JP4766647B2 - Sulfur-containing compounds - Google Patents

Description

  The present invention relates to an acrylate compound, a method for producing the same, and a sulfur-containing compound serving as a synthetic intermediate thereof. Furthermore, 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 acrylic ester 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. Optical components obtained by curing the polymerizable composition have good optical properties, thermal properties, mechanical properties, excellent productivity, high refractive index, and representative eyeglass lenses for correction. 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, and dental materials.

  Inorganic glass is used in a wide range of fields as a transparent optical material because it is excellent in various 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) to replace inorganic glass has been actively conducted.

  A fundamentally important characteristic as an optical resin is transparency. To date, polymethyl methacrylate (PMMA), bisphenol A polycarbonate (BPA-PC), polystyrene (PS), methyl methacrylate-styrene copolymer (MS), styrene- Acrylonitrile copolymer (SAN), poly (4-methylpentene-1) (TPX), polycycloolefin (COP), polydiethylene glycol bisallyl carbonate (EGAC), polythiourethane (PTU) and the like are known.

  PMMA is excellent in transparency and weather resistance, and has good moldability. However, there is a drawback 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 refractive index, but has a 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 put into practical use as optical resins.

  SAN is relatively high in refractive index and well-balanced in mechanical properties, but has some difficulty in heat resistance (thermal deformation temperature: 80-90 ° C) and is almost used as an optical resin. Absent.

  Although TPX and COP are excellent in transparency, low water absorption, and heat resistance, they have a problem of low refractive index (nd = 1.47 to 1.53) and poor impact resistance, gas barrier properties and dyeability.

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

  PTU is a thermosetting resin obtained by reaction of a diisocyanate compound and a polythiol compound, and is most frequently used for ultrahigh refractive index spectacle lens applications. It is an excellent material with particularly excellent transparency, impact resistance, and high refraction, and small chromatic aberration. However, it has the disadvantage that the thermal polymerization molding time is long (1 to 3 days). The problem remains in terms.

  A method of obtaining an optical lens 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 in order to enhance the productivity (for example, Patent Document 1: Japanese Patent Laid-Open No. 63-248811, Patent Document 2: Japanese Patent Laid-Open No. 3-217812, etc.), and an optical lens is obtained using a (meth) acrylic acid ester compound having a sulfur-containing alicyclic structure. A method (for example, Patent Document 3: Japanese Patent Laid-Open No. 3-215081) has been proposed.

  However, according to these methods, the obtained resin was never satisfied when used as an optical material. That is, for example, because the polymerizable compound (monomer) has a high viscosity and low fluidity, there is a problem that work efficiency is lowered during operations such as filtration and injection into a mold, or polymerization in a short time is Although it is possible, when the refractive index or Abbe number is not sufficiently high, or when used as a spectacle lens, those with a high refractive index have problems such as being brittle and easy to break, and having a large specific gravity. There has been a strong demand for the development of materials that have been overcome.

  As described above, although the conventional optical resins have excellent characteristics, the current situation is that they have drawbacks to be overcome. Under such circumstances, the development of a high refractive index optical resin having excellent transparency, thermal characteristics and mechanical characteristics and excellent workability and productivity is eagerly desired. Currently.

Japanese Patent Laid-Open No. 63-248811 Japanese Patent Laid-Open No. 3-217812 JP-A-3-215081

  The object of the present invention is to solve the disadvantages of the conventional optical resins as described above, have good transparency, thermal characteristics, mechanical characteristics, and high refractive index with excellent workability and productivity. It is to provide an optical resin.

The inventors of the present invention have arrived at the present invention as a result of intensive studies in order to solve the above problems. That is, the present invention
The present invention relates to an acrylate compound represented by the general formula (1).

（式中、Ｒ₁およびＲ₂はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族アルキル基または置換基を有していてもよい芳香族残基を表し、Ｒ₃は水素原子またはアルキル基を表し、Ａは２価の有機基を表し、Ｘは硫黄原子または酸素原子を表す。但し、Ｘが酸素原子である場合、Ｒ₁は置換基を有していてもよい芳香族残基を表す）

(In the formula, R ₁ and R ₂ each independently have 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)

  The present invention also relates to a polymerizable composition containing the acrylic ester compound represented by the general formula (1), a cured product obtained by polymerizing the polymerizable composition, and an optical component comprising the cured product.

  Moreover, it is a manufacturing method of the acrylic ester compound represented by the said General formula (1), Comprising: The sulfur-containing compound represented by following General formula (2) is acrylate-ized. In particular, the compound of the general formula (2) is reacted with a halopropionic acid or an acid halide thereof to form a halopropionic acid ester compound, and then dehydrohalogenated to form an acrylic ester. Regarding the method.

  Furthermore, it is related with the sulfur-containing compound represented by General formula (2) useful as a raw material of this acrylate compound.

(In the formula, R ₁ and R ₂ each independently have 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)

  The acrylic ester compound of the present invention is very useful as a monomer for a photocurable polymerizable composition in applications such as optical materials and dental materials. The 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. Thus, it is useful as various plastic lenses represented by correction eyeglass 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 is possible to provide a sulfur-containing compound represented by the general formula (2) that is very useful as a raw material for the acrylate compound.

  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 having a structural feature that it has a specific dithiolane ring structure.

In the general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an aromatic alkyl group that may have a substituent, or a substituent. An aromatic residue that may be present. Here, the term “aromatic alkyl group” and “aromatic residue” means that the former has an aromatic ring bonded via an alkyl group, whereas the latter has a direct bond to a constituent atom of the aromatic ring. This means that the aromatic ring in these groups may be an aromatic heterocyclic ring containing a hetero atom.

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 or / and R ₂ is an alkyl group which may have a substituent, the substituent contained in the alkyl group includes an alkoxy group, an alkoxyalkoxy group, an aromatic alkyloxy group, an aryloxy group Aryloxyalkyloxy group, alkylthio group, alkylthioalkylthio group, aromatic alkylthio group, arylthio group or 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 is substituted. Is preferred. As such substituents, alkyl groups, alkoxy groups, alkoxyalkoxy groups, aralkyloxy groups, aryl groups, aryloxy groups, aryloxyalkyloxy groups, alkylthio groups, alkylthioalkylthio groups, aralkylthio groups, arylthio groups, arylthioalkylthio groups Or a halogen atom etc. are mentioned.

R ₁ or / and R ₂ may have a substituted aromatic alkyl group or aromatic ring in the aromatic residue includes aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, or thiophene, Examples of the ring include aromatic rings such as pyridine, pyrrole, furan, γ-pyran, γ-thiopyran, thiazole, imidazole, pyrimidine, 1,3,5-triazine, indole, quinoline, and purine.

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

Specific examples of such substituents R ₁ and R ₂ include
Hydrogen atom,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, heptyl group, octyl group, cyclohexyl group, cyclohexyl group A linear, branched or cyclic alkyl group such as a methyl group,
A substituted or unsubstituted aromatic alkyl group such as benzyl group, 4-methylbenzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, β-phenylethyl group,
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-bromophenyl group, α-naphthyl group, β-naphthyl group, 2-furyl group, 3-furyl group, thiophen-2-yl group, thiophen-3-yl group, etc. Examples include substituted or unsubstituted aromatic residues.

More preferably, the substituent R ₁ and / or R ₂ is a hydrogen atom, methyl group, benzyl group, β-phenylethyl group, phenyl group, thiophen-2-yl group, thiophen-3-yl group, 4- A phenylphenyl group, an α-naphthyl group or a β-naphthyl group;

In consideration of the effect of the present invention, the substituent R ₁ may be a phenyl group, a thiophen-2-yl group, a thiophen-3-yl group, a 4-phenylphenyl group, an α-naphthyl group, or a β-naphthyl group. preferable.

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 that may contain an oxygen atom or a sulfur atom, and more preferably an alkylene group that may contain an oxygen atom or a sulfur atom having 1 to 10 carbon atoms. And more preferably a group represented by the following formula (a).

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

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

  In said formula (a), m is an integer of 1-3, Preferably, it is an integer of 1-2, More preferably, it is the integer 1.

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

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

In order to obtain various desired effects of the present invention, in 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.

As the acrylic ester compound represented by the general formula (1) of the present invention, for example,
4-acryloylthiomethyl-1,3-dithiolane,
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′-tert-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,
2- (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-methacryloylthiomethyl-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-methacryloylthiomethylthiomethyl-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-methacryloylthioethylthio) 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,
2-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-methacryloyloxymethylthio) propyl] -1,3-dithiolane,
Although 2-β-naphthyl-4- [2-methyl-2- (2-methacryloyloxymethylthio) ethyl] -1,3-dithiolane and the like are shown, the present invention is not limited to these.

The acrylic ester compound represented by the general formula (1) of the present invention is suitably produced by various known esterification methods using the sulfur-containing compound represented by the general formula (2) as a raw material. The That is, for the sulfur-containing compound represented by the following general formula (2),
<1> A method of reacting (meth) acrylic acids [for example, (meth) acrylic acid, acid halides or ester derivatives thereof, etc.] to form (meth) acrylic acid esters (for example, JP-A 64-26613 And the method described in JP-A No. 64-31759, JP-A No. 63-188660, etc.);
<2> A halopropionic acid (for example, 3-chloropropionic acid, 3-bromopropionic acid, 3-chloro-2-methylpropionic acid, 3-bromo-2-methylpropionic acid, etc.) or an acid halide thereof is reacted. , A method of dehalogenating and converting to an acrylate ester after forming a halopropionic ester compound (for example, JP-A-10-204056, JP-A-2-172968, JP-A-2-172969, The acrylic ester compound represented by the general formula (1) is produced by various known esterification methods, such as the method described in JP-A-4-29967).

（式中、Ｒ₁、Ｒ₂、ＡおよびＸは前記に同じ）

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

  Among the above methods, the method of the latter <2> is more preferable as a method for producing the acrylate compound represented by the general formula (1) of the present invention.

  Among these methods, the method shown in the following reaction pathway, that is, the sulfur-containing compound represented by the general formula (2) was reacted with an acid halide of a halopropionic acid to obtain a halopropionic ester compound (3). Thereafter, a method for producing an acrylic ester compound represented by the general formula (1) by dehydrohalogenating the halopropionic ester compound (3) in the presence of a base is further preferred.

（上式中、Ｒ₁、Ｒ₂、Ｒ₃、ＡおよびＸは前記に同じであり、Ｚ₁およびＺ₂はそれぞれ塩素原子または臭素原子を表す）

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

Hereinafter, this method will be described in more detail.
First, the method for producing the halopropionic acid ester compound (3) by the reaction of the sulfur-containing compound represented by the general formula (2) and the acid halide of halopropionic acids will be described in detail.

  In this reaction, halopropionic acids (for example, 3-chloropropionic acid, 3-bromopropionic acid, 3-chloro-2-methylpropionic acid) that act on the sulfur-containing compound represented by the general formula (2). , 3-bromo-2-methylpropionic acid and the like) is not particularly limited, but is usually 0.1 to 5 moles per mole of the sulfur-containing compound, Preferably, it is 0.2-3 mol, More preferably, it is 0.5-2 mol. The amount of the halopropionic acid halide used is particularly preferably 0.8 to 1.5 mol.

  The reaction may be carried out without solvent or in an inert solvent for the reaction. Such a solvent is not particularly limited as long as it is a reaction-inert solvent, and for example, water, an organic solvent, or a mixed system thereof may be used. Examples of the organic solvent include hydrocarbon solvents such as n-hexane, benzene and toluene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and 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 Examples include polar solvents such as imidazolidinone, dimethyl sulfoxide and sulfolane. These solvents may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in reaction temperature, Usually, it is the range of -78-150 degreeC, Preferably, it is -20-120 degreeC, More preferably, it is 0-100 degreeC.

  Although the reaction time depends on the reaction temperature, it is usually from several minutes to 100 hours, preferably from 30 minutes to 50 hours, and more preferably from 1 to 20 hours. In addition, the reaction can be stopped at an arbitrary reaction rate while the reaction rate is confirmed 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 using a dehydrohalogenating agent.

  Examples of the dehydrohalogenating agent include triethylamine, pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4. 0] An organic base such as undec-7-ene (DBU), or an inorganic base such as sodium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, etc. Illustrated.

  The amount of the dehydrohalogenating agent used is not particularly limited, but is 0.05 to 10 mol, preferably 0 to 1 mol of the sulfur-containing compound represented by the general formula (2). 0.1 to 5 mol, and more preferably 0.5 to 3 mol.

  Next, the 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.

  Examples of the base used in this reaction include 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-ene (DBU) and other organic bases, or sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, water Examples include inorganic bases such as calcium oxide and magnesium oxide.

  Although there is no restriction | limiting in particular as the usage-amount of this base, It is 0.05-10 mol with respect to 1 mol of halopropionic ester compounds (3), Preferably, it is 0.1-5 mol, More Preferably, it is 0.5-3 mol.

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

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

  There is no restriction | limiting in particular in reaction temperature, Usually, it is the range of -78-150 degreeC, Preferably, it is -20-120 degreeC, More preferably, it is 0-100 degreeC.

  Although the reaction time depends on the reaction temperature, it is usually from several minutes to 100 hours, preferably from 30 minutes to 50 hours, and more preferably from 1 to 20 hours. In addition, the reaction can be stopped at an arbitrary reaction rate while the reaction rate is confirmed by a known analysis means (for example, liquid chromatography, gas chromatography, thin layer chromatography, IR, etc.).

  In the reaction pathway described above, after the first stage halopropionate esterification reaction, the intermediate halopropionate compound represented by the general formula (3) is once taken out, and then the second stage dehalogenation. A stepwise method of performing hydrogen halide may be used, or among the methods of performing the next dehydrohalogenation reaction in one step (one-pot) without taking out the halopropionic ester compound in the middle, Either method can be used.

  In producing the acrylic ester 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. .

  Examples of such a polymerization inhibitor include various known compounds such as 4-methoxyphenol, 2,6-di-tert-butylcresol, hydroquinone, phenothiazine and the like.

  Although there is no restriction | limiting in particular in the usage-amount of a polymerization inhibitor, It is 0.001-5 mass% normally with respect to the raw material mixture or reaction product in a reaction system, Preferably, it is 0.05-3 mass%. Yes, more preferably from 0.01 to 1% by mass.

  After completion of the reaction, the acrylate ester compound represented by the general formula (1) of the present invention, which is a product, is a known operation, treatment method (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, etc. ) To be isolated by post-treatment. The acrylic ester compound represented by the general formula (1) obtained by the above method is further separated and purified by a known method (for example, distillation, recrystallization, chromatography, activated carbon treatment, etc.) as necessary. And isolated as a higher purity compound.

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

In the general formula (2), R ₁ , R ₂ , A and X represent the same meaning as R ₁ , R ₂ , A and X in the general formula (1) described above.

As the sulfur-containing compound represented by the general formula (2) of the present invention, for example,
4-mercaptomethyl-1,3-dithiolane,
2-methyl-4-mercaptomethyl-1,3-dithiolane,
2-ethyl-4-mercaptomethyl-1,3-dithiolane,
2-n-propyl-4-mercaptomethyl-1,3-dithiolane,
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,
2- (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- (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,
2- (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-Fryl-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,
The present invention is not limited to these exemplary compounds.

  In the general formula (2), the compound in which X is an oxygen atom is the same as the reaction per se known method [for example, the method described in Journal of Chemical Society (C), pages 415 to 419 (1966)]. Thus, it is preferably manufactured.

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

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

（上記式中、Ｒ₁、Ｒ₂、ＡおよびＸは、前記に同じ）

(In the above formula, R ₁ , R ₂ , A and X are the same as above)

  The sulfur-containing thiol compound in which X is a sulfur atom in the general formula (2) of the present invention is a method known per se by using a sulfur-containing hydroxy compound in which X is an oxygen atom in the general formula (2) as a raw material. Thus, it is suitably produced by converting a hydroxy group in the molecule into a thiol group.

  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 such as Journal of American Chemical Society, 68, pages 2103-2104 (1946), Journal of Organic Chemistry, 27, pages 93-95 (1962), Organic Synthesis, V, pages 401-403 (1963), etc. To be implemented.

  That is, a hydroxy compound in which X in the general formula (2) is an oxygen atom is allowed to react with, for example, hydrogen chloride or hydrogen bromide to induce the hydroxy compound to a halogen compound, and then thiourea is reacted with the halogen compound. Then, 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 hydrolyzing as a thioronium salt and then using a base such as aqueous ammonia or sodium hydroxide.

  Next, the polymerizable composition containing the acrylic ester compound represented by the general formula (1) of the present invention will be described in detail.

  The polymerizable composition of the present invention contains an acrylic ester compound represented by the general formula (1) of the present invention and a polymerization initiator as essential components. 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 later 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.

  Furthermore, the polymerizable composition of the present invention is a compound having a known polymerizable property in addition to containing the acrylate compound represented by the general formula (1) as necessary, as long as the desired effect is not impaired. (Light or / and thermopolymerizable monomer or oligomer, etc.) may be contained.

  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 or more with respect to the mass of the entire polymerizable composition. The amount is 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 (photopolymerization initiator). ) Can be used.

Examples of the photopolymerization initiator include benzophenone, 4-methylbenzophenone, 4,4′-dichlorobenzophenone, 2,4,6-trimethylbenzophenone, o-benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, 4- (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) benzenemethananium bromide, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2- Propenyloxy) ethyl] benzenemethananium 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) -N, N, N-trimethyl-1-propananium chloride, 2-benzoylmethylene-3-methylnaphtho (1 , 2-d) carbonyl compounds such as thiazoline;

Benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione (common name: camphorquinone), 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1 -Dicarbonyl compounds such as chloroanthraquinone, 2-amylanthraquinone, 9,10-phenanthrenequinone, α-oxobenzeneacetic acid methyl ester;
Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- [4- (2-hydroxy Ethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one,
1-hydroxycyclohexyl phenyl ketone,
Dimethoxyacetophenone, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-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-propanedione-2- (o-ethoxycarbonyl) oxime,
Acetophenone compounds such as 3,6-bis (2-methyl-2-morpholinopropanoyl) -9-butylcarbazole;
Benzoin ether compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether;
Allylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dichlorobenzoyl)-(4-n-propylphenyl) phosphine oxide;
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, 2,5′-bis (4-dimethylaminobenzal) cyclopentanone;

2,2,2-trichloro-1- (4′-tert-butylphenyl) ethane-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, 2,4-bis (trichloromethyl)- 6- (4-methoxystyryl) triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuryl) ethylidine] triazine, 2,4-bis (trichloromethyl) ) Halogen compounds such as -6- [2-furylethylidin] triazine;
9-phenylacridine, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole, 2,2-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) -benzene] iron (II) hexafluorophosphate, bis (5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-pyr-1-yl) phenyl] titanium, etc. The compound of can be illustrated. These may be used alone or in combination of two or more.

  The usage-amount of this photoinitiator is 0.001-50 mass parts with respect to 100 mass parts of acrylic ester compounds represented by General formula (1), Preferably, 0.01-30 mass parts More preferably, it is 0.1-10 mass parts, More preferably, it is 0.2-5 mass parts.

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

  The usage-amount of this thermal-polymerization initiator is 0.001-50 mass parts normally with respect to 100 mass parts of acrylic ester compounds represented by General formula (1), Preferably, it is 0.01-30. It is a mass part, More preferably, it is 0.1-10 mass part, More preferably, it is 0.2-5 mass part.

As a polymerizable compound used for the polymerizable composition of the present invention, as a compound having a known polymerizable property other than the acrylate compound represented by the general formula (1),
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, acryloylmorpholine, trifluoroethyl (meth) acrylate, Monofunctional acrylates such as tribromobenzyl (meth) acrylate and 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-methacrylic) (Royloxy) 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-Methacryloyloxy Toxi) 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′-bis (2-acryloyloxypropoxy) phenylsulfone, 4,4′-bis (2-methacryloyloxypropoxy) ) Bifunctional (meth) acrylates such as phenylsulfone;

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

Phenylglycidyl ether,
Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, resorcin diglycidyl ether, hydroquinone diglycidyl ether, bis (4-hydroxyphenyl) methane (common name, bisphenol F) diglycidyl ether, 2,2-bis (4-hydroxyphenyl) ) Propane (common name, bisphenol A) diglycidyl ether, 4,4′-bishydroxyphenyl sulfide diglycidyl ether, 4,4′-bishydroxyphenyl sulfone (common name, bisphenol S) diglycidyl ether, 4,4′-biphenol Monovalent or divalent or more such as diglycidyl ether, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol diglycidyl ether, tris (2,3-epoxypropyl) isocyanurate Respect of the epoxy compound, (meth) epoxy (meth) acrylates obtained by acting acrylic acid compounds;
Epoxy (meth) acrylates obtained by allowing a (meth) acrylic acid compound to act on an epoxy resin such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, a phenol zylock epoxy resin, or a bisphenol epoxy resin;

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

  In order to achieve the effects of the present invention, the amount of these used is usually 300 parts by mass or less with respect to 100 parts by mass of the acrylate compound represented by the general formula (1), preferably 200 The amount is not more than part by mass, and more preferably not more than 100 parts by mass.

  Specifically, as the method for producing the polymerizable composition of the present invention, the acrylic ester compound represented by the general formula (1) of the present invention is used, and if desired, various known polymerizable compounds are used in combination. Further, it can be obtained by adding the polymerization initiator and then mixing and dissolving. The polymerizable composition is used for polymerization and curing by removing insoluble matters, foreign matters and the like by filtration before polymerization as necessary, and sufficiently defoaming under reduced pressure.

  Further, when producing the polymerizable composition, an internal mold release agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a color pigment (for example, cyanine green, cyanine blue, etc.), a dye, Various known additives such as a flow regulator and an inorganic filler (for example, talc, silica, alumina, barium sulfate, magnesium oxide, etc.) can be added.

  The cured product of the present invention and the optical component comprising the cured product are obtained by polymerizing and curing the polymerizable composition. As these methods, various conventionally known methods are adopted and preferably carried out. Typically, the polymerizable composition obtained as described above is poured into a mold and started by heat or light. And cast polymerization using a radical polymerization reaction.

  The mold is composed of, for example, two molds that are mirror-polished through a gasket made of polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like. Examples of the mold include glass and glass, glass and plastic plate, glass and metal plate, and the like. Further, as the gasket, in addition to using the soft thermoplastic resin (polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, etc.), two molds may be fixed with a polyester adhesive tape or the like. Moreover, you may perform well-known processing methods, such as a mold release process, with respect to a casting_mold | template.

  As described above, as the radical polymerization reaction, a method using a polymerization reaction by heat (thermal polymerization), a polymerization reaction by light such as ultraviolet rays (photopolymerization), a polymerization reaction by gamma rays, or a combination of these is used. Examples are methods.

  When polymerization is performed by light, after curing, 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 or distortion. .

  Among these methods, thermal polymerization requires several hours to several tens of hours, whereas photopolymerization using ultraviolet rays or the like can be cured in several seconds to several minutes, and is produced during production of the optical component of the present invention. Considering the point of improving the property, this is a preferable method.

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

  As described above, examples of the molding method of the optical lens include a method of obtaining a lens by performing casting polymerization with light or / and heat (for example, JP-A-60-135901, JP-A-10-67736). No., JP-A-10-130250, etc.).

  That is, after defoaming the polymerizable composition containing the acrylate ester compound represented by the general formula (1) of the present invention produced by the above-described method by an appropriate method, if necessary, It is preferably carried out by a method of injecting into a mold and polymerizing by irradiation with light. In addition, the polymerization by heat is preferably carried out by a method of polymerizing by gradually heating from a low temperature to a high temperature.

  The obtained optical lens may be annealed as necessary after curing. If necessary, surface polishing, antistatic treatment, hard coat treatment, non-reflective coating treatment, dyeing treatment, dyeing treatment, antireflection, high hardness, wear resistance improvement, antifogging or fashionability. Various known physical or chemical treatments such as light treatment (for example, photochromic lens formation treatment) may be performed.

  As a method for forming a substrate of an optical disk or a magneto-optical disk, for example, a polymerizable composition containing an acrylate compound represented by the general formula (1) obtained by the above method is injected into a disk substrate mold cavity. This is polymerized by a radical polymerization method or the like, followed by post-heat treatment as necessary (Japanese Patent Laid-Open Nos. 58-130450, 58-137150, 62-280008, etc.), in a double-sided glass mold Conventionally well-known methods, such as photopolymerization method (Japanese Patent Laid-Open No. Sho 60-202557), and vacuum casting or liquid injection after pressurization to thermally polymerize a liquid resin (Japanese Patent Laid-Open No. Sho 60-203414). And the like.

  The cured product obtained by photopolymerization of the polymerizable composition of the present invention and the optical component comprising the cured product have a time required for polymerization and curing of several minutes to several hours, and the existing polydiethylene glycol diallyl carbonate, polythiol One of the characteristics is that it can be polymerized and molded in a short time as compared with a thermosetting optical resin typified by urethane, and has high productivity.

  Furthermore, the cured product and the optical component of the present invention have the characteristics that transparency, mechanical properties, and thermal properties are good, and that the refractive index is higher than that of known photopolymerizable monomers. Yes. Specific examples of the optical component include various plastic lenses represented by correction eyeglass lenses, optical information recording medium substrates, plastic substrates for liquid crystal cells, and optical fiber coating materials.

  The (meth) acrylic acid ester compound represented by the general formula (1) of the present invention is a novel compound having a cyclic thioacetal structure in the molecule, and is a resin raw material for optical components typified by correction eyeglass lenses. It is a very useful compound as a monomer.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

<1> Synthesis Production Example 1 of a sulfur-containing compound represented by the general formula (2) [Synthesis of 4-hydroxymethyl-1,3-dithiolane]
The method was described in Journal of Chemical Society (C), pages 415-419 (1966). That is, 250 ml of 30% formaldehyde aqueous solution and 250 ml of dioxane were weighed in a glass 1 liter reactor equipped with a stirrer and a condenser, and 186 g of 2,3-dimercaptopropanol was stirred with respect to these mixtures. 1.5 mol) was 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 in a nitrogen atmosphere. After confirming that the raw material 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 extraction with chloroform and further washing with water to obtain 133 g (0.98 mol) of 4-hydroxymethyl-1,3-dithiolane as a target product.
Yield 65%
Purity> 99% (Area method by gas chromatography analysis)
Boiling point: 124-125 ° C./266 kPa (2 mmHg)
EI-MS: 136 (M)

Example 1 [Synthesis of 4-mercaptomethyl-1,3-dithiolane; a compound in which R ₁ = hydrogen atom, R ₂ = hydrogen atom, A = -CH ₂ -group, X = sulfur atom in the general formula (2) ]
In a 500-ml glass reactor equipped with a stirrer and a condenser, 38.0 g (0.50 mol) of thiourea and 88 g of 48% hydrobromic acid (equivalent to 0.5 mol of hydrogen bromide) were placed. . To this mixture, 68 g (0.50 mol) of 4-hydroxymethyl-1,3-dithiolane synthesized in Production Example 1 was added dropwise at 60 ° C. over 35 minutes. Further, the reaction was carried out at 80 ° C. for 4 hours to carry out thulonium chloride. The reaction solution was analyzed by high performance liquid chromatography to confirm that the raw hydroxy compound had disappeared. To the reaction mixture, 300 g of 18% aqueous ammonia was added dropwise at 50 ° C. over 10 minutes. For 2 hours to hydrolyze the thiouronium salt. After 200 g of toluene was added for liquid separation and extraction, the toluene phase was washed with water until the waste water phase became neutral. Thereafter, the toluene phase was taken out, and toluene was distilled off at 40 ° C. under reduced pressure to give a crude yellow transparent liquid. The product was obtained. The crude product was purified by silica gel column chromatography (using toluene as a solvent) to give 61 g (0.40 mol) of 4-mercaptomethyl-1,3-dithiolane represented by the following formula (2-1) as a colorless liquid. )
Yield = 80%, purity> 99% (area method by gas chromatography analysis)
EI-MS: 152 (M)

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, X = Compounds that are sulfur atoms)
In a glass 1 liter reactor equipped with a stirrer and a condenser, 2,3-dimercaptopropanol 50.0 g (0.40 mol), 98% sulfuric acid 0.44 g (0.004 mol) and dioxane 80 g were weighed. Then, 46.8 g (0.442 mol) of benzaldehyde was added dropwise to the mixed solution at 25 ° C. over 30 minutes. The reaction was further completed by stirring at 70 ° C. for 5 hours, and then 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, and liquid separation was repeated, and then the organic layer was taken out. Toluene was distilled off under reduced pressure and concentrated, and n-hexane was added and left standing, and the precipitated crystals were filtered out. Further, it was washed with toluene / hexane (weight ratio = 60/40) to obtain 72.2 g of 2-phenyl-4-hydroxymethyl-1,3-dithiolane represented by the following formula (2-2) as a white crystal. .
Yield 85%
Purity 99% (calculated by gas chromatograph 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)
EI-MS: 212 (M)

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

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

Example 5 [Synthesis of 2- (thiophen-2-yl) -4-hydroxymethyl-1,3-dithiolane; In General Formula (2), R ₁ = thiophen-2-yl group, R ₂ = hydrogen atom, A = -CH2-group, X = oxygen atom compound]
In Example 2, instead of using benzaldehyde, the same procedure as described in Example 2 was used except that 2-formylthiophene was used, and 2- (thiophene-2 represented by the following formula (2-5) was used. -Yl) -4-hydroxymethyl-1,3-dithiolane was obtained.
EI-MS: 218 (M)

Example 6 [Synthesis of 2-phenyl-4-mercaptomethyl-1,3-dithiolane; in the general formula (2), R ₁ = phenyl group, R ₂ = hydrogen atom, A = —CH ₂ — group, X = sulfur Compound that is an atom)
In Example 1, instead of using 4-hydroxymethyl-1,3-dithiolane synthesized in Preparation Example 1, 2-phenyl-4-hydroxymethyl-1,3-dithiolane prepared in Example 2 is used. Except that, 2-phenyl-4-mercaptomethyl-1,3-dithiolane represented by the following formula (2-6) was obtained in the same manner as in Example 1.
270 MHz ¹ H-NMR δ (CDCl 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)

Example 7 [Synthesis of 2- (α-naphthyl) -4-mercaptomethyl-1,3-dithiolane; in general formula (2), R ₁ = α-naphthyl group, R ₂ = hydrogen atom, A = -CH ₂ -Compound wherein X is a sulfur atom]
In Example 1, instead of using 4-hydroxymethyl-1,3-dithiolane synthesized in Production Example 1, 2- (α-naphthyl) -4-hydroxymethyl-1,3- produced in Example 3 was used. Except that dithiolane is used, the same procedure as described in Example 1 is performed to obtain 2- (α-naphthyl) -4-mercaptomethyl-1,3-dithiolane represented by the following formula (2-7). It was.
EI-MS: 278 (M)

Example 8 [Synthesis of 2- (β-naphthyl) -4-mercaptomethyl-1,3-dithiolane; in general formula (2), R ₁ = β-naphthyl group, R ₂ = hydrogen atom, A = -CH ₂ -group, compound in which X = sulfur atom]
In Example 1, instead of using 4-hydroxymethyl-1,3-dithiolane synthesized in Preparation Example 1, 2- (β-naphthyl) -4-hydroxymethyl-1,3-prepared in Example 4 was used. Except that dithiolane is used, the same procedure as described in Example 1 is performed to obtain 2- (β-naphthyl) -4-mercaptomethyl-1,3-dithiolane represented by the following formula (2-8). It was.
EI-MS: 278 (M)

Example 9 [Synthesis of 2- (thiophen-2-yl) -4-mercaptomethyl-1,3-dithiolane; In General Formula (2), R ₁ = thiophen-2-yl group, R ₂ = hydrogen atom, Compound in which A = —CH ₂ — group and X = sulfur atom]
In Example 1, instead of using 4-hydroxymethyl-1,3-dithiolane synthesized in Production Example 1, 2- (thiophen-2-yl) -4-hydroxymethyl-1, produced in Example 5, was used. 2- (thiophen-2-yl) -4-mercaptomethyl-1,3 represented by the following formula (2-9) is carried out in the same manner as in Example 1 except that 3-dithiolane is used. -Dithiolane was obtained.
EI-MS: 234 (M)

<2> Synthesis of Acrylic Acid Ester Compound Represented by General Formula (1) Example 10 [Synthesis of 4-acryloylthiomethyl-1,3-dithiolane; R ₁ = hydrogen atom, R ₂ in general formula (1) = Hydrogen atom, R ₃ = Hydrogen atom, A = —CH ₂ — group, X = Sulfur atom]
In a glass 500 ml reaction vessel equipped with a stirrer and a cooling tube, 91.2 g (0.60 mol) of 4-mercaptomethyl-1,3-dithiolane (2-1) produced in Example 1 was weighed, To this, 80.0 g (0.63 mol) of 3-chloropropionic acid chloride was added dropwise at 40 ° C. for 15 minutes. Furthermore, after stirring and reacting at 40 ° C. for 8 hours, 200 g of toluene was added to the reaction mixture solution, dissolved, transferred to a separatory funnel, and washed three times with 300 g of 3% by mass aqueous sodium hydrogen carbonate solution. . Then, after washing with 300 g of pure water until the aqueous layer becomes neutral, the organic layer (toluene solution) is taken out, and toluene is distilled off under reduced pressure to remove colorless transparent liquid 4- (3-chloropropionylthio) methyl. 119 g of -1,3-dithiolane was obtained.

  Next, in a glass 1 liter reaction vessel, 119 g (0.49 mol) of 4- (3-chloropropionylthiomethyl) -1,3-dithiolane obtained as described above was dissolved in 200 g of acetone. On the other hand, 74 g (0.73 mol) of triethylamine was added dropwise at 25 ° C. over 1 hour. Then, after stirring and reacting at 25 ° C. for 6 hours, 400 g of toluene and 400 g of water were added to the reaction mixture, and the toluene phase was separated and extracted. The toluene solution was washed with 5% by mass aqueous hydrochloric acid and further washed with water until the aqueous phase became neutral, and then toluene was distilled off under reduced pressure to obtain a viscous colorless transparent liquid represented by the following formula (1-1). As a result, 99 g (0.48 mol) of 4-acryloylthiomethyl-1,3-dithiolane was obtained.

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

Example 11 [Synthesis of 2-phenyl-4-acryloylthiomethyl-1,3-dithiolane; in general formula (1), R ₁ = phenyl group, R ₂ = hydrogen atom, R ₃ = hydrogen atom, A = -CH ₂ -group, compound in which X = sulfur atom]
Instead of using 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material in Example 10 above, 2-phenyl-4-mercaptomethyl prepared in Example 6 was used. The target compound 2-phenyl-4-acryloyl represented by the following formula (1-2) was prepared in the same manner as in Example 10 except that -1,3-dithiolane (2-6) was used. Thiomethyl-1,3-dithiolane was obtained.
270 MHz ¹ H-NMR δ (CDCl ₃ ):
3.22 to 3.55 (m, 4H), 4.08 (dm, 1H),
5.68-5.77 (m, 2H), 6.35-6.40 (d, 2H), 7.25-7.55 (5H)
EI-MS: 282 (M)

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

Example 12 Synthesis of [2- (α-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane; in general formula (1), R ₁ = α-naphthyl group, R ₂ = hydrogen atom, R ₃ = hydrogen Atom, A = —CH ₂ — Group, X = Sulfur Atom]
In Example 10 above, instead of using 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material, 2- (α-naphthyl)-prepared in Example 7 was used. Except for the use of 4-mercaptomethyl-1,3-dithiolane (2-7), the same procedure as described in Example 10 was carried out, and the target compound 2- ( α-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane was obtained.
EI-MS: 332 (M)

Example 13 Synthesis of [2- (β-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane; in general formula (1), R ₁ = β-naphthyl group, R ₂ = hydrogen atom, R ₃ = hydrogen Atom, A = —CH ₂ — Group, X = Sulfur Atom]
In Example 10 above, instead of using 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material, 2- (β-naphthyl)-prepared in Example 8 was used. Except for the use of 4-mercaptomethyl-1,3-dithiolane (2-8), the same procedure as described in Example 10 was carried out, and the target compound 2- ( β-naphthyl) -4-acryloylthiomethyl-1,3-dithiolane was obtained.
EI-MS: 332 (M)

Example 14 Synthesis of [2- (thiophen-2-yl) -4-acryloylthiomethyl-1,3-dithiolane; in general formula (1), R ₁ = thiophen-2-yl group, R ₂ = hydrogen atom, Compound in which R ₃ = hydrogen atom, A = —CH ₂ —group, X = sulfur atom]
In Example 10, instead of using 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material, 2- (thiophen-2-yl) prepared in Example 9 was used. ) -4-mercaptomethyl-1,3-dithiolane (2-9), except that the method described in Example 10 was used, and 2 of the target compound represented by the following formula (1-5) -(Thiophen-2-yl) -4-acryloylthiomethyl-1,3-dithiolane was obtained.
EI-MS: 288 (M)

Example 15 [Synthesis of 2-phenyl-4-acryloyloxymethyl-1,3-dithiolane; in general formula (1), R ₁ = phenyl group, R ₂ = hydrogen atom, R ₃ = hydrogen atom, A = -CH ₂ -group, compound in which X = oxygen atom]
In Example 10 above, instead of using 4-mercaptomethyl-1,3-dithiolane (2-1) prepared in Example 1 as a reaction raw material, 2-phenyl-4-hydroxymethyl prepared in Example 2 was used. The target compound 2-phenyl-4-acryloyl represented by the following formula (1-6) was prepared in the same manner as in Example 10 except that -1,3-dithiolane (2-2) was used. Oxymethyl-1,3-dithiolane was obtained.
270 MHz ¹ H-NMR δ (CDCl ₃ ):
3.30 to 3.55 (m, 2H), 4.00 to 4.55 (m, 3H), 5.75 (s, 1H), 5.85 to 5.90 (dd, 1H), 6. 10 to 6.20 (dd, 1H), 6.40 to 6.50 (d, 1H), 7.20 to 7.60 (5H)
EI-MS: 266 (M)

<3> Production of polymerizable composition using acrylic ester compound represented by general formula (1) and production of cured product by curing thereof Cured product or optical component (lens) produced in the following Examples and Comparative Examples ) Physical properties (transparency, thermal characteristics, mechanical characteristics) were evaluated by the following methods.
Appearance: The color and transparency were confirmed visually.
Refractive index and Abbe number: Measured at 20 ° C. using a Purfrich refractometer.
Heat resistance: The glass transition temperature of the cured product was measured using TMA (needle penetration method).
Impact resistance: An iron ball having a height of 127 cm to 28.7 g was dropped on the center of a minus lens having a center thickness of 1.5 mm, and the presence or absence of cracks was examined.

Example 16
With respect to 30 g of the acrylic ester compound (4-acryloylthiomethyl-1,3-dithiolane) obtained in Example 10, 2-hydroxy-2-methyl-1-phenylpropane-1- was used as a photopolymerization initiator. 150 mg of ON (“Darocur-1173”, registered trademark of Ciba) was added and mixed well to dissolve. The obtained liquid was sufficiently degassed under reduced pressure, and then poured into a mold comprising a glass mold and a gasket. Polymerization was performed by irradiating with ultraviolet rays for 60 seconds using a metal halide lamp (80 W / cm). After the polymerization was completed, the mixture was gradually cooled, and the molded cured product was taken out from the mold.

  The obtained cured product was colorless and transparent, and no optical distortion was observed. The refractive index (nd) was 1.660, and the Abbe number was 36 (νd).

Examples 17-21
Hereinafter, in Example 16 above, instead of using the acrylic ester compound (4-acryloylthiomethyl-1,3-dithiolane) obtained in Example 10, the acrylic ester produced in Examples 11 to 15 was used. Instead of using a compound and using 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photopolymerization initiator, 2,4,6-trimethoxybenzoyldiphenylphosphine oxide (manufactured by BASF) is used. The polymerization composition was prepared, polymerized, and cured in the same manner as in Example 16 except that it was used.

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

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

Example 22
24 g of the acrylic acid ester compound (2-phenyl-4-acryloylthiomethyl-1,3-dithiolane) obtained in Example 11 above, 3 g of trimethylolpropane trimethacrylate and 3 g of bisphenol A diglycidyl ether dimethacrylate were mixed. As a photopolymerization initiator, 30 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF) is added to the resulting mixture, and mixed and dissolved. A polymerizable composition was prepared. The obtained composition was sufficiently degassed under reduced pressure, and then poured into a mold comprising a glass mold and a gasket. Polymerization was performed by irradiating with ultraviolet rays for 60 seconds using a metal halide lamp (120 W / cm). Thereafter, after gradually cooling to room temperature, the cured product was taken out of the mold, and further annealed by heating at 130 ° C. for 2 hours in an inert oven.

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

  The glass transition temperature of the cured product was such that there was no practical problem 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, it is a known acrylate compound (described in JP-A-3-217212). Polymerization was carried out in the same manner as described in Example 22, except that 24 g of 1,4-bis (2-methacryloyloxyethylthio) xylylene and 6 g of 2,2-bis (4-methacryloyloxyethoxyphenyl) propane were used. A lens composition was prepared.

  The lens was colorless and transparent, the refractive index (nd) was 1.588, and the Abbe number (νd) was 39.

Comparative Example 2
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 (used in Example 1 of JP-A-3-215801) is used. A polymerizable composition was prepared in the same manner as described in Example 22 except that 2-methacryloyloxymethyl-1,4-dithiane, which is a compound), was used, and a cured product was produced. The cured product was colorless and transparent with 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 (described on page 61 in the text of JP-T-12-509075) The polymerizable composition is prepared in the same manner as described in Example 22 except that 6-methacryloyloxy-1,4-dithiacycloheptane, which is a compound that has been prepared, is used, and a cured product is obtained. Produced. The cured product was colorless and transparent with a refractive index (nd) of 1.545 and an Abbe number (νd) of 43.5.

  Since the acrylic ester compound of the present invention has a low viscosity compared to conventionally known monomers, it easily flows when preparing a polymerizable composition or when producing an optical component using the polymerizable composition. Excellent workability during handling.

  In addition, the polymerizable composition containing the acrylic ester compound of the present invention can be polymerized and cured in a short time by a compound (polymerization initiator) that starts polymerization by light irradiation, and can be cured with high production efficiency or a lens. The optical component can be obtained. The obtained cured product or lens is practically satisfactory in terms of physical properties such as heat resistance and impact resistance, and has a high refractive index as compared with known acrylate compounds.

Claims (1)

A sulfur-containing compound represented by the following general formula (2).

(In the formula, R ₁ and R ₂ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aromatic alkyl group which may have a substituent, or a substituent. Represents a good aromatic residue,
The substituent that the alkyl group may have is an alkoxy group, an alkoxyalkyl group, an aromatic alkyloxy group, an aryloxy group, an aryloxyalkyloxy group, an alkylthio group, an alkylthioalkylthio group, an aromatic alkylthio group, an arylthio group. And an arylthioalkylthio group,
The aromatic alkyl group or aromatic residue may have a substituent on the aromatic ring, and the substituent is an alkyl group, an alkoxy group, an alkoxyalkoxy group, an aralkyloxy group, an aryl group, an aryl group Selected from an oxy group, an aryloxyalkyloxy group, an alkylthio group, an alkylthioalkylthio group, an aralkylthio group, an arylthio group, an arylthioalkylthio group and a halogen atom;
A is the following formula (a)

(In said formula (a), B represents a C1-C3 alkylene group, Y is an oxygen atom or a sulfur atom, m is an integer of 1-3, n is an integer of 0-3. .) 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 a thiophen-2-yl group, a thiophen-3-yl group, a 4-phenylphenyl group, an α-naphthyl group or a β-naphthyl group , and X is a sulfur atom. And when A is a methylene group, one of R ₁ and R ₂ is a hydrogen atom, and the other has a hydrogen atom, an α- or β-naphthyl group, a thiophen-2-yl group, or the substituent described above. Represents an aromatic residue, or both R ₁ and R ₂ are simultaneously methyl groups, simultaneously phenyl groups or a combination of methyl and phenyl groups. )