BA53P BC83P CA01 CA03 DA62 FA08 JA32 JA33 JA35 JA46 JA50 JA52

Claims (10)

[Claims] 1. An acrylate compound represented by the general formula (1). Embedded image (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or a substituent. R ₃ represents a hydrogen atom or an alkyl group, A represents a divalent organic group, X represents a sulfur atom or an oxygen atom, provided that when X is an oxygen atom, R
₁ represents an aromatic residue which may have a substituent) 2. In the formula (1), R ₁ represents an aromatic residue which may have a substituent, and A represents — (CH ₂ ) _m —
(M is an integer of 1 to 3), and X is a sulfur atom. 3. A polymerizable composition containing the acrylate compound according to claim 1 or 2. 4. A cured product obtained by polymerizing the polymerizable composition according to claim 3. 5. An optical component comprising the cured product according to claim 4. 6. The method for producing an acrylate compound according to claim 1, wherein the sulfur-containing compound represented by the following general formula (2) is converted into an acrylate. Embedded image (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or a substituent. A represents a divalent organic group, X represents a sulfur atom or an oxygen atom, provided that when X is an oxygen atom, R ₁ may have a substituent. Represents a good aromatic residue) 7. In the general formula (2), R ₁ represents an aromatic residue which may have a substituent, and A represents — (CH ₂ ) _m
7. The method according to claim 6, wherein-(m is an integer of 1 to 3), and X is a sulfur atom. 8. The acrylic acid esterification is carried out by reacting the compound of the general formula (2) with a halopropionic acid or an acid halide thereof to form a halopropionic acid ester compound, followed by dehydrohalogenation to obtain an acrylic ester. The method according to claim 6, wherein the esterification is performed. 9. A sulfur-containing compound represented by the general formula (2). Embedded image (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent or a substituent. A represents a divalent organic group, X represents a sulfur atom or an oxygen atom, provided that when X is an oxygen atom, R ₁ may have a substituent. Represents a good aromatic residue) 10. In the general formula (2), R ₁ represents an optionally substituted aromatic residue, and A represents — (C
H _{2) m} - _(m is an integer from 1 to 3), X is 9. sulfur-containing compound of wherein the sulfur atom.