JP2001316355A - Sulfur-containing unsaturated carboxylic ester compound and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical resin, in which defects of conventional optical resins are solved, excellent in optical characteristics, mechanical characteristics and thermal characteristics and having high productivity and high refractive index. SOLUTION: This sulfur-containing unsaturated carboxylic acid ester compound has a sulfur-containing substituent and at least two α,β-unsaturated carboxylic acid residues, which are each attached to a secondary or tertiary carbon atom via an oxygen atom. A polymerizable composition comprises the above sulfur-containing unsaturated carboxylate compound. A cured product is prepared by polymerizing the polymerizable composition. An optical component consists of the above cured product. New intermediate compounds are used for preparation of the above carboxylic acid ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an α, β-unsaturated carboxylic acid residue via a sulfur-containing substituent and at least two or more oxygen atoms bonded to secondary or tertiary carbon atoms. And a sulfur-containing unsaturated carboxylic acid ester compound having the formula: Further, the present invention relates to a polymerizable composition containing the sulfur-containing unsaturated carboxylic acid ester compound, and an optical component obtained by polymerizing the polymerizable composition.

[0002] The sulfur-containing unsaturated carboxylic acid ester compound of the present invention has a substituent containing a sulfur atom in the molecule and is bonded to at least two or more secondary or tertiary carbon atoms. It is structurally characterized by having an α, β-unsaturated carboxylic acid residue via an oxygen atom.

The sulfur-containing unsaturated carboxylic acid ester compound is useful as a monomer for a photocurable or heat-curable polymerizable composition, and is suitably used for various optical materials and dental materials. An optical component obtained by curing the polymerizable composition has excellent optical properties, thermal properties, and mechanical properties, and has good productivity, a high refractive index, and is represented by a corrective spectacle lens. It is useful as various plastic lenses, optical information recording medium substrates, plastic substrates for liquid crystal cells, optical fiber coating materials, and the like.

[0004]

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

[0005] A fundamentally important property as an optical material is transparency. Up to the present, polymethyl methacrylate (PMMA), bisphenol A polycarbonate (BPA-PC), polystyrene (PS), methyl methacrylate-styrene copolymer (MS), styrene-acrylonitrile Polymerized polymer (SAN), poly (4-methylpentene-1)
(TPX), polycycloolefin (COP), polydiethylene glycol bisallyl carbonate (EGA)
C), polythiourethane (PTU) and the like are known.

[0006] 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.

Although BPA-PC is excellent in transparency, heat resistance, impact resistance and high refraction, it has a 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.

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

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

EGAC is a thermosetting resin having diethylene glycol bisallyl carbonate as a monomer,
Most commonly used for general-purpose spectacle lens applications. Although it has excellent transparency and heat resistance and extremely 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 a reaction between a diisocyanate compound and a polythiol compound. PTU has high transparency, impact resistance and high refractive index, which are most often used for ultra-high refractive index spectacle lenses. Although this material is particularly excellent and has a small chromatic aberration, it is an extremely excellent material, but it has a drawback that it has a long thermopolymerization molding time (1 day to 3 days), and has a problem in productivity.

A method of obtaining an optical lens by photopolymerization using an acrylate containing a bromine atom or a sulfur atom for the purpose of polymerizing / curing in a short time to enhance the productivity is proposed. (For example,
JP-A-4-161410, JP-A-3-21741
No. 2 publication). However, according to this method, although polymerization can be performed in a short time, the obtained resin is not always satisfactory as an optical component. That is, for example, when used as a spectacle lens, a high-refractive-index lens has problems such as being brittle and fragile and having a large specific gravity. Therefore, development of a material that overcomes these problems has been strongly desired.

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

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the drawbacks of the conventional optical resin and to provide an optical resin having excellent optical properties, mechanical properties and thermal properties, high productivity and high refractive index. To provide.

[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 has <1> a sulfur-containing substituent and at least two or more α, β-unsaturated carboxylic acid residues via an oxygen atom bonded to a secondary or tertiary carbon atom. A sulfur-containing unsaturated carboxylic acid ester compound,

<2> a sulfur-containing unsaturated carboxylic acid ester compound represented by the following general formula (1):

[0018]

Embedded image[Wherein, R₁₁Represents a divalent organic group, and X₁₁Is German
First, an oxygen atom, a sulfur atom, a -COO- group or-(CH
_Two)_lX₁₂-Group (X₁₂Represents an oxygen atom or a sulfur atom,
l represents an integer of 1 to 3);₁₂Are independent
Represents a hydrogen atom or an alkyl group;₁₃Is German
Stands for a substituent containing a sulfur atom; ₁₄Are each
Independently represents an α, β-unsaturated carboxylic acid residue]

<3> The above sulfur-containing unsaturated carboxylic acid ester compound obtained by reacting a sulfur-containing dihydroxy compound represented by the following general formula (2) with an α, β-unsaturated carboxylic acid derivative:

[0020]

Embedded image [Wherein, R ₁₁ represents a divalent organic group, and X ₁₁ each independently represent an oxygen atom, a sulfur atom, a —COO— group, or — (CH
₂ ) ₁ X ₁₂ -group (X ₁₂ represents an oxygen atom or a sulfur atom, 1 represents an integer of 1 to 3), R ₁₂ each independently represents a hydrogen atom or an alkyl group, and R ₁₃ represents Independently represents a substituent containing a sulfur atom]

<4> The α, β-unsaturated carboxylic acid residue is
(Meth) acrylic acid residue, crotonic acid residue, tiglic acid residue, 3,3-dimethylacrylic acid residue, maleic acid residue, citraconic acid residue, 2,3-dimethylmaleic acid residue, itaconic acid The sulfur-containing unsaturated carboxylic acid ester compound which is a residue or a cinnamic acid residue,

<5> The divalent organic group R ₁₁ is represented by the following formula (3-
a) the above sulfur-containing unsaturated carboxylic acid ester compound, which is any group represented by (a), (4-a), (5-a) or formula (6-a);

[0023]

Embedded image (Wherein, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each a hydrogen atom,
Represents an alkyl group, an alkoxy group, a nitro group or a halogen atom)

[0024]

Embedded image Wherein Y ₄₁ is a single bond, a —C (R ₄₁ ) ₂ — group (R ₄₁ each independently represents a hydrogen atom or a methyl group), —O—
Group, -S- group or -SO ₂ - represents a group, R ₄₂ and R
₄₃ each independently represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an alkylthio group,
Represents a nitro group or a halogen atom, and m and n each represent an integer of 0 to 4]

[0025]

Embedded image (Wherein, R ₅₁ independently represents a hydrogen atom or an alkyl group)

[0026]

Embedded image (Wherein, R ₆₁ and R ₆₂ each represent a hydrogen atom or an alkyl group)

[0027] <6> substituents R ₁₃ is represented by the following formula having a sulfur atom (7-a) or formula (8-a) the sulfur-containing a group represented by the unsaturated carboxylic acid ester compound, R ₇₁ - O- (7-a) (wherein, R ₇₁ represents a monovalent organic group containing at least one or more sulfur atoms) R ₈₁ -S- (8-a) (wherein, R ₈₁ is Represents a monovalent organic group which may contain a sulfur atom)

<7> The above sulfur-containing unsaturated carboxylic acid ester compound, wherein the sulfur atom-containing substituent R ₁₃ is a group represented by the following formula (9-a):

[0029]

Embedded image (Wherein, R ₉₁ and R ₉₂ each represent a hydrogen atom or an alkyl group, and may combine with each other to form a ring;
₉₃ represents an oxygen atom or a sulfur atom, p represents an integer of 0 to 3, and q represents an integer of 1 to 4)

<8> The divalent organic group R ₁₁ is represented by the following formula (3-a-
i) wherein X ₁₁ is an oxygen atom, —COO—
A group or — (CH ₂ ) _l X ₁₂ — group (X ₁₂ represents an oxygen atom or a sulfur atom, 1 represents an integer of 1 to 3);
₁₃ is a group represented by the formula (7-a) or (8-a), and R ₁₄ is a (meth) acrylic acid residue;

[0031]

Embedded image

<9> The divalent organic group R ₁₁ has the following formula (4-a-
i), a group represented by the formula (4-a-ii) or (4-a-iii), X ₁₁ is an oxygen atom, and R ₁₃ is a group represented by the formula (7-
a) or a group represented by the formula (8-a), wherein R ₁₄ is a (meth) acrylic acid residue;

[0033]

Embedded image (Wherein R ₄₂ and R ₄₃ each represent a hydrogen atom or a methyl group)

[0034]

Embedded image (Wherein, R ₄₁ independently represents a hydrogen atom or a methyl group)

[0035]

Embedded image

<10> When the divalent organic group R ₁₁ is represented by the following formula (5-a-
a group represented by i), X ₁₁ is an oxygen atom, R ₁₃
Is a group represented by the formula (7-a) or the formula (8-a), and R ₁₄ is a (meth) acrylic acid residue;

[0037]

Embedded image (Wherein, R ₅₁ independently represents a hydrogen atom or an alkyl group)

<11> When the divalent organic group R ₁₁ has the following formula (6-a-
i) wherein X ₁₁ is an oxygen atom or —CO
An O- group, wherein R ₁₃ is a group represented by the formula (7-a) or the formula (8-
a) a group represented by a), wherein the sulfur-containing unsaturated carboxylic acid ester compound wherein R ₁₄ is a (meth) acrylic acid residue,

[0039]

Embedded image

<12> A polymerizable composition containing the sulfur-containing unsaturated carboxylic acid ester compound according to any one of the above <1> to <11>,
<13> A cured product obtained by polymerizing the polymerizable composition of <12>, <14> relates to an optical component comprising the cured product of <13>, and the sulfur-containing unsaturated carboxylic acid described above. <15> a hydroxy compound represented by the following general formula (2), which is a raw material intermediate of an ester compound;

[0041]

Embedded image [Wherein, R ₁₁ represents a divalent organic group, and X ₁₁ each independently represent an oxygen atom, a sulfur atom, a —COO— group, or — (CH
₂ ) ₁ X ₁₂ -group (X ₁₂ represents an oxygen atom or a sulfur atom, 1 represents an integer of 1 to 3), R ₁₂ each independently represents a hydrogen atom or an alkyl group, and R ₁₃ represents Independently represents a substituent containing a sulfur atom]

<16> When the divalent organic group R ₁₁ is represented by the following formula (3-
a) the aforementioned hydroxy compound which is a group represented by (a), (4-a), (5-a) or formula (6-a);

[0043]

Embedded image (Wherein, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each a hydrogen atom,
Represents an alkyl group, an alkoxy group, a nitro group or a halogen atom)

[0044]

Embedded image Wherein Y ₄₁ is a single bond, a —C (R ₄₁ ) ₂ — group (R ₄₁ each independently represents a hydrogen atom or a methyl group), —O—
Group, -S- group or -SO ₂ - represents a group, R ₄₂ and R
₄₃ each independently represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an alkylthio group,
Represents a nitro group or a halogen atom, and m and n each represent an integer of 0 to 4]

[0045]

Embedded image (Wherein, R ₅₁ independently represents a hydrogen atom or an alkyl group)

[0046]

Embedded image Wherein R ₆₁ and R ₆₂ each represent a hydrogen atom or an alkyl group.

[0047]

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

The sulfur-containing unsaturated carboxylate compound of the present invention has a substituent containing a sulfur atom in the molecule and has an oxygen atom bonded to at least two or more secondary or tertiary carbon atoms. This is a novel compound characterized in that it has an α, β-unsaturated carboxylic acid residue via a structure.

The sulfur-containing unsaturated carboxylic acid ester compound of the present invention will be described later in detail, but is typically a secondary or tertiary carboxylic acid.
An unsaturated carboxylic acid ester compound obtained by an ester bond formation reaction between a sulfur-containing hydroxy compound having two or more hydroxyl groups bonded to a secondary carbon atom in a molecule and an α, β-unsaturated carboxylic acid.

The α, β-unsaturated carboxylic acid residue is a group derived from the α, β-unsaturated carboxylic acid compound which is one of the reaction raw materials. It means the remaining acyl group residue portion obtained by removing the hydroxy group from the carboxyl group. In the case of an α, β-unsaturated carboxylic acid compound having two or more (plural) carboxyl groups, it means an acyl residue obtained by removing a hydroxy group from only one of the carboxyl groups.

The sulfur-containing unsaturated carboxylic acid ester compound of the present invention has at least two unsaturated carboxylic acid residues in the molecule.

The number of the unsaturated carboxylic acid residues is preferably 2 to 5, more preferably 2 to 4, and still more preferably 2 or 3. It is particularly preferred that the number of the unsaturated carboxylic acid residues is two.

Another feature of the structure of the sulfur-containing unsaturated carboxylic acid ester compound of the present invention is that it has a substituent containing a sulfur atom. The number is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 4.

In view of the desired effects of the present invention, the sulfur-containing unsaturated carboxylic acid ester compound of the present invention preferably has at least two sulfur atoms in the molecule, more preferably three or more sulfur atoms. Yes, and more preferably four or more.

When considering the use of the sulfur-containing unsaturated carboxylic acid ester compound of the present invention for optical parts such as lenses, the characteristics of the compound include curing of a polymerizable composition containing the compound. Refractive index of cured product (nd)
Is preferably 1.58 or more. The refractive index of the cured product is more preferably 1.59 or more, and even more preferably 1.60 or more.

When the sulfur-containing unsaturated carboxylate compound of the present invention is considered for use in optical parts such as lenses, the characteristics of the compound include a polymerizable composition containing the compound. Is preferably 28 or more, more preferably 30 or more, and still more preferably 33 or more.

As a preferable representative specific example of such a sulfur-containing unsaturated carboxylic acid ester compound, a sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) can be mentioned.

Hereinafter, the sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) will be described in detail.

In the general formula (1), R ₁₁ represents a divalent organic group, particularly a divalent aliphatic group or aromatic group, or a combination thereof. These divalent organic groups R ₁₁ may have a substituent, and as an atom constituting the organic group, a hetero atom other than a carbon atom or a hydrogen atom (eg, an oxygen atom, a sulfur atom, a nitrogen atom) Atoms). In particular, it is preferable to contain a sulfur atom in order to achieve a high refractive index and a high Abbe number, which are one of the desired effects in the present invention.

As the organic group, more preferably, an alkylene group having 2 to 30 carbon atoms in a chain, cyclic or combination thereof, an aralkylene group having 5 to 30 carbon atoms or an arylene group having 4 to 30 carbon atoms, or A group in which two or more of such arylene groups are bonded by one or more divalent linking groups.

When the organic group R ₁₁ has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a nitro group and a halogen atom (for example, a bromine atom, an iodine atom or a chlorine atom). And preferably an alkyl group having 1 to 4 carbon atoms and 1 carbon atom.
To 4 alkoxy groups, an alkylthio group having 1 to 4 carbon atoms,
It is a bromine atom or an iodine atom, more preferably a methyl group, a methoxy group, a methylthio group or a bromine atom.

[0062] Examples of the organic group R _11, it is not particularly limited, for example, methylene, 1,2-ethylene, 1,1-ethylene group, 1-methyl-1,2-ethylene group, 1 , 2-dimethyl-1,2-ethylene group, 1,3
A trimethylene group,

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image Is mentioned.

Among these divalent organic groups, the organic group R
As _11, a group represented by the following formula (3-a), formula (4
The group represented by a), the group represented by the formula (5-a) or the group represented by the formula (6-a) is more preferable.

[0068]

Embedded image (Wherein, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each a hydrogen atom,
Represents an alkyl group, an alkoxy group, a nitro group or a halogen atom)

[0069]

Embedded image Wherein Y ₄₁ is a single bond, a —C (R ₄₁ ) ₂ — group (R ₄₁ each independently represents a hydrogen atom or a methyl group), —O—
Group, -S- group or -SO ₂ - represents a group, R ₄₂ and R
₄₃ each independently represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an alkylthio group,
Represents a nitro group or a halogen atom, and m and n each represent an integer of 0 to 4]

[0070]

Embedded image (Wherein, R ₅₁ independently represents a hydrogen atom or an alkyl group)

[0071]

Embedded image (Wherein, R ₆₁ and R ₆₂ each represent a hydrogen atom or an alkyl group)

Hereinafter, the divalent organic groups represented by the formulas (3-a) to (6-a) will be described. Formula (3-a)
In the above, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom, and preferably have a hydrogen atom or a substituent A good linear, branched or cyclic alkyl group, a linear or branched or cyclic alkoxy group which may have a substituent, represents a nitro group or a halogen atom,
More preferably, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent,
It represents a linear, branched or cyclic C1-C20 alkoxy group, nitro group or halogen atom which may have a substituent.

Specific examples of the substituents R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ include, for example, a hydrogen atom, a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n
-Pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group,
n-tetradecyl group, n-octadecyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group,
Cyclohexylmethyl group, cyclohexylethyl group, tetrahydrofurfuryl group, 2-methoxyethyl group, 2-
Ethoxyethyl group, 2-n-butoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-
Propoxypropyl group, 3-n-butoxypropyl group,
3-n-hexyloxypropyl group, 2-methoxyethoxyethyl group, 2-ethoxyethoxyethyl group, phenoxymethyl group, 2-phenoxyethoxyethyl group, chloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 2 , 2,2-trichloroethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-
Butoxy group, isobutoxy group, sec-butoxy group, n
-Pentyloxy, n-hexyloxy, 2-ethylhexyloxy, n-octyloxy, n-decyloxy, n-dodecyloxy, n-tetradecyloxy, n-octadecyloxy, cyclopentyl Oxy group, cyclohexyloxy group, 4-tert-butylcyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclohexylmethoxy group, cyclohexylethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n- Butoxyethoxy group, 3-methoxypropoxy group, 3-ethoxypropoxy group, 3-n-propoxypropoxy group, 3-n-butoxypropoxy group, 3-n-hexyloxypropoxy group, 2-methoxyethoxyethoxy group, phenoxymethoxy Group, 2-fe A xyethoxyethoxy group, a chloromethoxy group, a 2-chloroethoxy group, a 3-chloropropoxy group, a 2,2,2-trichloroethoxy group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. .

The substituents R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are more preferably a hydrogen atom, an unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms, A substituted linear or branched alkoxy group, a nitro group, a chlorine atom, a bromine atom, more preferably a hydrogen atom,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, te
It is an rt-butoxy group, a nitro group, a bromine atom or an iodine atom.

A hydrogen atom is particularly preferred as the substituents R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ .

In the above formula (4-a), Y ₄₁ is a single bond, a —C (R ₄₁ ) ₂ — group (R ₄₁ independently represents a hydrogen atom or a methyl group), a —O— group, a —S -Group or-
Represents an SO ₂ — group.

In the above formula (4-a), Y ₄₁ is preferably a single bond, a methylene group, an ethylidene group, an isopropylidene group, a —S— group or a —SO ₂ — group, and more preferably a single bond. Bond, methylene group, isopropylidene group,
—S— group or —SO ₂ — group, more preferably a single bond, a methylene group, an isopropylidene group or a
S-group.

In the formula (4-a), R ₄₂ and R ₄₃ each independently represent an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an alkylthio group, a nitro group or a halogen atom.

As the substituents R ₄₂ and R ₄₃ , a chain alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, a chain or cyclic alkenyl group having 2 to 6 carbon atoms is preferable. , An aralkyl group having 5 to 20 carbon atoms and 6 to 6 carbon atoms
20 aryl groups, a chain alkoxy group having 1 to 4 carbon atoms,
Represents a cyclic alkoxy group having 5 to 12 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a nitro group, a bromine atom or an iodine atom, more preferably a methyl group, an allyl group, a benzyl group, a phenyl group, a methoxy group, a methylthio group; Group or a bromine atom.

In the formula (4-a), m and n each represent an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

The group represented by the formula (4-a) is preferably represented by the following formula (4-ai), formula (4-a-ii) or formula (4-a-iii) Group.

[0082]

Embedded image (Wherein, R ₄₂ and R ₄₃ each independently represent a hydrogen atom or a methyl group)

[0083]

Embedded image (Wherein, R ₄₁ independently represents a hydrogen atom or a methyl group)

[0084]

Embedded image

In the formula (5-a), R ₅₁ each independently represents a hydrogen atom or an alkyl group. The substituent R ₅₁
Is preferably a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the formula (6-a), R ₆₁ and R ₆₂ each represent a hydrogen atom or an alkyl group. The substituent R
_{Each of 61} and _R62 is preferably a hydrogen atom or a chain alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the general formula (1), the substituents R ₁₂ each independently represent a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.

In the general formula (1), the substituents R ₁₃ each independently represent a substituent containing a sulfur atom, and the structure of the substituent contains at least one sulfur atom. .

Preferred specific examples of the substituent R ₁₃ include a group represented by the following formula (7-a) or (8-a).

R ₇₁ —O— (7-a) (wherein, R ₇₁ represents a monovalent organic group containing at least one sulfur atom) R ₈₁ —S— (8-a) (formula Wherein R ₈₁ represents a monovalent organic group which may contain a sulfur atom.

In the above formula, the substituent R ₇₁ represents a monovalent organic group containing at least one sulfur atom. The substituent R ₇₁ is preferably an alkyl group, an aralkyl group, an aryl group, or an acyl group containing at least one sulfur atom, and more preferably a carbon number containing at least one sulfur atom. An alkyl group having 1 to 20 linear, branched or cyclic structures, having 5 to 2 carbon atoms
It is an aralkyl group having 0, an aryl group having 4 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms. These monovalent organic groups may have a substituent and contain a hetero atom other than a sulfur atom (for example, a substituent containing a heterocycle).
It may be.

In the above formula, the substituent R ₈₁ represents a monovalent organic group which may contain a sulfur atom. The substituent R
₈₁ is preferably an alkyl group, an aralkyl group, an aryl group, or an acyl group which may contain a sulfur atom, and more preferably has 1 carbon atom which may contain at least one sulfur atom. To 20 alkyl groups having a linear, branched or cyclic structure, having 5 to 20 carbon atoms
, An aryl group having 4 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms. These monovalent organic groups may have a substituent, and may contain a hetero atom other than a sulfur atom (for example, a heterocyclic-containing substituent or the like). In order to obtain the desired effects of the present invention (for example, high refractive index, high Abbe number, etc.), it is more preferable that the substituent R ₈₁ contains a sulfur atom.

As the above substituent R ₁₃ , more preferably,
Linear, branched or cyclic alkoxy group containing at least one sulfur atom, aralkyloxy group containing at least one sulfur atom, aryl containing at least one sulfur atom Oxy group, acyloxy group containing at least one sulfur atom, alkylthio group having a linear, branched or cyclic structure optionally containing a sulfur atom, aralkylthio optionally containing a sulfur atom And arylthio groups optionally containing a sulfur atom and acylthio groups optionally containing a sulfur atom.

Examples of the substituent R ₁₃ include a methylthioethoxy group, an ethylthioethoxy group, a propylthioethoxy group, a butylthioethoxy group, a methylthioethylthioethoxy group, a methylthioethylthioethylthioethoxy group, a 2,2- Di (methylthio) ethoxy group, 2,2-
Di (ethylthio) ethoxy group, 2,2-di (propylthio) ethoxy group, 2,2-di (butylthio) ethoxy group, 3,3-di (methylthio) propoxy group, 3,3-
Di (ethylthio) propoxy group, 3,3-di (propylthio) ethoxy group, 3,3-di (butylthio) ethoxy group, (1,3-dithiolan-2-yl) methoxy group, 2
-(1,3-dithiolan-2-yl) ethoxy group, 3-
A (1,3-dithiolan-2-yl) propoxy group,
(1,3-dithiolan-4-yl) methoxy group, 2-
(1,3-dithiolan-4-yl) ethoxy group, 3-
(1,3-dithiolan-4-yl) propoxy group,
(1,4-dithian-2-yl) methoxy group, 2-
(1,4-dithian-2-yl) ethoxy group, 3-
(1,4-dithian-2-yl) propoxy group, (1,
3,5-trithian-2-yl) methoxy group, 2-
(1,3,5-trithian-2-yl) ethoxy group, 3
-(1,3,5-trithian-2-yl) propoxy group, 4-methylthiobenzyloxy group, 3-methylthiobenzyloxy group, 2-methylthiobenzyloxy group,
2,4-di (methylthio) benzyloxy group, 3,4-
Di (methylthio) benzyloxy group, 2,4,6-tri (methylthio) benzyloxy group, (4-methylthiophenyl) ethoxy group, (3-methylthiophenyl) ethoxy group, (2-methylthiophenyl) ethoxy group,
[2,4-di (methylthio) phenyl] ethoxy group,
[3,4-di (methylthio) phenyl] ethoxy group,
[2,4,6-tri (methylthio) phenyl] ethoxy, 4-methylthiophenyloxy, 3-methylthiophenyloxy, 2-methylthiophenyloxy,
2,4-di (methylthio) phenyloxy group, 2,5-
Di (methylthio) phenyloxy group, 2,6-di (methylthio) phenyloxy group, 3,4-di (methylthio)
Phenyloxy group, 3,5-di (methylthio) phenyloxy group, 2,4,6-tri (methylthio) phenyloxy group, 2,3,4,5,6-penta (methylthio) phenyloxy group, methylthio group , Ethylthio, propylthio, butylthio, methoxyethylthio, butoxyethylthio, methoxypropylthio, cyclohexylthio, 2-methylthioethylthio, 2-ethylthioethylthio, 2-propylthioethylthio Group,
2-butylthioethylthio group, methylthioethylthioethylthio group, methylthioethylthioethylthioethylthio group, 2,2-di (methylthio) ethylthio group, 2,2
-Di (ethylthio) ethylthio group, 2,2-di (propylthio) ethylthio group, 2,2-di (butylthio) ethylthio group, 3,3-di (methylthio) propylthio group,
3,3-di (ethylthio) propylthio group, 3,3-di (propylthio) propylthio group, 3,3-di (butylthio) propylthio group, (1,3-dithiolan-2-yl) methylthio group, 2- ( 1,3-dithiolan-2-yl) ethylthio group, 3- (1,3-dithiolan-2-yl) propylthio group, (1,3-dithiolan-4-yl) methylthio group, 2- (1,3- Dithiolan-4-yl) ethylthio group, 3- (1,3-dithiolan-4-yl) propylthio group, (1,3-dithian-2-yl)
Methylthio group, 2- (1,3-dithian-2-yl) ethylthio group, 3- (1,3-dithian-2-yl) propylthio group, (1,4-dithian-2-yl) methylthio group, -(1,4-dithian-2-yl) ethylthio group, 3- (1,4-dithian-2-yl) propylthio group, (1,3,5-trithian-2-yl) methylthio group, 2- ( 1,3,5-trithian-2-yl) ethylthio group, 3- (1,3,5-trithian-2-yl) propylthio group, benzylthio group, 4-methylbenzylthio group, 4-methoxybenzylthio group, 4-methylthiobenzylthio group, 3-methylthiobenzylthio group, 2-methylthiobenzylthio group, 2,4-di (methylthio) benzylthio group, 3,4-di (methylthio) benzylthio group, 2,4,6- Li (methylthio) benzylthio group,
(4-methylthiophenyl) ethylthio group, (3-methylthiophenyl) ethylthio group, (2-methylthiophenyl) ethylthio group, [2,4-di (methylthio) phenyl] ethylthio group, [3,4-di (methylthio) Phenyl] ethylthio group, [2,4,6-tri (methylthio) phenyl] ethylthio group, phenylthio group, 4-methylphenylthio group, 4-methoxyphenylthio group,
-Methylthiophenylthio group, 3-methylthiophenylthio group, 2-methylthiophenylthio group, 2,4-di (methylthio) phenylthio group, 2,5-di (methylthio) phenylthio group, 2,6-di (methylthio) Phenylthio group, 3,4-di (methylthio) phenylthio group,
3,5-di (methylthio) phenylthio group, 2,4,6
A tri (methylthio) phenylthio group, 2,3,4
5,6-penta (methylthio) phenylthio group, thiazolin-2-ylthio group, methylthiomethylcarbonyloxy group, methylthioethylcarbonyloxy group, (1,
3-dithiolan-2-yl) carbonyloxy group,
(1,3-dithiolan-4-yl) carbonyloxy group, (1,3-dithian-2-yl) carbonyloxy group, (1,4-dithian-2-yl) carbonyloxy group, (1,3 5-trithian-2-yl) carbonyloxy group, 4-methylthiobenzoyloxy group, thiophen-2-carbonyloxy group, thiazole-2-carbonyloxy group, methylthiomethylcarbonylthio group,
Methylthioethylcarbonylthio group, (1,3-dithiolan-2-yl) carbonylthio group, (1,3-dithiolan-4-yl) carbonylthio group, (1,3-dithian-2-yl) carbonylthio group , (1,4-dithian-2-yl) carbonylthio group, (1,3,5-trithian-2-yl) carbonylthio group, benzoylthio group, 4-methylthiobenzoylthio group, thiophen-2
-Carbonylthio group, thiazole-2-carbonylthio group and the like, but are not limited thereto.

As the substituent R ₁₃ , the following formula (9-a)
The group represented by is particularly preferred.

[0096]

Embedded image (Wherein, R ₉₁ and R ₉₂ each represent a hydrogen atom or an alkyl group, and may combine with each other to form a ring;
₉₃ represents an oxygen atom or a sulfur atom, p represents an integer of 0 to 3, and q represents an integer of 1 to 4)

In the general formula (1), the substituents R ₁₄ each independently represent an α, β-unsaturated carboxylic acid residue. The sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) of the present invention will be described in detail later, but typically, a hydroxy compound represented by the general formula (2) and an α, β-unsaturated compound. It is obtained by reaction with a saturated carboxylic acid, and the substituent R ₁₄ is a group (residue) derived from the α, β-unsaturated carboxylic acid as a reactant. As such a substituent R ₁₄ , preferably,
(Meth) acrylic acid residue, crotonic acid residue, tiglic acid residue, 3,3-dimethylacrylic acid residue, maleic acid residue, citraconic acid residue, 2,3-dimethylmaleic acid residue, itaconic acid Or a cinnamic acid residue, and more preferably a (meth) acrylic acid residue or a maleic acid residue. Among these, a (meth) acrylic acid residue is particularly preferred as the substituent R ₁₄ .

Among the sulfur-containing unsaturated carboxylic acid ester compounds represented by the general formula (1) of the present invention, preferably, the following formulas (1-a), (1-b), (1-c), (1-c) 1-
d), (1-e), (1-f), (1-g), (1-
h), (1-i), (1-j) or a structure represented by the formula (1-k).

[0099]

Embedded image

[0100]

Embedded image (In the above formula, R ₁₂ , R ₁₃ and R ₁₄ are the same as described above, R ₄₂ and R ₄₃ each independently represent a hydrogen atom or a methyl group, and R ₅₁ each independently represent a hydrogen atom or a methyl group. )

Of the above structural formulas, more preferably,
Formulas (1-a), (1-c), (1-d), (1-e),
(1-f), (1-g), (1-h) or the formula (1-
i), and more preferably the structure represented by the formula (1)
-A), (1-d), (1-e), (1-f), (1-
g), (1-h) or the structure represented by the formula (1-i), and the formula (1-a), (1-d), or the formula (1-f)
Is particularly preferable.

As specific examples of the sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) of the present invention, the following 1
The compounds shown in the table are exemplified, but the present invention is not limited to these.

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

[Table 5]

[0108]

[Table 6]

[0109]

[Table 7]

[0110]

[Table 8]

[0111]

[Table 9]

[0112]

[Table 10]

[0113]

[Table 11]

[0114]

[Table 12]

[0115]

[Table 13]

[0116]

[Table 14]

[0117]

[Table 15]

[0118]

[Table 16]

[0119]

[Table 17]

[0120]

[Table 18]

[0121]

[Table 19]

[0122]

[Table 20]

[0123]

[Table 21]

[0124]

[Table 22]

[0125]

[Table 23]

[0126]

[Table 24]

[0127]

[Table 25]

[0128]

[Table 26]

[0129]

[Table 27]

[0130]

[Table 28]

[0131]

[Table 29]

[0132]

[Table 30]

[0133]

[Table 31]

[0134]

[Table 32]

[0135]

[Table 33]

[0136]

[Table 34]

[0137]

[Table 35]

[0138]

[Table 36]

[0139]

[Table 37]

[0140]

[Table 38]

[0141]

[Table 39]

[0142]

[Table 40]

[0143]

[Table 41]

[0144]

[Table 42]

[0145]

[Table 43]

[0146]

[Table 44]

[0147]

[Table 45]

[0148]

[Table 46]

[0149]

[Table 47]

[0150]

[Table 48]

[0151]

[Table 49]

[0152]

[Table 50]

[0153]

[Table 51]

[0154]

[Table 52]

[0155]

[Table 53]

[0156]

[Table 54]

[0157]

[Table 55]

[0158]

[Table 56]

[0159]

[Table 57]

[0160]

[Table 58]

[0161]

[Table 59]

[0162]

[Table 60]

[0163]

[Table 61]

[0164]

[Table 62]

[0165]

[Table 63]

[0166]

[Table 64]

[0167]

[Table 65]

[0168]

[Table 66]

[0169]

[Table 67]

[0170]

[Table 68]

[0171]

[Table 69]

[0172]

[Table 70]

[0173]

[Table 71]

[0174]

[Table 72]

[0175]

[Table 73]

[0176]

[Table 74]

[0177]

[Table 75]

[0178]

[Table 76]

[0179]

[Table 77]

[0180]

[Table 78]

[0181]

[Table 79]

[0182]

[Table 80]

[0183]

[Table 81]

[0184]

[Table 82]

[0185]

[Table 83]

[0186]

[Table 84]

[0187]

[Table 85]

[0188]

[Table 86]

[0189]

[Table 87]

[0190]

[Table 88]

[0191]

[Table 89]

[0192]

[Table 90]

[0193]

[Table 91]

[0194]

[Table 92]

[0195]

[Table 93]

[0196]

[Table 94]

[0197]

[Table 95]

[0198]

[Table 96]

[0199]

[Table 97]

[0200]

[Table 98]

[0201]

[Table 99]

[0202]

[Table 100]

[0203]

[Table 101]

[0204]

[Table 102]

[0205]

[Table 103]

[0206]

[Table 104]

The sulfur-containing unsaturation of the present invention having an α, β-unsaturated carboxylic acid residue via a sulfur atom-containing substituent and at least two or more oxygen atoms bonded to secondary or tertiary carbon atoms. Although the saturated carboxylic acid ester compound is a novel compound, the production method itself is suitably produced using a known synthesis reaction method.

A typical example of the specific structure of the sulfur-containing unsaturated carboxylic acid ester compound is a sulfur-containing unsaturated carboxylic acid ester compound having a chemical structure represented by the general formula (1) of the present invention. In a typical method, the compound represented by the general formula (1) is suitably produced by a synthetic route represented by the following [Scheme A].

[0209]

Embedded image (In the above scheme, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and X ₁₁
Is the same as above)

The sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) of the present invention is, for example, (a) (meth) Acrylic acids, crotonic acids, tiglic acids, 3,
Α, β-unsaturated carboxylic acids such as 3-dimethylacrylic acids, maleic acids, citraconic acids, 2,3-dimethylmaleic acids, itaconic acids or cinnamic acids (α, β-unsaturated carboxylic acids, ester derivatives thereof, (B) halopropionic acids (e.g., 3-acid halides or acid halides);
Chloropropionic acid, 3-bromopropionic acid, 3-chloro-2-methylpropionic acid, 3-bromo-2-methylpropionic acid) or an acid halide thereof to give a halopropionic acid ester compound. It is produced by an unsaturated carboxylic acid esterification method utilizing a known synthesis reaction such as a method of subjecting to (meth) acrylic acid esterification with hydrogen halide.

The sulfur-containing dihydroxy compound represented by the general formula (2) of the present invention can be obtained by using the sulfur-containing unsaturated compound represented by the general formula (1) of the present invention in the synthetic route shown in the above [Scheme A]. It is a compound useful as a synthetic intermediate when producing a carboxylic acid ester compound, and a novel compound.

In the general formula (2), R ₁₁ , R ₁₂ ,
R ₁₃ , R ₁₄ and X ₁₁ represent R ₁₁ ,
It has the same meaning as R ₁₂ , R ₁₃ , R ₁₄ and X ₁₁ .

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

[0214]

[Table 105]

[0215]

[Table 106]

[0216]

[Table 107]

[0219]

[Table 108]

[0218]

[Table 109]

[0219]

[Table 110]

[0220]

[Table 111]

[0221]

[Table 112]

[0222]

[Table 113]

[0223]

[Table 114]

[0224]

[Table 115]

[0225]

[Table 116]

[0226]

[Table 117]

[0227]

[Table 118]

[0228]

[Table 119]

[0229]

[Table 120]

[0230]

[Table 121]

[0231]

[Table 122]

[0232]

[Table 123]

[0233]

[Table 124]

[0234]

[Table 125]

[0235]

[Table 126]

[0236]

[Table 127]

[0237]

[Table 128]

[0238]

[Table 129]

[0239]

[Table 130]

[0240]

[Table 131]

[0241]

[Table 132]

[0242]

[Table 133]

[0243]

[Table 134]

[0244]

[Table 135]

[0245]

[Table 136]

[0246]

[Table 137]

[0247]

[Table 138]

[0248]

[Table 139]

[0249]

[Table 140]

[0250]

[Table 141]

[0251]

[Table 142]

[0252]

[Table 143]

[0253]

[Table 144]

[0254]

[Table 145]

[0255]

[Table 146]

[0256]

[Table 147]

[0257]

[Table 148]

[0258]

[Table 149]

[0259]

[Table 150]

[0260]

[Table 151]

[0261]

[Table 152]

[0262]

[Table 153]

[0263]

[Table 154]

[0264]

[Table 155]

[0265]

[Table 156]

[0266]

[Table 157]

[0267]

[Table 158]

[0268]

[Table 159]

[0269]

[Table 160]

[0270]

[Table 161]

[0271]

[Table 162]

[0272]

[Table 163]

[0273]

[Table 164]

[0274]

[Table 165]

[0275]

[Table 166]

[0276]

[Table 167]

[0277]

[Table 168]

[0278]

[Table 169]

[0279]

[Table 170]

[0280]

[Table 171]

The method for producing the sulfur-containing hydroxy compound represented by the general formula (2) in the above scheme (A) will be described below.

[0282] sulfur-containing dihydroxy compound represented by the general formula (2) of the present invention, with respect represented diepoxy compound of general formula (10), compounds containing sulfur atom (sulfur-containing compound) R ₁₃ - H [specifically, for example, by reacting with a sulfur-containing compound represented by the following general formula (7) or (8) or the like] to effect ring-opening addition to an epoxy group, thereby producing the compound suitably. You. The reaction method itself is known and is carried out according to conventionally known reaction conditions. For example, if necessary, the reaction is suitably carried out in the presence of a suitable catalyst (eg, an acid catalyst, a base catalyst, etc.). Will be

[0283]

Embedded image (Wherein R ₁₁ , R ₁₂ and X ₁₁ are the same as described above) R ₇₁ —OH (7) (wherein, R ₇₁ represents a monovalent organic group containing at least one or more sulfur atoms) R ₈₁ -SH (8) (in the formula, R ₈₁ represents a monovalent organic group optionally containing a sulfur atom)

The diepoxy compound represented by the general formula (10) as a raw material is typically a known epoxidation reaction using a diol compound or a dithiol compound and epihalohydrin as raw materials (for example, available as an industrial raw material). It is suitably manufactured according to an existing method for industrial production of a diepoxy compound).

In such a reaction, the amount of the sulfur-containing compound to act on the diepoxy compound represented by the general formula (10) is not particularly limited, but is usually represented by the general formula (10) 0.1 to 10 moles (0.0% per epoxy group, based on 1 mole of diepoxy compound)
5 to 5 equivalents), preferably 0.5 to 5 mol (0.25 to 2.5 equivalents per epoxy group),
More preferably, it is 0.8 to 3 mol (0.4 to 1.5 equivalents per epoxy group).

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

The reaction temperature is not particularly limited, but is usually in the range of 0 ° C. to 200 ° C., preferably 0 ° C.
１００100 ° C.

The reaction time depends on conditions such as the reaction temperature, but is usually from several minutes to several tens of hours.

The sulfur-containing compound represented by the formula (9) of the present invention is a novel compound and is a halogen compound, a hydroxy compound or a thiol compound characterized by having a cyclic thioacetal structure in the molecule.

[0290]

Embedded image (Wherein, R ₉₁ and R ₉₂ each represent a hydrogen atom or an alkyl group, and may combine with each other to form a ring;
₉₃ represents a halogen atom, a hydroxy group or a thiol group, p represents an integer of 0 to 3, and q represents an integer of 1 to 4.) In the above formula (9), R ₉₁ and R ₉₂ each represent a hydrogen atom Or, it represents an alkyl group, and R ₉₁ and R ₉₂ may be bonded to each other to form a ring.

The substituents R ₉₁ and R ₉₂ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group. When R ₉₁ and R ₉₂ are combined to form a ring, the ring is preferably a cycloalkane ring, more preferably a cycloalkane ring having 5 to 7 carbon atoms,
More preferably, it is a cyclohexane ring.

In the above formula (9), p is an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably an integer of 0 or 1.

In the formula (9), q is 1 to 4
, Preferably 1 to 3, and more preferably 1 or 2.

In the formula (9), R ₉₃ represents a halogen atom, a hydroxy group or a thiol group, preferably a halogen atom or a thiol group, and more preferably a thiol group. When R ₉₃ represents a hydroxy group or a thiol group, the above formula (7) or (8)
Corresponds to the lower concept of.

Specific examples of the sulfur-containing compound represented by the formula (9) of the present invention include the compounds shown in Table 3 below.

[0296]

[Table 172]

[0297]

[Table 173]

[0298]

[Table 174]

[0299]

[Table 175]

[0300]

[Table 176]

[0301]

[Table 177]

In the sulfur-containing compound of the present invention represented by the formula (9), the compound in which R ₉₃ is a halogen atom is typically represented by an aldehyde represented by the following formula (11) or an acetal derivative thereof. Is preferably produced by reacting a dithiol represented by the following formula (12) in the presence of an acid catalyst.

[0303]

Embedded image (In the above formula, R ₉₁ , R ₉₂ , p and q represent the same meaning as described above, and R ₁₁₃ represents a halogen atom.)

Further, in the formula (9) of the present invention, the compound wherein R ₉₃ is a hydroxy group and the compound wherein R ₉₃ is a thiol group are the cyclic thioacetal compounds represented by the formula (9) wherein R ₉₃ is a halogen atom. Is a known synthetic chemical method, for example, a method in which a halogen atom is alkali-hydrolyzed to convert it to a hydroxy group, or a method in which a thiourea is acted on a halogen atom to thiuronium chloride and then alkali-treated to give a thiol group. It is suitably manufactured by a method of converting into.

Hereinafter, first, the aldehyde represented by the formula (11) or the acetal derivative thereof is reacted with a dithiol represented by the formula (12) in the presence of an acid catalyst, whereby In the formula (9) of the invention, R ₉₃
Is a method for producing a compound having a halogen atom,
This will be described in more detail.

Examples of the aldehyde represented by the formula (11) or an acetal derivative thereof include haloalkylaldehydes such as chloroacetaldehyde, 3-chloropropionaldehyde, and 3-bromopropionaldehyde; 2-chloroacetaldehyde dimethyl acetal, -Chloroacetaldehyde diethyl acetal,
2-chloropropionaldehyde dimethyl acetal,
2-chloropropionaldehyde diethyl acetal,
2-bromopropionaldehyde dimethyl acetal,
2-bromopropionaldehyde diethyl acetal,
2-bromopropionaldehyde ethylene acetal [or 2- (2'-bromoethyl) -1,3-dioxolane], 2-bromopropionaldehyde trimethylene acetal [or 2- (2'-bromoethyl)
-1,3-dioxane] or a dialkyl acetal derivative or a cyclic alkylene acetal derivative of a haloalkyl aldehyde.

Examples of the dithiol derivative represented by the formula (12) include ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,2-butanedithiol, 1,3-butanedithiol, , 4-
Butanedithiol, 1,2-pentanedithiol, 1,
3-pentanedithiol, 1,4-pentanedithiol, 1,2-hexanedithiol, 1,3-hexanedithiol, 1,4-hexanedithiol, 1,2-heptanedithiol, 1,2-octanedithiol, 1,2
Chain alkanedithiols such as nonanedithiol and 1,2-decanedithiol; cyclopentane-1,2-
Cycloalkanedithiols such as dithiol and cyclohexane-1,2-dithiol; and 1,2-benzenedithiol.

An aldehyde represented by the formula (11) or an acetal derivative thereof is reacted with a dithiol represented by the formula (12) to obtain a compound represented by the formula (9).
When producing a compound in which ₉₃ is a halogen atom, the amount of the dithiols used is not particularly limited, but is usually based on 1 mol of the aldehyde represented by the formula (11) or a derivative thereof. , 0.5 to 5 mol, preferably 0.8 to 2 mol, more preferably 0.1 to 2 mol.
9 to 1.2 mol.

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

Examples of the reaction catalyst include sulfuric acid, hydrochloric acid,
Protic acids such as hydrobromic acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid; titanium trichloride, titanium tetrachloride, tin dichloride, tin tetrachloride, boron trifluoride ether complex, etc. Lewis acids and the like.

The use amount of the reaction catalyst is not particularly limited, but is usually 0.001 to 1 mol of the aldehyde represented by the formula (11) or an acetal derivative thereof.
Mol to 20 mol, preferably from 0.01 mol to 1 mol.
0 mol, more preferably 0.1 mol to 5 mol.

[0312] These reaction catalysts may be used alone or in combination of two or more.

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

There is no particular limitation on the amount of the reaction solvent used, but if the amount is too large, it is not preferable in terms of production efficiency and the like. Usually, the aldehyde represented by the formula (11) or an acetal derivative thereof is used. Is 300 times by mass or less, preferably 100 times by mass or less.

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

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

The reaction time varies depending on the reaction temperature, but may be usually in the range of several minutes to several tens of hours. The reaction may be carried out by a known analytical means (for example, liquid chromatography, thin-layer chromatography, IR, etc.). Tracking can determine the endpoint of the reaction.

In order to convert the substituent R ₉₃ , that is, the halogen atom in the compound represented by the formula (9) produced by the above method into a thiol group, a known method, for example, Jo
urnal of Organic Chemistry, Vol. 27, pp. 93-95 (1962
Year), Organic Synthesis, IV, pp. 401-403 (1963)
Year) is suitably used. That is, in a typical method, a compound in which R ₉₃ is a halogen atom in the formula (9) is reacted with thiourea and then hydrolyzed using an alkali such as aqueous ammonia or sodium hydroxide. , In equation (9)
Compounds wherein ₉₃ is a thiol group are suitably prepared.

In order to convert the substituent R ₉₃ , that is, the halogen atom in the compound represented by the formula (9) produced by the above method into a hydroxy group, a known method may be used.
For example, the method described in Experimental Chemistry Course, 4th Edition, Volume 20, pages 49 to 51 (edited by The Chemical Society of Japan), Synthesis, page 763 (1986) is preferably used. That is, in a typical method, a compound in which R ₉₃ in Formula (9) is a halogen atom is hydrolyzed using an alkali such as sodium hydroxide, whereby R ₉₃ in Formula (9) is a hydroxy group. Are preferably prepared.

After the completion of the above reaction, the sulfur-containing compound represented by the formula (9) is subjected to a usual post-treatment operation (eg, neutralization, filtration, solvent extraction, water washing, liquid separation, solvent distillation) from the reaction product. And the like). Also, known operations,
Purification methods (eg, distillation, recrystallization, column chromatography, activated carbon treatment, etc.) can increase the purity as needed.

Next, from the sulfur-containing dihydroxy compound represented by the general formula (2) as a raw material, among the sulfur-containing unsaturated carboxylic acid ester compounds represented by the general formula (1) of the present invention,
In particular, a method for producing a sulfur-containing (meth) acrylate compound will be described in detail.

As described above, as a method for converting a sulfur-containing dihydroxy compound represented by the general formula (2) into a sulfur-containing unsaturated carboxylic acid ester, typically, (a) (meth) acrylic acid or its ester derivative is used. Or a method of reacting with an acid halide thereof to perform esterification by a dehydration reaction, transesterification reaction or dehydrohalogenation reaction, and (b) chloropropionic acids (chloropropionic acid, an ester derivative thereof, or an acid halide thereof) After the reaction is performed to obtain a chloropropionate compound, a method of dehydrohalogenating to obtain a (meth) acrylate compound is exemplified.

Hereinafter, as the most typical example of the above-mentioned methods, the sulfur-containing dihydroxy compound represented by the general formula (2) is reacted with (meth) acrylic acid, its ester derivative or its acid halide. The method will be described in more detail.

That is, as the method, a known method,
For example, J. Org. Chem., 45, 5364 (1980), Eur. Poly.
m. J., 19, 399 (1983). For example, (a) under stirring, in the presence of a base,
A method in which an acid halide of (meth) acrylic acid is allowed to act on the sulfur-containing dihydroxy compound represented by the general formula (2) while performing an operation such as dropping, and (b) a method in which a general formula ( 2) a method of performing a dehydration reaction between the sulfur-containing dihydroxy compound and (meth) acrylic acid, or (c) a sulfur-containing dihydroxy compound and (meth) acrylic acid in the presence of a catalyst (acid catalyst or base catalyst). Acid ester derivatives [eg, (meth) acrylic acid methyl ester,
(Meth) acrylic acid ethyl ester, (meth) acrylic acid methyl ester and other (meth) acrylic acid alkyl esters, etc.].

In the above reaction, (meth) acrylic acids [eg, (meth) acrylic acid, its ester derivative or its acid halide, etc.] acting on the sulfur-containing dihydroxy compound represented by the general formula (2) Although the use amount is not particularly limited, it is usually 0.1 to 10 mol (0.05 to 5 equivalents per hydroxy), relative to 1 mol of the sulfur-containing dihydroxy compound, and preferably
0.5-5 mol (0.25-2.
5 equivalents), and more preferably 0.8 to 3 mol (0.4 to 1.5 mol per hydroxy).

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

The reaction temperature is not particularly limited, but is a temperature at which the (meth) acrylic acid as a raw material or the (meth) acrylic acid ester compound as a reaction product is not polymerized.
The temperature is in the range of 8 to 150 ° C, preferably -20 to 12 ° C.
It is 0 degreeC, More preferably, it is 0-100 degreeC.

Although the reaction time depends on the reaction temperature, it is generally 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 confirming the reaction rate by a known analysis means (for example, liquid chromatography, thin-layer chromatography, IR, etc.).

In producing the sulfur-containing (meth) acrylate compound of the present invention by reacting the sulfur-containing dihydroxy compound represented by the general formula (2) with an acid halide of (meth) acrylic acid, Since hydrogen halide (for example, hydrogen chloride) is produced as a by-product, for example, triethylamine,
Pyridine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.
0] Removal of organic bases such as undec-7-ene (DBU) or inorganic bases such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide and the like. It may be used as a hydrogen chloride agent.

The amount of the dehydrohalogenating agent to be used is not particularly limited, but is preferably 0.1 to 10 mol with respect to 1 mol of the sulfur-containing dihydroxy compound represented by the general formula (2). Is 0.5 to 5 mol, more preferably 0.8 to 3 mol.

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

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

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

In the above-described method, the sulfur-containing dihydroxy compound represented by the general formula (2) is reacted with a halopropionic acid or an acid halide thereof to form a halopropionic ester compound, and then dehalogenated. As a method for producing a sulfur-containing (meth) acrylate compound represented by the general formula (1) by hydrogenation, for example, a method disclosed in
The method described in JP-A-67736 is exemplified.

Of the unsaturated carboxylic acid ester compounds represented by the general formula (1) of the present invention, other unsaturated carboxylic acids (for example, crotonic acid, tiglin, etc.) other than the sulfur-containing (meth) acrylate compound Acid, 3,3-dimethylacrylic acid, maleic acid, citraconic acid, 2,3-dimethylmaleic acid, itaconic acid, or cinnamic acid) ester compounds are crotonic acids (crotonic acid, Ester derivatives or acid anhydrides thereof, etc.), tiglic acids (tiglic acid, ester derivatives or acid anhydrides thereof), 3,3-dimethylacrylic acids (3,3-dimethylacrylic acid, ester derivatives or acid thereof) Anhydrides), maleic acids (such as maleic acid, its ester derivatives or acid anhydrides),
Citraconic acids (citraconic acid, its ester derivatives or acid anhydrides thereof), 2,3-dimethylmaleic acids (2,3-dimethylmaleic acid, its ester derivatives or acid anhydrides thereof), and itaconic acids (itaconic acid, (Meth) acrylic esters described above except that ester derivatives or acid anhydrides thereof, and cinnamic acids (itaconic acid, ester derivatives thereof, acid anhydrides or acid halides thereof), etc. are used as reaction raw materials. It is suitably manufactured according to a method similar to the chemical conversion method.

In producing the sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1), it is not possible to use a polymerization inhibitor during or after the reaction in order to prevent polymerization of the product. It is preferable. Examples of such a polymerization inhibitor include various known compounds such as 4-methoxyphenol, hydroquinone, and phenothiazine.

The amount of the polymerization inhibitor is not particularly limited,
It is usually 0.01 to 5% by mass, preferably 0.05% by mass, based on the raw material mixture or the reaction product in the reaction system.
３3% by mass.

After the completion of the reaction, the product, the sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1), is subjected to known procedures and treatment methods (eg, neutralization, solvent extraction, water washing, liquid separation,
The solvent is removed by post-treatment. Further, if necessary, the obtained sulfur-containing (meth) acrylate derivative represented by the general formula (1) is separated and purified by a known method (for example, distillation, recrystallization or chromatography). Can be isolated as a highly pure compound.

The polymerizable composition of the present invention using the sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) of the present invention, a cured product obtained by polymerizing the polymerizable composition, When producing optical components, these mixtures can be used as they are without separation and purification.

Next, the polymerizable composition containing the sulfur-containing unsaturated carboxylic acid 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, as essential components, a sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) of the present invention, and a light and / or thermal polymerization initiator. . In this case, the sulfur-containing unsaturated carboxylic acid ester compound may be used alone, or
A plurality of different sulfur-containing unsaturated carboxylic acid ester compounds may be used in combination.

The polymerizable composition of the present invention may further contain, if necessary, a sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) as long as the desired effect is not impaired. It may contain a known polymerizable compound (such as a photo- or thermo-polymerizable monomer or oligomer).

The amount of the sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) contained in the polymerizable composition is not particularly limited, but is usually based on the total mass of the polymerizable composition. 10% by mass or more, preferably 20% by mass.
It is at least 30% by mass, more preferably at least 30% by mass, even more preferably at least 50% by mass.

The polymerization initiator used in the polymerizable composition of the present invention is not particularly limited, and various known thermal polymerization initiators or photopolymerization initiators can be used.

Examples of the photopolymerization initiator include benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 1,1-dimethoxy-1-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone. 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropane-1-
ON, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-
tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,
4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4′-
Examples thereof include dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, and Michler's ketone. These can be used alone or
Two or more can be used in combination.

The amount of the photopolymerization initiator used is determined by the general formula (1)
A sulfur-containing unsaturated carboxylic acid ester compound 100 represented by the formula:
The amount is 0.001 to 50 parts by mass, preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably,
0.2 to 5 parts by mass.

Examples of the thermal polymerization initiator include 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)
A sulfur-containing unsaturated carboxylic acid ester compound 100 represented by the formula:
The amount 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, and further preferably 0 to 10 parts by mass with respect to parts by mass. 0.2 to 5 parts by mass.

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

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

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

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

In order to further achieve the effects of the present invention, the amount of these additives is usually 3 parts by weight per 100 parts by mass of the sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1).
It is at most 00 parts by mass, preferably at most 200 parts by mass, more preferably at most 100 parts by mass.

As a method for producing the polymerizable composition of the present invention,
Specifically, the sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) of the present invention is used, and if necessary, the above-mentioned known various polymerizable compounds are used in combination. After that, it is obtained by mixing and dissolving. The polymerizable composition is insoluble before polymerization, if necessary,
Foreign matter and the like are removed by filtration, and further sufficiently defoamed under reduced pressure to be used for polymerization and curing. When producing the polymerizable composition, if desired, an internal release agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a coloring pigment (for example, cyanine green, cyanine blue, etc.), a dye, Flow regulators, inorganic fillers (eg, talc, silica, alumina,
It is also possible to add various known additives such as barium sulfate and magnesium oxide.

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 molds which are mirror-polished via a gasket made of a soft thermoplastic resin such as 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 gasket made of the above-mentioned soft thermoplastic resin, two molds may be fixed with a polyester adhesive tape or the like.

[0357] The mold may be subjected to a known treatment method such as a mold release treatment.

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.

In these methods, thermal polymerization requires several hours to several tens of hours, whereas photopolymerization by ultraviolet rays 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 for molding an optical lens, as described above, for example, a method for obtaining a lens by performing cast polymerization using light or / and heat (for example, Japanese Unexamined Patent Application Publication No.
0-135901, JP-A-10-67736, JP-A-10-130250, etc.).

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

The obtained optical lens may be subjected to surface polishing, antistatic treatment, hard coat treatment, or the like for the purpose of imparting anti-reflection, imparting high hardness, improving abrasion resistance, imparting anti-fogging property or imparting fashion, if necessary. Non-reflective coating treatment, dyeing treatment,
Various known physical or chemical treatments such as a light control treatment (for example, a photochromic lens formation treatment) may be performed.

As a method for molding a substrate of an optical disk or a magneto-optical disk, for example, a polymerizable composition containing a sulfur-containing unsaturated carboxylic acid ester compound represented by the general formula (1) obtained by the above method may be used. A method of injecting the mixture into a substrate mold cavity, polymerizing the mixture by a radical polymerization method or the like, and performing a post-heat treatment if necessary (Japanese Patent Laid-Open No. 58-130450)
JP-A-58-137150, JP-A-62-280
008), a method of photopolymerization in a double-sided glass mold (Japanese Patent Application Laid-Open No. 60-202557), a method of thermally polymerizing a liquid resin by applying pressure after completion of vacuum casting or liquid injection (Japanese Patent Application Laid-Open No. 60-202557). -203414) and conventionally known methods.

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

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

[0367]

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.

<Production of sulfur-containing compound represented by general formula (9)> Synthesis example 1 [Exemplary compound number 9-2 in Table 3; in formula (9), R ₉₁ = R ₉₂ = hydrogen atom, R ₉₃ = bromine atom, p = 0, q =
Synthesis of Compound 2] 50 made of glass equipped with a stirrer
In a 0 ml reactor, 25.4 g of ethanedithiol
(0.27 mol), boron trifluoride ether complex 25m
and 100 g of toluene. To this mixture, 55.4 g (0.275 mol) of 90% 2- (2′-bromoethyl) -1,3-dioxolane was added at 20 ° C. for 1 hour.
It was dropped over time. Further, after reacting at 20 ° C. for 5 hours, 150 g of ice water and 50 g of toluene were added to the reaction mixture, and the mixture was stirred for 15 minutes, allowed to stand still, and separated to extract a toluene phase. The toluene phase was alkali-washed with 150 g of a 3% aqueous sodium hydrogen carbonate solution, and further washed with water until the aqueous phase became neutral. The toluene phase was separated and taken out, and the toluene was distilled off under reduced pressure at 40 ° C., and the obtained crude product was distilled under reduced pressure to obtain colorless liquid 2- (2′-bromoethyl) -1,3-dithiolane. 51.8 g were obtained. Yield = 90%, Purity> 99% (Area method by gas chromatography analysis) Boiling point: 93-96 ° C./0.22 mmHg ¹ H-NMR δ (CDCl ₃ ): 2.2-2.3 (m,
2H), 3.2 (s, 4H), 3.4 to 3.5 (m, 2
H) 4.6-4.7 (t, 1H) FD-MS: 213 (M ^<+> )

Synthesis Example 2 [Exemplary Compound No. 9-18 in Table 3; R ₉₁ = R ₉₂ = hydrogen atom, R ₉₃ = thiol group, p = 0 in formula (9)]
Synthesis of Compound with q = 2] In a glass reactor of 500 ml equipped with a stirrer, 32.0 g of thiourea (0.
42 mol) and 175 g of ethanol. To this mixture, 44.8 g of 2- (2′-bromoethyl) -1,3-dithiolane prepared in Synthesis Example 1 was added dropwise at 50 ° C. over 35 minutes. Further, the reaction was carried out at 80 ° C. for 4 hours to thiuronium chloride. The reaction solution was analyzed by high performance liquid chromatography to confirm that the raw material bromo compound had disappeared.
200 g of aqueous ammonia was dropped at 50 ° C. over 10 minutes,
The reaction was further performed at 50 ° C. for 2 hours to hydrolyze the thyuronium salt. After 100 g of toluene was added for liquid separation and extraction, the toluene phase was washed with water until the drainage phase became neutral. Thereafter, the toluene phase was taken out and the toluene was removed at 40 ° C. under reduced pressure.
The crude product obtained by distillation under reduced pressure was distilled under reduced pressure to obtain 31.6 g of colorless liquid 2- (2'-mercaptoethyl) -1,3-dithiolane.

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

Synthesis Example 3 [Exemplary Compound No. 9-32 in Table 3; R ₉₁ = R ₉₂ = hydrogen atom, R ₉₃ = hydroxyl group, p =
Synthesis of Compounds with 0, q = 2] In a 100 ml glass reactor equipped with a stirrer, 2
-(2′-bromoethyl) -1,3-dithiolane 21.
3 g (0.10 mol), sodium formate 13.6 g
(0.20 mol) and 1.61 g (0.005 mol) of tetramethylammonium bromide. This mixture was heated and stirred at 110 ° C. for 1.5 hours. After completion of the reaction, 8.8 g of a 50% aqueous sodium hydroxide solution was added dropwise to the reaction mixture with stirring over 15 minutes. After the reaction product was extracted with toluene and washed with water, the toluene was distilled off at 40 ° C. under reduced pressure, and the obtained crude product was distilled under reduced pressure to give 2- (2′-hydroxyethyl)-as a colorless liquid. 1,
13.5 g of 3-dithiolane were obtained.

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

Synthesis Example 4 [Exemplified Compound No. 9-5 in Table 3; R ₉₁ = methyl group, R ₉₂ = hydrogen atom, R ₉₃ = bromine atom, p in formula (9)]
= 0, q = 2] A colorless liquid 2-(-) was prepared in the same manner as in Synthesis Example 1 except that 1,2-propanedithiol was used instead of ethanedithiol. 2'-bromoethyl) -4-methyl-
1,3-Dithiolane was obtained.

Synthesis Example 5 [Exemplified Compound No. 9-21 in Table 3; R ₉₁ = methyl group, R ₉₂ = hydrogen atom, R ₉₃ = thiol group, p = 0, q = 2 in formula (9)] Synthesis of Compound] In Synthesis Example 2, instead of using 2- (2′-bromoethyl) -1,3-dithiolane prepared in Synthesis Example 1 as a raw material, 2- (2′-bromoethyl) prepared in Synthesis Example 4 was used. Synthesis Example 2 except that) -4-methyl-1,3-dithiolane was used
Was performed in the same manner as described above to obtain colorless liquid 2- (2′-mercaptoethyl) -4-methyl-1,3-dithiolane.

<Production Example of Sulfur-Containing Dihydroxy Compound Represented by General Formula (2) of the Present Invention> Example 1 220.4 g (2.00 mol) of benzenethiol, 3.0 g (0.075 mol) of sodium hydroxide ), And 300 g of a raw material mixture of methanol, 222.2 g of resorcin diglycidyl ether represented by the following formula (10-1):
(1.00 mol) dissolved in 400 g of methanol was added dropwise at 10 ° C. for 1 hour. After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 3 hours, and after confirming that no raw material remained by HPLC (high performance liquid chromatography), the reaction solution was discharged into ice water.

The oily product was extracted with 300 g of toluene, washed repeatedly with water until the drainage layer became neutral, and separated to separate the organic layer.

The toluene was distilled off under reduced pressure at 40 ° C. to obtain a viscous, slightly yellow transparent liquid of the formula (2-1) (the second liquid).
Sulfur-containing dihydroxy compound 4 of Exemplified Compound No. 39) in the table
20.0 g were obtained.

The yield was 95% and the purity was 99% (by the area method of HPLC analysis). The results of nuclear magnetic resonance spectrum and mass spectrometry of the product are shown below.

¹ H-NMR (400 MHz) δ (CDC
_{l 3): 2.8~2.9 (m,} 2H), 3.1~3.3
(M, 4H), 3.9-4.1 (m, 4H), 4.1-
4.4 (d, 2H), 6.4 to 6.5 (m, 3H),
7.1-7.4 (m, 11H) FD-MS: 442 (M ⁺ )

[0380]

Embedded image

[0381]

Embedded image

Example 2 Example 1 was repeated, except that the 2- (2′-mercaptoethyl) -1,3-dithiolane prepared in Synthesis Example 2 was used instead of using benzenethiol.
In the same manner as described in the above, a colorless transparent liquid of the following formula (2)
-2) (Sulfur-containing dihydroxy compound represented by (Exemplary Compound No. 27 in Table 2 above)). FD-MS: 554
(M +)

[0383]

Embedded image

Example 3 A colorless transparent liquid was prepared in the same manner as in Example 1, except that 1,3-dithiolan-2-carboxylic acid was used instead of benzenethiol. The following formula (2-3) (Exemplary Compound No. 4 in Table 2 above)
A sulfur-containing dihydroxy compound represented by 5) was obtained. FD-MS: 522 (M @ +)

[0385]

Embedded image

Example 4 22 g (0.2 mol) of benzenethiol, 0.3 g (0.0075 mol) of sodium hydroxide, 30 g of methanol
A solution obtained by dissolving 29.8 g (0.1 mol) of 4,4′-diglycidyloxybiphenyl in 40 g of methyl ethyl ketone was added dropwise to the raw material mixture at 10 ° C. for 1 hour. After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 3 hours, and after confirming that no raw material remained by HPLC (high performance liquid chromatography), the reaction solution was discharged into ice water.

The oily product was extracted with 250 g of toluene, washed repeatedly with water until the drainage layer became neutral, and separated to separate the organic layer. After distilling off toluene at 40 ° C. under reduced pressure, purification was carried out by column chromatography (400 g of silica gel, toluene of mobile phase), and as a viscous transparent liquid, the following formula (2-4)
49.2 g of a sulfur-containing dihydroxy compound represented by (Exemplary Compound No. 111 in Table 2) was obtained.

Yield = 95%, Purity = 99.6% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0389]

[Table 178]

[0390]

Embedded image

Example 5 Example 4 was repeated, except that 33.3 g (0.2 mol) of 2- (2'-mercaptoethyl) -1,3-dithiolane was used instead of using benzenethiol. And then purified by column chromatography to obtain 58.1 g of a dihydroxy compound represented by the formula (2-5) (Exemplary Compound No. 112 in Table 2) as a colorless transparent liquid. Was.

Yield = 92%, Purity = 99.5% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0393]

[Table 179]

[0394]

Embedded image

Example 6 In Example 4, 30.0 g of 1,3-dithiolan-2-carboxylic acid was used instead of using benzenethiol.
After reacting in the same manner as described in Example 4 except that (0.2 mol) was used, purification by column chromatography was carried out to obtain a viscous colorless transparent liquid of the formula (2-6)
49.1 g of a dihydroxy compound represented by (Exemplary Compound No. 113 in Table 2 above) was obtained. Yield = 94%, Purity = 99.4% (by HPLC analysis area method) The results of elemental analysis and mass spectrometry of the product are shown below.

[0396]

[Table 180]

[0397]

Embedded image

Example 7 In Example 4, instead of using 4,4'-diglycidyloxybiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl 3
Except for using 5.4 g (0.1 mol), the reaction was carried out in the same manner as in Example 4, followed by column chromatography purification to obtain a viscous colorless and transparent liquid (Formula 2-7).
54.6 g of a dihydroxy compound represented by (Exemplary Compound No. 103 in Table 2 above) was obtained.

Yield = 90%, Purity = 99.5% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0400]

[Table 181]

[0401]

Embedded image

Example 8 In Example 5, instead of using 4,4′-diglycidyloxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-diglycidyloxybiphenyl 3
After reacting in the same manner as in Example 5 except that 5.4 g (0.1 mol) was used, purification was carried out by column chromatography, and a colorless transparent liquid of the following formula (2-8) (the second 62.5 g of a sulfur-containing dihydroxy compound represented by the exemplified compound number 102) in the table was obtained. Yield = 91%, Purity = 99.5% (by the area method of HPLC analysis) The results of elemental analysis and mass spectrometry of the product are shown below.

[0403]

[Table 182]

[0404]

Embedded image

Example 9 To a raw material mixture of 18.4 g (0.2 mol) of methylthioethanol, 0.3 g (0.0075 mol) of sodium hydroxide and 30 g of methanol, 3,3 ′, 5,5′-
35.4 g (0.1 mol) of tetramethyl-4,4'-diglycidyloxybiphenyl was added to methyl ethyl ketone 40
g was added dropwise at 10 ° C. for 1 hour.
After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 3 hours.
After confirming that no raw material remained by PLC (high performance liquid chromatography), the reaction solution was discharged into ice water. The oily product was extracted with 300 g of toluene, washed repeatedly with water until the drainage layer became neutral, and then separated to remove the organic layer. After toluene was distilled off under reduced pressure at 40 ° C., column chromatography (silica gel 400) was performed.
g, mobile phase toluene) to obtain 51.6 g of a sulfur-containing dihydroxy compound represented by the formula (2-9) (exemplified compound number 86 in Table 2) as a colorless transparent liquid.

Yield = 96%, Purity = 99.5% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0407]

[Table 183]

[0408]

Embedded image

Example 10 In Example 5, instead of using 4,4′-diglycidyloxybiphenyl, 3,3 ′, 5,5′-tetramethoxy-4,4′-diglycidyloxybiphenyl 4
After the reaction was carried out in the same manner as in Example 5 except that 1.8 g (0.1 mol) was used, purification was carried out by column chromatography, and a viscous colorless and transparent liquid of formula (2-1) was obtained.
0) (Example compound number 107 in Table 2 above) to obtain 66.1 g of a sulfur-containing dihydroxy compound. Yield = 88%, Purity = 99.7% (by the area method of HPLC analysis) The results of elemental analysis and mass spectrometry of the product are shown below.

[0410]

[Table 184]

[0411]

Embedded image

Example 11 To a raw material mixture of 18.4 g (0.2 mol) of methylthioethanol, 0.3 g (0.0075 mol) of sodium hydroxide and 30 g of methanol, 3,3 ′, 5,5′-
64.2 g (0.1 mol) of tetrabromo-4,4'-diglycidyloxybiphenyl was added to methyl ethyl ketone 10
A solution dissolved in 0 g was added dropwise at 10 ° C. for 1 hour. After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 3 hours, and after confirming that no raw material remained by HPLC (high performance liquid chromatography), the reaction solution was discharged into ice water. Extracting the oily product with 400 g of toluene,
Further, after repeatedly washing with water until the drainage layer became neutral, liquid separation was performed to take out an organic layer. 40 ° C under reduced pressure of toluene
After purification by column chromatography, purification was performed by column chromatography (600 g of silica gel, toluene in mobile phase) to obtain a viscous transparent liquid containing the compound represented by the formula (2-11) (exemplified compound number 114 in Table 2 above). Sulfuric dihydroxy compound 7
1.0 g was obtained. Yield = 86%, Purity = 99.2% (by HPLC analysis area method) The results of elemental analysis and mass spectrometry of the product are shown below.

[0413]

[Table 185]

[0414]

Embedded image

Example 12 22 g (0.2 mol) of benzenethiol, 0.3 g (0.0075 mol) of sodium hydroxide, 30 g of methanol
34.0 g (0.1 mol) of 2,2-bis (4-glycidyloxyphenyl) propane based on the raw material mixture of
Was dissolved in 50 g of methanol at 10 ° C. over 1 hour. After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 3 hours. HPLC (High Performance Liquid Chromatography)
After confirming that no raw materials remained, the reaction solution was discharged into ice water. The oily product was extracted with 350 g of toluene, washed repeatedly with water until the drainage layer became neutral, and then separated to take out an organic layer. After toluene was distilled off under reduced pressure at 40 ° C., purification was carried out by column chromatography (500 g of silica gel, mobile phase toluene) to obtain a viscous transparent liquid of the formula (2-12) (the second liquid).
53.8 g of a sulfur-containing dihydroxy compound represented by the exemplified compound number 175) in the table was obtained.

Yield = 96%, Purity = 99.5% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0417]

[Table 186]

[0418]

Embedded image

Example 13 In Example 12, 30.0 g of 1,3-dithiolan-2-carboxylic acid was used instead of using benzenethiol.
After reacting in the same manner as described in Example 12 except that (0.2 mol) was used, purification by column chromatography was carried out to obtain a colorless transparent liquid of the formula (2-13) (the exemplified compound in Table 2 above). No. 177) was obtained. Yield = 97%, purity = 99.6
% (By the area method of HPLC analysis) The results of elemental analysis and mass spectrometry of the product are shown below.

[0420]

[Table 187]

[0421]

Embedded image

Example 14 Example 12 was repeated, except that 33.3 g (0.2 mol) of 2- (2′-mercaptoethyl) -1,3-dithiolane was used instead of using benzenethiol. , And then purified by column chromatography to obtain a viscous, colorless, transparent liquid of sulfur-containing dihydroxy compound represented by the formula (2-14) (exemplified compound No. 176 in Table 2). 62.5 g were obtained.

Yield = 93%, Purity = 99.5% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0424]

[Table 188]

[0425]

Embedded image

Example 15 In place of using 2,2-bis (4-glycidyloxyphenyl) propane in Example 12, 2,2-bis (3,5-dimethyl-4-glycidyloxyphenyl) propane was used. After reacting in the same manner as in Example 12 except that 6 g (0.1 mol) was used, purification was carried out by column chromatography and the viscous formula (2-1) was obtained.
5) 56.7 g of a dihydroxy compound represented by (exemplary compound number 167 in Table 2 above) was obtained. Yield = 92%, Purity = 99.6% (by HPLC analysis area method) The results of elemental analysis and mass spectrometry of the product are shown below.

[0427]

[Table 189]

[0428]

Embedded image

Example 16 In Example 13, instead of using 2,2-bis (4-glycidyloxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-glycidyloxyphenyl) propane was used. After reacting in the same manner as in Example 13 except that 6 g (0.1 mol) was used, purification was carried out by column chromatography, and a colorless transparent liquid of the formula (2)
-16) (65.5 g of a dihydroxy compound represented by the above-exemplified compound number 170 in Table 2).

Yield = 94%, Purity = 99.8% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0431]

[Table 190]

[0432]

Embedded image

Example 17 To a raw material mixture of 18.4 g (0.2 mol) of methylthioethanol, 0.3 g (0.0075 mol) of sodium hydroxide, and 30 g of methanol, 2,2-bis (4-glycidyloxy) was added. 34.0 g of phenyl) propane (0.1
(Mol) in 40 g of methyl ethyl ketone was added dropwise at 10 ° C. for 1 hour. After completion of dropping, room temperature (2
(5 ° C.) for 3 hours, and after confirming that no raw material remains by HPLC (high performance liquid chromatography),
The reaction solution was discharged into ice water. The oily product is dissolved in toluene 3
Extraction was performed using 00 g, and washing with water was repeated until the drainage layer became neutral. Then, liquid separation was performed to take out an organic layer. After toluene was distilled off under reduced pressure at 40 ° C., purification was carried out by column chromatography (400 g of silica gel, toluene of mobile phase), and 53.5 g of a sulfur-containing dihydroxy compound represented by the formula (2-17) as a colorless and transparent liquid. I got

Yield = 96%, Purity = 99.5% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0435]

[Table 191]

[0436]

Embedded image

Example 18 In Example 14, 2,2-bis (3,5-dimethoxy-4-glycidyloxyphenyl) propane was used instead of 2,2-bis (4-glycidyloxyphenyl) propane. After the reaction was carried out in the same manner as in Example 14 except that 0 g (0.1 mol) was used, purification was carried out by column chromatography, and a viscous colorless and transparent liquid of the formula (2-18) (the second Exemplified compound number 1 in the table
71.2 g of the sulfur-containing dihydroxy compound represented by the formula (71) was obtained.

Yield = 90%, Purity = 99.7% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0439]

[Table 192]

[0440]

Embedded image

Example 19 To a raw material mixture of 18.4 g (0.2 mol) of methylthioethanol, 0.3 g (0.0075 mol) of sodium hydroxide and 30 g of methanol, 2,2-bis (3,5
-Dibromo-4-glycidyloxyphenyl) propane (65.6 g, 0.1 mol) in methyl ethyl ketone 100
g was added dropwise at 10 ° C. for 1 hour.
After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 3 hours. HP
After confirming that no raw material remained by LC (high performance liquid chromatography), the reaction solution was discharged into ice water. The oily product was extracted with 400 g of toluene, washed repeatedly with water until the drainage layer became neutral, and then separated to take out an organic layer. After distilling off toluene at 40 ° C. under reduced pressure, column chromatography (600 g of silica gel,
Purification was performed using toluene (mobile phase), and a viscous transparent liquid of formula (2-19) (Exemplified Compound No. 17 in Table 2 above)
58.4 g of the sulfur-containing dihydroxy compound represented by 8) was obtained.

Yield = 89%, Purity = 99.2% (HPL
The results of elemental analysis and mass spectrometry of the product are shown below.

[0443]

[Table 193]

[0444]

Embedded image

Examples 20 to 61 By a method similar to the method described in Examples 1 to 19 above, the reaction of a diepoxy compound and a sulfur-containing compound shown in Table 4 below gave a general product of the present invention. A sulfur-containing dihydroxy compound represented by the formula (2) was produced.

[0446]

[Table 194]

[0447]

[Table 195]

[0448]

[Table 196]

[0449]

[Table 197]

[0450]

[Table 198]

[0451]

[Table 199]

[0452]

[Table 200]

[0453]

[Table 201]

[0454]

[Table 202]

[0455]

[Table 203]

<Production of sulfur-containing unsaturated carboxylic acid ester compound represented by general formula (1) of the present invention> Example 62 Sulfur-containing dihydroxy compound represented by formula (2-1) produced in Example 1 55.5 g (0.10 mol), pyridine 1
To a mixed solution of 9.0 g (0.24 mol) and 200 g of chloroform, 19.9 g (0.22 mol) of acrylic acid chloride was added dropwise under ice-water cooling (10 ° C.). After the completion of the dropwise addition, the reaction was carried out by stirring at 10 ° C. for further 3 hours, and then the by-product pyridine hydrochloride was removed by filtration. The chloroform solution of the filtrate was further washed with 200 g of dilute hydrochloric acid water, washed with water until the drainage layer became neutral, separated, and the organic layer was taken out. Chloroform under reduced pressure
The residue was distilled at ℃ to obtain a crude product as a pale yellow transparent liquid. The crude product is purified by silica gel chromatography to give a viscous colorless transparent liquid of the following formula (1-1)
63.0 g of a sulfur-containing acrylic acid ester compound (Exemplary Compound No. 39 in Table 1) was obtained.

The yield is 95% and the purity is 99% or more (HPL
C analysis area method). The results of nuclear magnetic resonance spectrum and mass spectrometry of the product are shown below.

¹ H-NMR (400 MHz) δ (CD
_{Cl 3): 3.3~3.4 (m,} 4H), 4.1~4.
3 (m, 4H), 5.3 to 5.4 (m, 2H), 5.8
To 5.9 (d, 2H), 6.0 to 6.1 (dd, 2
H), 6.3-6.5 (m, 5H), 7.1-7.5
(M, 11H) FD-MS: 550 (M ⁺ )

[0459]

Embedded image

Example 63 Example 63 was repeated except that the dihydroxy compound represented by the formula (2-2) produced in Example 2 was used instead of using the dihydroxy compound represented by the formula (2-1). In the same manner as in Example 62, a sulfur-containing acrylate compound represented by the following formula (1-2) (Exemplary Compound No. 27 in Table 1) was obtained as a colorless transparent liquid. FD-MS: 663 (M ⁺ )

[0461]

Embedded image

Example 64 The procedure of Example 62 was repeated, except that the dihydroxy compound represented by the formula (2-3) produced in Example 3 was used instead of using the dihydroxy compound represented by the formula (2-1). In the same manner as in the method described in Example 62, a sulfur-containing acrylate compound represented by the following formula (1-3) (Exemplified Compound No. 45 in Table 1) was obtained as a colorless transparent liquid. FD-MS: 630 (M @ +)

[0463]

Embedded image

Example 65 A colorless transparent liquid was prepared in the same manner as in Example 62 except that methacrylic acid chloride was used instead of acrylic acid chloride. -4) (Exemplary Compound No. 7 in Table 1 above)
A sulfur-containing methacrylate compound represented by 1) was obtained. FD-MS: 578 (M ⁺ )

[0465]

Embedded image

Example 66 26.0 g (0.05 mol) of the sulfur-containing dihydroxy compound represented by the formula (2-4) produced in Example 4 above, 9.5 g (0.12 mol) of pyridine, and 100 g of chloroform 9.95 g (0.11 mol) of acrylic acid chloride was added dropwise to the mixed solution of (1) under ice-water cooling (10 ° C.). After the completion of the dropwise addition, the reaction was carried out by stirring at 10 ° C. for further 3 hours, and then the by-product pyridine hydrochloride was removed by filtration. The chloroform solution of the filtrate was further washed with 100 g of dilute hydrochloric acid water, washed with water until the drainage layer became neutral, separated, and the organic layer was taken out. Chloroform under reduced pressure
The residue was distilled at ℃ to obtain a crude product as a pale yellow transparent liquid. The crude product is purified by silica gel chromatography to give a viscous colorless transparent liquid of the following formula (1-5)
29.4 g of a sulfur-containing acrylate compound represented by (Exemplary Compound No. 126 in Table 1 above) was obtained. Yield = 94%, Purity = 99.2% (by the area method of HPLC analysis) The results of elemental analysis and mass spectrometry of the product are shown below.

[0467]

[Table 204]

[0468]

Embedded image

Example 67 Instead of using the sulfur-containing dihydroxy compound represented by the formula (2-4) in Example 66, the sulfur-containing dihydroxy compound represented by the formula (2-7) obtained in Example 7 was used. Except for using 28.7 g (0.05 mol) of the dihydroxy compound, the reaction was carried out in the same manner as described in Example 66 above, followed by column chromatography purification to obtain a viscous colorless transparent liquid represented by the following formula (1) -6) (Sulfur-containing acrylate compound of Exemplified Compound No. 118 in Table 1) 32.4
g was obtained. Yield = 95%, Purity = 99.7% (by the area method of HPLC analysis) The results of elemental analysis and mass spectrometry of the product are shown below.

[0470]

[Table 205]

[0471]

Embedded image

Example 68 31.6 g (0.05 mol) of the sulfur-containing dihydroxy compound of the formula (2-5) obtained in Example 5 was reacted in the same manner as in Example 66, and then reacted with a column. After performing chromatographic purification, the following formula (1) was obtained as a viscous colorless transparent liquid.
-7) 34.7 g of a sulfur-containing acrylate compound (Exemplary Compound No. 127 in Table 1 above) was obtained. Yield = 94%, Purity = 99.6% (by HPLC analysis area method) The results of elemental analysis and mass spectrometry of the product are shown below.

[0473]

[Table 206]

[0474]

Embedded image

Example 69 34.4 g (0.05 mol) of the sulfur-containing dihydroxy compound of the formula (2-8) obtained in Example 8 was reacted in the same manner as in Example 66, and then reacted with a column. After performing chromatographic purification, the following formula (1) was obtained as a viscous colorless transparent liquid.
-8) 32.4 g of a sulfur-containing acrylate compound (Exemplified Compound No. 117 in Table 1) was obtained. Yield = 95%, Purity = 99.7% (by the area method of HPLC analysis) The results of elemental analysis and mass spectrometry of the product are shown below.

[0476]

[Table 207]

[0477]

Embedded image

Example 70 The procedure of Example 69 was repeated, except that methacrylic acid chloride was used instead of acrylic acid chloride. 9) (Exemplary Compound No. 14 in Table 1 above)
A sulfur-containing methacrylate compound represented by 1) was obtained. The results of elemental analysis and the results of mass spectrometry of the product are shown below.

[0479]

[Table 208]

[0480]

Embedded image

Example 71 41.3 g (0.05 mol) of the sulfur-containing dihydroxy compound of the formula (2-11) obtained in Example 11 was reacted in the same manner as described in Example 66, and then reacted with a column. Chromatographic purification was performed to obtain 44.4 g of a sulfur-containing acrylate compound represented by the following formula (1-10) (exemplified compound No. 129 in Table 1) as a viscous colorless transparent liquid. Yield = 98%, Purity = 99.8% (by the area method of HPLC analysis) The results of elemental analysis and mass spectrometry of the product are shown below.

[0482]

[Table 209]

[0483]

Embedded image

Example 72 28.0 g (0.05 mol) of the sulfur-containing dihydroxy compound represented by the formula (2-12) produced in Example 12, 9.5 g (0.12 mol) of pyridine and 100 g of chloroform were prepared. 9.95 g (0.11 mol) of acrylic acid chloride was added dropwise to the mixed solution under ice-water cooling (10 ° C.). After the completion of the dropwise addition, the reaction was carried out by stirring at 10 ° C. for further 3 hours, and then the by-product pyridine hydrochloride was removed by filtration. The chloroform solution of the filtrate was further washed with 100 g of dilute hydrochloric acid water, washed with water until the drainage layer became neutral, separated, and the organic layer was taken out. Chloroform under reduced pressure
The residue was distilled at ℃ to obtain a pale yellow transparent liquid crude product. The crude product is purified by silica gel chromatography to give a viscous colorless transparent liquid of the following formula (1-11)
30.7 g of a sulfur-containing acrylate compound (Exemplary Compound No. 190 in Table 1) was obtained. Yield = 92%, Purity = 99.0% (by HPLC analysis area method) The results of elemental analysis and mass spectrometry of the product are shown below.

[0485]

[Table 210]

[0486]

Embedded image

Example 73 32.0 g (0.05 mol) of the sulfur-containing dihydroxy compound represented by the formula (2-13) obtained in Example 13 was reacted in the same manner as in Example 72. Thereafter, purification by column chromatography was performed to obtain a viscous colorless transparent liquid of the following formula (1-12) (Exemplified Compound No. 1 in Table 1 above).
34.8 g of the sulfur-containing acrylate compound of the above 92) was obtained. Yield = 93%, Purity = 99.5% (by HPLC analysis area method) The results of elemental analysis and the results of mass spectrometry of the product are shown below.

[0488]

[Table 211]

[0489]

Embedded image

Example 74 33.6 g (0.05 mol) of the sulfur-containing dihydroxy compound of the formula (2-14) obtained in Example 14 was reacted in the same manner as in Example 72, and then reacted with a column. Chromatographic purification was performed to obtain 36.7 g of a sulfur-containing acrylate compound represented by the following formula (1-13) (exemplified compound No. 191 in Table 1) as a viscous colorless transparent liquid. Yield = 94%, Purity = 99.5% (by the area method of HPLC analysis) The results of elemental analysis and the results of mass spectrometry of the product are shown below.

[0490]

[Table 212]

[0492]

Embedded image

Example 75 30.8 g (0.05 mol) of the sulfur-containing dihydroxy compound of the formula (2-15) obtained in Example 15 was reacted in the same manner as in Example 72, and then reacted with a column. Chromatographic purification was performed to obtain 32.9 g of a sulfur-containing acrylate compound represented by the following formula (1-14) (exemplified compound number 182 in Table 1) as a viscous colorless transparent liquid. Yield = 91%, Purity = 99.2% (by the area method of HPLC analysis) The results of elemental analysis and mass spectrometry of the product are shown below.

[0494]

[Table 213]

[0495]

Embedded image

Example 76 The procedure of Example 74 was repeated, except that methacrylic acid chloride was used instead of acrylic acid chloride, to give a colorless transparent liquid of the following formula (1- 15) (Exemplary Compound No. 2 in Table 1 above)
The sulfur-containing methacrylate compound represented by the formula (05) was obtained.

The results of elemental analysis and the results of mass spectrometry of the product are shown below.

[0498]

[Table 214]

[0499]

Embedded image

Example 77 34.8 g (0.05 mol) of the sulfur-containing dihydroxy compound of the formula (2-16) obtained in Example 16 was reacted in the same manner as in Example 72, and then reacted with a column. Chromatographic purification was performed to obtain 38.2 g of a sulfur-containing acrylate compound represented by the following formula (1-16) (exemplified compound number 185 in Table 1) as a viscous colorless transparent liquid.

Yield = 95%, Purity = 99.1% (HPL
The results of elemental analysis of the product and the results of mass spectrometry are shown below.

[0502]

[Table 215]

[0503]

Embedded image

Example 78 26.2 g (0.05 mol) of the sulfur-containing dihydroxy compound of the formula (2-17) obtained in Example 17 was used in Example 72.
And then purified by column chromatography to obtain a viscous colorless and transparent liquid as a sulfur-containing acrylate compound 3 of the following formula (1-17):
0.4 g was obtained. Yield = 96%, Purity = 99.5% (by the area method of HPLC analysis) The results of elemental analysis and mass spectrometry of the product are shown below.

[0505]

[Table 216]

[0506]

Embedded image

Example 79 In Example 72, 39.6 g (0.05 mol) of the sulfur-containing dihydroxy compound of the formula (2-18) obtained in Example 18 was used.
And then purified by column chromatography to obtain a viscous colorless and transparent liquid as a sulfur-containing acrylate compound 4 of the following formula (1-18).
2.8 g were obtained.

Yield = 95%, Purity = 99.4% (HPL
The results of elemental analysis of the product and the results of mass spectrometry are shown below.

[0509]

[Table 217]

[0510]

Embedded image

Example 80 32.8 g (0.05 mol) of the sulfur-containing dihydroxy compound of the formula (2-19) obtained in Example 19 was reacted in the same manner as in Example 72, and then reacted with a column. Chromatographic purification was performed to obtain 42.7 g of a sulfur-containing acrylate compound represented by the following formula (1-19) (exemplified compound number 193 in Table 1) as a viscous colorless transparent liquid.

Yield = 90%, Purity = 99.1% (HPL
The results of elemental analysis of the product and the results of mass spectrometry are shown below.

[0513]

[Table 218]

[0514]

Embedded image

Examples 81 to 137 By the same method as described in Examples 62 to 80, the sulfur-containing sulfur-containing non-sulfuric acid represented by the general formula (1) of the present invention shown in Table 5 below was obtained. A saturated carboxylic ester compound was produced.

[0516]

[Table 219]

[0517]

[Table 220]

[0518]

[Table 221]

[0519]

[Table 222]

[0520]

[Table 223]

[0521]

[Table 224]

[0522]

[Table 225]

[0523]

[Table 226]

[0524]

[Table 227]

[0525]

[Table 228]

[0526]

[Table 229]

[0527]

[Table 230]

[0528]

[Table 231]

[0529]

[Table 232]

<Preparation of Polymerizable Composition Using Sulfur-Containing Unsaturated Carboxylic Acid Ester Compound Represented by General Formula (1) of the Present Invention, Production of Cured Product by Curing and Evaluation of Physical Properties>
The physical properties of the cured product or optical component (lens) produced in each of the following examples were evaluated by the following methods. -Appearance: Color and transparency were visually confirmed. -Refractive index, Abbe number: 20 using a Pulfrich refractometer
Measured in ° C.

Example 138 To 30 g of the sulfur-containing acrylate compound of the formula (1-1) obtained in Example 62, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
30 mg of ON ("Darocur-1173", Ciba-Geigy) was added, mixed well and dissolved. The resulting liquid was sufficiently defoamed under reduced pressure, and then poured into a mold composed of a glass mold and a gasket. Use a metal halide lamp (80 W / cm) to emit 60 UV rays.
The polymerization was performed by irradiation for 2 seconds. After completion of the polymerization, the mixture was gradually cooled, and the formed cured product was taken out of the mold.

[0532] The obtained cured product was colorless and transparent, and no optical distortion was observed. The refractive index (nd) was 1.614 and the Abbe number (νd) was 30.0.

Examples 139 to 167 Instead of using the sulfur-containing acrylate compound of the formula (1-1) in Example 138, Examples 63 to 80 were used.
In the same manner as in Example 138, except that each of the sulfur-containing unsaturated carboxylic acid ester compounds shown in Table 5 and Formulas (1-2) to (1-19) and Table 5 was used, A cured product was obtained. Table 6 shows the physical properties of the cured product obtained after the polymerization.

[0534]

[Table 233]

[0535]

[Table 234]

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

[0537] The physical properties of the cured product or optical component (lens) produced in each of the following examples were evaluated by the following methods. -Appearance: Color and transparency were visually confirmed. -Refractive index, Abbe number: 20 using a Pulfrich refractometer
Measured in ° C. Impact resistance: An iron ball of 28.7 g from a height of 127 cm was dropped on the center of a minus lens having a center thickness of 1.5 mm to check for cracks. The evaluation is as follows. ：: There is no crack in the lens. X: The lens was cracked.

Example 168 20 g of a sulfur-containing acrylate compound of the formula (1-2) obtained in Example 63, 5 g of an epoxy acrylate of resorcin diglycidyl ether represented by the following formula (13-1) and divinylbenzene To 5 g of the mixture, 60 mg of 2-hydroxy-2-methyl-1-phenylpropan-1-one (0.2% by mass relative to the polymerizable monomer) was added, mixed well, and dissolved. After sufficiently defoaming the obtained liquid, it was poured into a mold (adjusted to a minus lens shape) comprising a glass mold and a tape. After irradiating with ultraviolet rays for 60 seconds by a metal halide lamp,
The polymerization was carried out by heating for an hour. After completion of the polymerization, the mixture was allowed to cool to room temperature to obtain a minus lens having a diameter of 30 mm and a center thickness of 1.5 mm.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.611 and Abbe number (νd) was 36.5. Glass transition temperature (Tg) by TMA method is 110 ° C
And no drop was observed. Further, as a result of the impact resistance test by the above method, there was no crack of the lens.

[0540]

Embedded image

Example 169 In Example 168, instead of using 20 g of the sulfur-containing acrylate compound of the formula (1-2) and 5 g of the epoxy acrylate of resorcin diglycidyl ether represented by the formula (13-1), Sulfur-containing acrylate compound 2 represented by formula (1-7) obtained in Example 68
0g and 3,3 ′,
A minus lens was produced in the same manner as in Example 168 except that 5 g of 5,5'-tetramethyl-4,4'-diphenylglycidyloxybiphenyl epoxy acrylate was used.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.608 and Abbe number (νd) was 33.3. The glass transition temperature (Tg) according to the TMA method was 86 ° C., and no depression was observed. Further, as a result of the impact resistance test by the above method, there was no crack of the lens.

[0543]

Embedded image

Example 170 A minus lens was manufactured in the same manner as in Example 169 except that 5 g of ethylene glycol dimethacrylate was used instead of divinylbenzene.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.595 and Abbe number (νd) was 35.0. The glass transition temperature (Tg) by TMA method was 71 ° C., and no drop was observed. Further, as a result of the impact resistance test by the above method, there was no crack of the lens.

Example 171 The procedure of Example 169 was repeated, except that 5 g of phenyl methacrylate was used instead of divinylbenzene.
According to a method similar to that described in Example 169 above,
A minus lens was produced.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.607, and Abbe number (νd) was 34.9. The glass transition temperature (Tg) by TMA method was 84 ° C., and no drop was observed. Further, as a result of the impact resistance test by the above method, there was no crack of the lens.

Example 172 In Example 168, instead of using 20 g of the sulfur-containing acrylate compound represented by the formula (1-2) and 5 g of the epoxy acrylate of resorcin diglycidyl ether represented by the formula (13-1), 20 g of the sulfur-containing acrylate compound represented by the formula (1-13) obtained in Example 74 and 2,2-bis (4-glycidyloxyphenyl) propane represented by the following formula (13-3) Example 16 except that 5 g of epoxy acrylate was used.
According to the same method as described in No. 8, a minus lens was produced.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.607 and Abbe number (νd) was 35.9. The glass transition temperature (Tg) by TMA method was 81 ° C., and no depression was observed. Further, as a result of the impact resistance test by the above method, there was no crack of the lens.

[0550]

Embedded image

Example 173 A minus lens was manufactured in the same manner as in Example 172 except that 5 g of ethylene glycol dimethacrylate was used instead of divinylbenzene.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.604 and Abbe number (νd) was 36.4. The glass transition temperature (Tg) by TMA method was 83 ° C., and no depression was observed. Further, as a result of the impact resistance test by the above method, there was no crack of the lens.

Example 174 The procedure of Example 172 was repeated, except that 5 g of phenyl methacrylate was used instead of divinylbenzene.
According to a method similar to that described in Example 172 above,
A minus lens was produced.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.610 and Abbe number (νd) was 34.3. The glass transition temperature (Tg) according to the TMA method was 80 ° C., and no depression was observed. Further, as a result of the impact resistance test by the above method, there was no crack of the lens.

Example 175 The procedure of Example 172 was repeated, except that 5 g of ethylene glycol dimethacrylate was used instead of the epoxy acrylate of the formula (13-3). A minus lens was produced.

The lens is colorless and transparent, and has a refractive index (n
d) was 1.607 and Abbe number (νd) was 36.7. The glass transition temperature (Tg) by TMA method was 89 ° C., and no drop was observed. Further, as a result of the impact resistance test by the above method, there was no crack of the lens.

Examples 176 to 181 In the same manner as in Example 168, a polymerizable composition having the composition shown in Table 7 was prepared to prepare a lens. Table 7 shows the results of evaluation of the physical properties of the lens.

Comparative Example 1 In Example 168, instead of using the acrylate compound of the present invention as a polymerizable monomer, a known acrylate compound (described in JP-A-4-161410) was used. -Bis (acryloyloxyethylthiomethyl) -1,4-dithiane (hereinafter DT)
A polymerizable composition was prepared in the same manner as in Example 168 except that 24 g of AET) and 6 g of dimethylol tricyclodecane acrylate (hereinafter, referred to as DCPA) were used to prepare a lens. . Table 7 shows the results of evaluation of the physical properties of the lens.

Comparative Example 2 In Example 168, instead of using the acrylate compound of the present invention as a polymerizable monomer, a known acrylate compound (described in JP-A-3-217412) was used. -Bis (2-methacryloyloxyethylthio) xylylene (hereinafter referred to as XDMET) 24 g and 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (hereinafter BSAM)
A polymerizable composition was prepared and a lens was prepared in the same manner as in Example 168 except that 6 g was used. Table 7 shows the results of evaluation of the physical properties of the lens.

Comparative Example 3 In Example 168, instead of using the acrylate compound of the present invention as a polymerizable monomer, a known acrylate compound described in JP-A-63-248814 was used. -Bis [2-methacryloyloxy-3- (2,4,6-tribromophenoxy)
Propoxy] benzene (hereinafter referred to as BMPB) 18
g and chlorostyrene (hereinafter referred to as CST) 12
A polymerizable composition was prepared and a lens was prepared in the same manner as in Example 168 except that g was used. Table 7 shows the results of evaluation of the physical properties of the lens.

[0561]

[Table 235] In the table, DVB indicates divinylbenzene, EGDMA indicates ethylene glycol dimethacrylate, and PMA indicates phenyl methacrylate.

The cured product and the optical component obtained by polymerizing the polymerizable composition containing the sulfur-containing unsaturated carboxylic acid ester compound of the present invention have optical properties, thermal properties, and mechanical properties (impact resistance). It is excellent, can be polymerized and cured in a short time (high productivity), and has a high refractive index.

[0563]

The sulfur-containing unsaturated carboxylic acid 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. An optical component obtained by curing the polymerizable composition has excellent optical properties, thermal properties, and mechanical properties, and
It has good productivity, high refractive index, and is useful as various plastic lenses typified 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 dihydroxy compound represented by the general formula (2), which is a novel compound which is very useful as a raw material for synthesizing a raw material monomer for such an optical resin. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C07C 323/64 C07C 323/64 4J100 C07D 277/12 C07D 277/12 277/16 277/16 277/56 277 / 56 333/40 333/40 339/06 339/06 339/08 339/08 341/00 341/00 C08F 20/38 C08F 20/38 22/24 22/24 C08J 5/00 CEY C08J 5/00 CEY G02B 1/04 G02B 1/04 6/00 391 6/00 391 G02C 7/02 G02C 7/02 // C08L 33:14 C08L 33:14 (31) Priority claim number Japanese Patent Application No. 2000-24152 (P2000-24152) (32) Priority date February 1, 2000 (2000.2.1) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 2000-45348 (P2000-45348) (32) ) Priority date February 23, 2000 (Feb. 23, 2000) (33) Countries claiming priority Japan (JP) (72) Akiya Atsushi Atsushi 580-32 Nagaura, Sodegaura-shi, Chiba Prefecture Mitsui Chemicals, Inc. (72) Inventor Kenichi Fujii 580-32, Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals Inc. Address 32 Mitsui Chemicals, Inc. (72) Inventor Masatoshi Takagi 580, Nagaura, Sodegaura-shi, Chiba Prefecture Mitsui Chemicals, Inc. Inventor Keisuke Takuma 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals Co., Ltd. AL66P AL82P AL83P AL87P BA02P BA05P BA15P BA41P BA51P BA53P BA55P BA58P BB01P BB03P BC04P BC43P BC44P BC45P BC48P BC49P BC83P CA01 CA04 CA05 CA06 DA42 JA32 JA33

Claims (16)

[Claims] 1. Sulfur-containing unsaturated compounds having an α, β-unsaturated carboxylic acid residue via a sulfur-containing substituent and at least two oxygen atoms bonded to secondary or tertiary carbon atoms. Carboxylic acid ester compounds. 2. The method according to claim 1, which is represented by the following general formula (1).
Sulfur-containing unsaturated carboxylic acid ester compounds. Embedded image[Wherein, R₁₁Represents a divalent organic group, and X₁₁Is German
First, an oxygen atom, a sulfur atom, a -COO- group or-(CH
_Two)_lX₁₂-Group (X₁₂Represents an oxygen atom or a sulfur atom,
l represents an integer of 1 to 3);₁₂Are independent
Represents a hydrogen atom or an alkyl group;₁₃Is German
Stands for a substituent containing a sulfur atom; ₁₄Are each
Independently represents an α, β-unsaturated carboxylic acid residue] 3. The sulfur-containing unsaturated carboxylic acid ester compound according to claim 2, which is obtained by reacting a sulfur-containing dihydroxy compound represented by the following general formula (2) with an α, β-unsaturated carboxylic acid derivative. Embedded image [Wherein, R ₁₁ represents a divalent organic group, and X ₁₁ each independently represent an oxygen atom, a sulfur atom, a —COO— group, or — (CH
₂ ) ₁ X ₁₂ -group (X ₁₂ represents an oxygen atom or a sulfur atom, 1 represents an integer of 1 to 3), R ₁₂ each independently represents a hydrogen atom or an alkyl group, and R ₁₃ represents Independently represents a substituent containing a sulfur atom] 4. An α, β-unsaturated carboxylic acid residue comprising a (meth) acrylic acid residue, a crotonic acid residue, a tiglic acid residue, a 3,3-dimethylacrylic acid residue, a maleic acid residue, 3. A citraconic acid residue, a 2,3-dimethylmaleic acid residue, an itaconic acid residue or a cinnamic acid residue.
And a sulfur-containing unsaturated carboxylic acid ester compound. 5. The divalent organic group R ₁₁ is represented by the following formula (3-
3. The sulfur-containing unsaturated carboxylic acid ester compound according to claim 2, which is any group represented by a), (4-a), (5-a) or formula (6-a). Embedded image (Wherein, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each a hydrogen atom,
Represents an alkyl group, an alkoxy group, a nitro group or a halogen atom) Wherein Y ₄₁ is a single bond, a —C (R ₄₁ ) ₂ — group (R ₄₁ each independently represents a hydrogen atom or a methyl group), —O—
Group, -S- group or -SO ₂ - represents a group, R ₄₂ and R
₄₃ each independently represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an alkylthio group,
Represents a nitro group or a halogen atom, and m and n each represent an integer of 0 to 4]. (In the formula, R ₅₁ independently represents a hydrogen atom or an alkyl group.) (Wherein, R ₆₁ and R ₆₂ each represent a hydrogen atom or an alkyl group) 6. The sulfur-containing unsaturated carboxylic acid ester compound according to claim 2, wherein the substituent R ₁₃ containing a sulfur atom is a group represented by the following formula (7-a) or (8-a). R ₇₁ —O— (7-a) (wherein, R ₇₁ represents a monovalent organic group containing at least one or more sulfur atoms) R ₈₁ —S— (8-a) (wherein R ₈₁ represents a monovalent organic group which may contain a sulfur atom) 7. The sulfur-containing unsaturated carboxylic acid ester compound according to claim 2, wherein the substituent R ₁₃ containing a sulfur atom is a group represented by the following formula (9-a). Embedded image (Wherein, R ₉₁ and R ₉₂ each represent a hydrogen atom or an alkyl group, and may combine with each other to form a ring;
₉₃ represents an oxygen atom or a sulfur atom, p represents an integer of 0 to 3, and q represents an integer of 1 to 4) 8. The divalent organic group R ₁₁ represented by the following formula (3-a-
i) wherein X ₁₁ is an oxygen atom, —COO—
A group or — (CH ₂ ) _l X ₁₂ — group (X ₁₂ represents an oxygen atom or a sulfur atom, 1 represents an integer of 1 to 3);
₁₃ is a group represented by the following formula (7-a) or (8-a), and R ₁₄ is a (meth) acrylic acid residue.
And a sulfur-containing unsaturated carboxylic acid ester compound. Embedded image R ₇₁ —O— (7-a) (wherein, R ₇₁ represents a monovalent organic group containing at least one or more sulfur atoms) R ₈₁ —S— (8-a) (wherein R ₈₁ represents a monovalent organic group which may contain a sulfur atom) 9. The divalent organic group R ₁₁ has the following formula (4-a-
i), a group represented by the formula (4-a-ii) or (4-a-iii), X ₁₁ is an oxygen atom, and R ₁₃ is a group represented by the following formula (7-
The sulfur-containing unsaturated carboxylic acid ester compound according to claim 2, wherein the compound is a) or a group represented by the formula (8-a), and R ₁₄ is a (meth) acrylic acid residue. Embedded image (In the formula, R ₄₂ and R ₄₃ each independently represent a hydrogen atom or a methyl group.) (In the formula, R ₄₁ each independently represents a hydrogen atom or a methyl group.) R ₇₁ —O— (7-a) (wherein, R ₇₁ represents a monovalent organic group containing at least one or more sulfur atoms) R ₈₁ —S— (8-a) (wherein R ₈₁ represents a monovalent organic group which may contain a sulfur atom) 10. The divalent organic group R ₁₁ represented by the following formula (5-a-
a group represented by i), X ₁₁ is an oxygen atom, R ₁₃
Is a group represented by the following formula (7-a) or formula (8-a), and R ₁₄ is a (meth) acrylic acid residue. Embedded image (Wherein, R ₅₁ independently represents a hydrogen atom or an alkyl group) R ₇₁ —O— (7-a) (wherein, R ₇₁ is a monovalent organic compound containing at least one or more sulfur atoms) R ₈₁ -S- (8-a) (in the formula, R ₈₁ represents a monovalent organic group which may contain a sulfur atom) 11. A divalent organic group R ₁₁ represented by the following formula (6-a-
i) wherein X ₁₁ is an oxygen atom or —CO
An O- group, wherein R ₁₃ is a group represented by the following formula (7-a) or (8-
3. The sulfur-containing unsaturated carboxylic acid ester compound according to claim 2, wherein R ₁₄ is a (meth) acrylic acid residue. Embedded image R ₇₁ —O— (7-a) (wherein, R ₇₁ represents a monovalent organic group containing at least one or more sulfur atoms) R ₈₁ —S— (8-a) (wherein R ₈₁ represents a monovalent organic group which may contain a sulfur atom) 12. A polymerizable composition containing the sulfur-containing unsaturated carboxylic acid ester compound according to claim 1. Description: 13. A cured product obtained by polymerizing the polymerizable composition according to claim 12. 14. An optical component comprising the cured product according to claim 13. 15. A hydroxy compound represented by the following general formula (2). Embedded image [Wherein, R ₁₁ represents a divalent organic group, and X ₁₁ each independently represent an oxygen atom, a sulfur atom, a —COO— group, or — (CH
₂ ) ₁ X ₁₂ -group (X ₁₂ represents an oxygen atom or a sulfur atom, 1 represents an integer of 1 to 3), R ₁₂ each independently represents a hydrogen atom or an alkyl group, and R ₁₃ represents Independently represents a substituent containing a sulfur atom] 16. The divalent organic group R ₁₁ is represented by the following formula (3-
The hydroxy compound according to claim 15, which is a group represented by a), (4-a), (5-a) or formula (6-a). Embedded image (Wherein, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each a hydrogen atom,
Represents an alkyl group, an alkoxy group, a nitro group or a halogen atom) Wherein Y ₄₁ is a single bond, a —C (R ₄₁ ) ₂ — group (R ₄₁ each independently represents a hydrogen atom or a methyl group), —O—
Group, -S- group or -SO ₂ - represents a group, R ₄₂ and R
₄₃ each independently represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an alkylthio group,
Represents a nitro group or a halogen atom, and m and n each represent an integer of 0 to 4]. (In the formula, R ₅₁ each independently represents a hydrogen atom or an alkyl group.) (Wherein, R ₆₁ and R ₆₂ each represent a hydrogen atom or an alkyl group)