JPH1067736A - Thiol compound, sulfur-containing o-(meth)acrylate compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new sulfur-containing O-(meth)acryalte compound being polymerized in a short time and useful for producing optical resins exhibiting good optical physical properties, especially having high refractive indexes and an excellent impact resistance and little in the generation of smells on their processing treatments. SOLUTION: A sulfur-containing O-(meth)acrylate compound of formula I [R is H, methyl; (1) is 1-3; B is methine, C(=O), NHC(=O); when B is the methine, (n) is 2, and (m) is 1, 2; A is a group of formula II, a group of formula III, etc.], e.g. bis(2-acryloyloxyethyl) dithioacetalbenzene of formula IV. The compound of formula I is obtained by converting a new thiol compound of formula V to a dithioacetal compound, a thioester compound or a thiourethane compound and subsequently removing a hydrogen halide from the compound. The compound of formula I is polymerized singly or copolymerized with a copolymerizable monomer or a polythiol to produce an optical resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel sulfur-containing O-
(Meth) acrylate compounds and novel thiol compounds are subjected to dithioacetalization, thioesterification or thiourethane formation and then dehydrohalogenated sulfur-containing O-
The present invention relates to a method for producing a (meth) acrylate compound, an optical resin composition containing the compound, an optical resin obtained by polymerizing the composition, and an optical resin.

[0002]

2. Description of the Related Art Plastic lenses are lighter and harder to break than inorganic lenses, and can be dyed. Therefore, plastic lenses have recently been rapidly used in optical elements such as spectacle lenses and camera lenses. Currently, resins widely used for these purposes include diethylene glycol bis (allyl carbonate)
(Hereinafter referred to as DAC) by radical polymerization. This resin has various characteristics such as being excellent in impact resistance, being lightweight, being excellent in dyeing properties, being excellent in workability such as cutting property and polishing property, and the like. . However, this resin has a refractive index n _d of 1.50.
Since the center thickness and the edge thickness of the lens are large before and after, the resin for the lens having a higher refractive index has been desired.

As a resin having a higher refractive index than that of a DAC resin, a polythiourethane resin (Japanese Patent Application Laid-Open No. 63-46213) or a sulfur-containing O- (meth)
Acrylate resin (JP-A-1-128966, JP-A-3
217412, JP-A-4-161410 and thio (meth) acrylate resins (JP-A-63-18866).
0, Japanese Patent Publication No. 3-59060, etc.). Polythiourethane resin is a well-balanced resin, such as high refractive index and good impact resistance.However, if it is attempted to polymerize in a short time, the polymerization tends to be non-uniform and optically homogeneous. To obtain a lens, it was necessary to lengthen the polymerization time. Further, when the resin is cut and polished for processing, there is a case where a sulfur odor sometimes occurs during the work.

[0004] Sulfur-containing O- (meth) acrylate resins and thio (meth) acrylate resins can be polymerized in a short time by ultraviolet rays or the like, but generally the obtained resin has sufficient strength and impact resistance. In some cases, the resin was brittle and easily broken. Particularly in recent years, it has been required to have a processing strength suitable for two-point processing widely used for spectacle lenses, and the center thickness of the spectacle lens tends to be small, and a resin having higher strength and impact resistance Was desired. Furthermore, the stability of the thio (meth) acrylate compound is low, causing gelation,
Further, the workability may be complicated, for example, the polymerization may easily run away and the control may be difficult. Therefore, further improvement has been desired to solve these problems.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an optical system which can be polymerized in a short time, has good optical properties, especially has a high refractive index, has excellent impact resistance, and has a low odor during processing. An object of the present invention is to provide an optical resin composition having excellent handling properties.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that certain sulfur-containing O- (meth) acrylate compounds are effective. The invention has been completed. That is, the present invention provides a sulfur-containing O-form represented by the following formula (1) (Formula 11).
It relates to a (meth) acrylate compound.

[0007]

Embedded image [Wherein, R represents a hydrogen atom or a methyl group;
3 represents an integer, B represents a methine group, a —C (＝ O) — group or a —NHC (＝ O) — group, and when B is a methine group, n is 2 and m is 1 or 2 And A represents any group represented by the following formula (Formula 12);

[0008]

Embedded image (In the above formula, m represents 1 or 2, and each ring may be substituted with one or more alkyl, alkylthio, or alkoxy groups having 1 or 2 carbon atoms, and p and q represent 0 or 1. Where, when p is 1, m is 1.) When B is a —C (＝ O) — group, n is 1, m is 2 or 3, and A is a compound represented by the following formula: 13) represents any group represented by

[0009]

Embedded image (Wherein, r and s represent an integer of 1 to 3) When B is a —NHC (＝ O) — group, n is 1, m is 2, and A is the following formula (Formula 14) Any group represented

[0010]

Embedded image (Wherein, r and s represent an integer of 1 to 3). In addition, the present invention provides a method for dithioacetalizing a thiol compound represented by the following formula (2) using a compound having at least one aldehyde group in the molecule,
After thioesterification using a compound having at least two carboxyl groups in the molecule, or
The present invention relates to a process for producing a sulfur-containing O- (meth) acrylate compound of the above formula (1), which comprises subjecting a compound having two isocyanate groups to thiourethanization and then dehydrohalogenation.

[0011]

Embedded image (In the formula, X represents a chlorine atom or a bromine atom, R represents a hydrogen atom or a methyl group, and l represents an integer of 1 to 3.) Further, the present invention provides the above sulfur-containing O- (meth) The present invention relates to a composition for an optical resin containing an acrylate compound, a sulfur-containing resin obtained by polymerizing the composition, and a lens made of the resin. Further, the compound of the formula (2) is also novel and is included in the present invention as an intermediate of the sulfur-containing O- (meth) acrylate compound of the formula (1).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The sulfur-containing O- (meth) acrylate compound represented by the formula (1) of the present invention can be produced using the thiol compound represented by the formula (2). That is, a compound having a functional group capable of reacting with a mercapto group, such as aldehydes, carboxylic acids, and isocyanates, can be obtained by dithioacetalization, thioesterification, or thiourethane formation, and further dehydrohalogenation. .

The thiol compound represented by the formula (2) of the present invention can be obtained by the following method. That is, a solvent is formed from 2-mercaptoethanol, 3-mercaptopropanol, or the like and 3-chloropropionic acid, 3-bromopropionic acid, or 3-chloro-2-methylpropionic acid, 3-bromo-2-methylpropionic acid, or the like. In the presence of a catalyst such as p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, etc., it can be obtained by heating to 10 to 200 ° C. and performing dehydration esterification while removing generated water. In addition, in consideration of the stability of 2-mercaptoethanol, 3-mercaptopropanol and the like as raw materials, it can be obtained by performing dehydration esterification under reduced pressure of 20 to 400 mmHg without heating the reaction system much. .

By utilizing the thiol compound of the present invention, a sulfur atom can be easily introduced into a molecule,
It is possible to further improve the refractive index of the obtained compound. In addition, the thiol compound of the present invention is a compound having a functional group that can be derived to an O- (meth) acrylate compound by reacting with a mercapto group and then dehydrohalogenating to react with the mercapto group. ,
For example, a desired sulfur-containing O- (meth) acrylate compound can be easily and highly purified from aldehydes, carboxylic acids, and isocyanates.

In the sulfur-containing O- (meth) acrylate compound represented by the formula (1) of the present invention, when B is a methine group,
It can be produced from the compound having at least one aldehyde group in the molecule and the thiol compound of the above formula (2) by the following two-stage method. First, a compound having at least one aldehyde group and the above thiol compound are heated to 10 to 200 ° C. in a solvent in the presence of a catalyst such as p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, and the like. While removing the dithioacetal. Then, the base is reacted at −20 ° C. to 60 ° C., and is produced by a method of (meth) acrylation by dehydrohalogenation.
The base used as a halogen-hydrogen scavenger used in the subsequent (meth) acrylation reaction is not particularly limited. Examples of a commonly used base include trialkylamines such as trimethylamine and triethylamine, pyridine, sodium hydroxide, and potassium hydroxide. And the like.

Compounds having at least one aldehyde group in the molecule include readily available aldehyde compounds,
A compound having the following structure (Formula 16) is exemplified.

[0017]

Embedded image (In the above formula, m represents 1 or 2, each ring may be substituted by one or more alkyl or alkoxy groups having 1 or 2 carbon atoms, and p and q represent 0 or 1. , P is 1
At the time, m is 1. )

Specifically, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4
-Ethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 3,4
-Dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde,
2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5
-Dimethoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 2-methylthiobenzaldehyde, 4-methylthiobenzaldehyde, 4-
Methylthiomethylbenzaldehyde, phenylacetaldehyde, 2-thiophenaldehyde, 3-thiophenaldehyde, 3-methyl-2-thiophenaldehyde,
4-methyl-2-thiophenaldehyde, 5-methyl-
2-thiophenaldehyde, 5-ethyl-2-thiophenaldehyde, 5-methylthiothiophen-2-aldehyde, 2,3-thiophendialdehyde, 2,5-thiophendialdehyde, 1-naphthaldehyde, 2-naphthaldehyde, 1 , 2-Naphthalenedialdehyde, 2,
For example, 3-naphthalenedialdehyde can be used. Since the sulfur-containing O- (meth) acrylate compound represented by the formula (1) of the present invention has the same main chain structure, the distance between crosslinking points in the molecule is almost the same, and the heat of the obtained resin is By changing the aldehyde compound serving as the mother skeleton without significantly changing the physical properties, mechanical properties, and the like, it becomes possible to select resins having different optical properties.

Similarly, in the sulfur-containing O- (meth) acrylate compound represented by the formula (1) of the present invention, B is -C
When it is a (＝ O) — group, two steps of thioesterification and dehalogenation from a sulfur-containing carboxylic acid compound having at least two carboxyl groups in the molecule and the thiol compound of the above formula (2). It can be manufactured by the method of. Further, among the sulfur-containing O- (meth) acrylate compounds represented by the formula (1) of the present invention, when B is a —NHC (＝ O) — group, a compound having two isocyanate groups in the molecule And a thiol compound of the above formula (2) by a two-stage method of thiourethane formation and dehydrohalogenation.

When B is a —C (＝ O) — group, the sulfur-containing O
The sulfur-containing carboxylic acid serving as the mother skeleton for obtaining the-(meth) acrylate compound is a sulfur-containing carboxylic acid that can be easily obtained, and is a compound represented by the following structural formula (Formula 17).

[0021]

Embedded image (In the above formula, r and s each represent an integer of 1 to 3.)

Specifically, thiodiglycolic acid, thiodipropionic acid, 4,4-thiodibutanoic acid, dithiodiglycolic acid, dithiodipropionic acid, 4,4-dithiodibutanoic acid, methylene bis (thioglycolic acid), methylene bis (Thiopropionic acid), methylene bis (thiobutanoic acid), ethylene bis (thioglycolic acid), ethylene bis (thiopropionic acid), ethylene bis (thiobutanoic acid), methine tris (thioglycolic acid), methine tris (thiopropionic acid), methine tris (Thiobutanoic acid) and the like can be used. Since these sulfur-containing O- (meth) acrylate compounds contain a large number of ester bonds in the molecule, the hydrophilicity is increased, and when a lens is used, an improvement in dyeability can be expected.

When B is a —NHC (＝ O) — group, an isocyanate compound serving as a mother skeleton for obtaining a sulfur-containing O- (meth) acrylate compound is represented by the following formula (Formula 18). Compound.

[0024]

Embedded image (In the above formula, r and s each represent an integer of 1 to 3.)

Specifically, diisocyanate methyl sulfide, diisocyanate ethyl sulfide, diisocyanate propyl sulfide, diisocyanate methyl disulfide, diisocyanate ethyl disulfide,
Examples thereof include diisocyanatepropyl disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, and bis (isocyanatopropyllthio) methane. These sulfur-containing O- (meta)
The acrylate compound has a thiourethane bond in the molecule, and can be expected to improve the refractive index and further improve the resin strength such as impact resistance.

In these reactions, if necessary,
An organic solvent may be used. The organic solvent used is not particularly limited, but those having no reactivity with the raw materials necessary for the reaction can be used. As the organic solvent, for example, benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride, aliphatic or aromatic hydrocarbons such as ethylene chloride, or halogenated hydrocarbons, diethyl ether, dioxane, Ethers such as tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; and N, N-dimethylformamide. The type of organic solvent used
It is appropriately determined depending on the starting materials used, the type of reaction, and the like.
These thiol compounds, aldehyde compounds, sulfur-containing carboxylic acid compounds and isocyanate compounds can be subjected to purification treatment such as distillation if necessary.

The sulfur-containing O- (meth) acrylate compound of the present invention obtained by these methods has improved stability as a monomer as compared with a thio (meth) acrylate compound, and has relatively low gelation. Less likely to occur and easy to handle.

The composition for an optical resin of the present invention contains the sulfur-containing O- (meth) acrylate compound of the present invention, and further comprises the sulfur-containing O- (meth) acrylate compound of the present invention, and And at least one copolymerizable monomer or polythiol compound. In the case of a composition containing another monomer or polythiol compound, the sulfur-containing O- (meth) acrylate compound of the present invention is obtained by mixing the sulfur-containing O- (meth) acrylate compound with another monomer or polythiol compound. 2 for all
It is at least 0% by weight, preferably at least 40% by weight, more preferably at least 60% by weight.

The monomer or polythiol compound copolymerizable with the sulfur-containing (meth) acrylate compound of the present invention comprises:
It is selected according to the purpose, such as adjustment of optical properties such as refractive index, adjustment of various properties such as impact resistance and specific gravity, and adjustment of viscosity and other handling of monomers, and is not particularly limited. These copolymerizable monomers or polythiol compounds can be used alone or in combination of two or more.

Examples of the copolymerizable monomer include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate,
Hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate , Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylic Over DOO, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2
Bis (4-acryloxyethoxyphenyl) propane,
2,2-bis (4-methacryloxyethoxyphenyl)
Propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate,
1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxyphenyl) methane, 1,1- Bis (4-methacryloxydiethoxyphenyl) methane, 1,1-bis (4-
Acryloxyethoxyphenyl) sulfone, 1,1-bis (4-methacryloxyethoxyphenyl) sulfone,
1,1-bis (4-acryloxydiethoxyphenyl)
Sulfone, 1,1-bis (4-methacryloxydiethoxyphenyl) sulfone, dimethylol tricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate,
(Meth) acrylate compounds such as methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, allyl glycidyl ether,
Diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, allyl compounds such as diethylene glycol bisallyl carbonate,
Styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9
-Vinyl compounds such as divinylspirobi (m-dioxane), diisopropenylbenzene and the like.

Examples of the polythiol compound include 1,2-ethanedithiol, 1,3-propanedithiol,
2,3-propanetrithiol, 2,3-dimercapto-1-propanol, diethylene glycol bis (2-
Mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), trimethylolpropanebis (2-mercaptoacetate), trimethylolpropanebis (3-mercaptopropionate),
Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2- Bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene,
1,4-bis (mercaptomethyl) benzene, 1,2,2
3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene,
1,2,3-tris (mercaptomethyl) benzene,
1,2,4-tris (mercaptomethyl) benzene,
1,3,5-tris (mercaptomethyl) benzene,
4,4'-thiobisbenzenethiol, bis (2-mercaptoethylthio) methane, bis (2-mercaptoethylthio) methane, 1,2-bis (2-mercaptoethylthio) ethane, 1,3-bis (2 -Mercaptoethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, tetrakis (2-mercaptoethylthiomethyl) methane, 1,2-bis (2-mercaptoethylthio) -3-mercapto Propane, 4,8-bis (mercaptomethyl) -3,6,9-trithia-1,1
1-undecanedithiol, 2,5-dimercapto-
1,4-dithiane, 2,5-dimercaptomethyl-1,
4-dithiane, 2,5-dimercaptomethyl-2,5-
Dimethyl-1,4-dithiane and the like. As the copolymerizable monomer, a compound represented by the formula (3) (Formula 19) is preferably used.

[0032]

Embedded image [Wherein, R represents a hydrogen atom or a methyl group, t, u represents an integer of 0 to 4, E _{is, -CH 2 -, - C (} C
H ₃ ) ₂ —, —S—, and —SO ₂ —. ]

The optical resin of the present invention is obtained by polymerizing the optical resin composition of the present invention, and is obtained by polymerizing the sulfur-containing O- (meth) acrylate compound of the present invention alone, or It is obtained by copolymerizing a sulfur-containing O- (meth) acrylate compound with another copolymerizable monomer or a polythiol compound. The polymerization method for obtaining the optical resin of the present invention is not particularly limited,
A known radical polymerization method can be used. In this case, as the polymerization initiation means, use of radical initiators such as various peroxides and azo compounds, or irradiation of ultraviolet rays, visible rays, α rays, β rays, γ rays, electron rays, or the like, Combination is mentioned.

As the radical initiator, known ones can be used. Representative examples thereof include benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-t-butylperoxyazelate, and t-butylperoxide. Oxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, bis ( Peroxides such as 4-t-butylcyclohexyl) peroxydicarbonate and t-butylperoxyisopropylcarbonate; and azo compounds such as azobisisobutyronitrile. These may be used alone or in combination of two or more. Can also be used.

When the polymerization is started by irradiating ultraviolet rays or the like, a known photoinitiator or the like can be used. Representative photoinitiators include benzophenone, 4,4
-Diethylaminobenzophenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-
Phenylacetophenone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2,
2-diethoxyacetophenone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxide, etc. These may be used alone or in combination of two or more, and may be used in combination with the above-mentioned radical initiator.

A typical polymerization method for obtaining the optical resin (for example, a plastic lens) of the present invention includes cast polymerization. That is, the composition (also referred to as a monomer mixture) for an optical resin of the present invention containing a radical initiator and / or a photoinitiator is injected between molds held by a gasket or a tape or the like. At this time, if necessary, any treatment such as defoaming may be performed. Then, the polymer can be irradiated with ultraviolet rays or the like, heated in an oven, or cured by using these together, and the polymer can be taken out.

A polymerization method for obtaining the optical resin of the present invention,
The polymerization conditions and the like cannot be unconditionally limited depending on the type and amount of the initiator and the like used and the type and ratio of the monomer. For example, when irradiating with ultraviolet rays or the like, a treatment such as cooling may be performed to prevent overheating of the monomer mixture, and a wavelength cut filter or the like capable of cutting a specific wavelength or less to irradiate only a wavelength region necessary for polymerization. Can also be used. When heating in an oven, the temperature may be controlled in order to select the optimal temperature condition. When heating in an oven, generally, a method of gradually heating from a low temperature and holding at a high temperature to complete the polymerization is employed. Also, the polymerization time is affected by the type and amount of the initiator and the like used, and the type and ratio of the monomer, and therefore cannot be unconditionally limited. Generally, it is possible to shorten the polymerization time by irradiation with ultraviolet rays or the like.

When molding the resin of the present invention, a chain extender, a crosslinking agent,
Various substances such as a light stabilizer, an ultraviolet absorber, an antioxidant, a coloring inhibitor, a dye, a fragrance, and a filler may be added.
The removed resin molded body may be subjected to a treatment such as annealing, if necessary.

The optical resin obtained by using the sulfur-containing O- (meth) acrylate of the present invention has a high refractive index, low dispersion, excellent heat resistance, excellent weather resistance, and particularly excellent impact resistance. It has excellent characteristics and has a characteristic that odor generated during processing is small. Furthermore, the resin of the present invention can be obtained as molded articles of various forms by changing the mold at the time of casting polymerization, and is used for various uses as optical element materials such as eyeglass lenses and camera lenses, and transparent resins. can do. In particular, it is suitable as an optical element material for eyeglass lenses, camera lenses, and the like. Further, in the lens using the optical resin of the present invention, if necessary, antireflection, high hardness, improved wear resistance, improved chemical resistance, imparted anti-fog properties,
Alternatively, physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, and dyeing treatment can be performed to improve the fashionability.

[0040]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples. In the performance test of the obtained optical resin, the refractive index, Abbe number, specific gravity, impact resistance, odor during polishing, and appearance were evaluated by the following test methods. -Refractive index, Abbe number: 20 ° C using a Pulfrich refractometer
Was measured.・ Appearance: Observed visually. -Shock resistance: Height 127 at the center of the manufactured lens
The impact resistance was evaluated by dropping iron balls of various weights from cm. It represents the weight of the largest iron ball that did not crack the lens. Odor during polishing: The edge of the lens was cut and polished by an edger to determine whether there was an unpleasant sulfur odor as follows. ：: Those with no unpleasant sulfur odor △: Those with little sulfur odor ×: Those with unpleasant sulfur odor

Example 1 A reaction flask equipped with a Dean-Stark tube equipped with a stir bar, a thermometer, and a condenser was charged with 65.1 g (0.60 mol) of 3-chloropropionic acid and 56.3 g (0.03 mol) of 2-mercaptoethanol. .72 mol), 400 ml of toluene,
3.0 g of p-toluenesulfonic acid was charged, and 40-70.
The pressure was adjusted to reflux at 40 ° C. under a reduced pressure of mmHg, and the dehydration esterification reaction was performed for 9 hours. next,
After washing the organic layer with a 5% aqueous sodium bicarbonate solution, it was further washed several times with water. After the organic layer was dried over anhydrous magnesium sulfate, toluene was distilled off under reduced pressure, and 97.7 g of a colorless liquid 3-chloropropionic acid (2-mercaptoethyl ester) represented by the following formula (Formula 20) was obtained. (0.5
8 mol).

[0042]

Embedded image The elemental analysis values of this product are shown below. Composition: C ₅ H ₉ ClO ₂ S CH S Cl Analytical value (%) 35.4 5.3 19.3 21.1 Calculated value (%) 35.6 5.4 19.0 21.0 ¹ An H-NMR (in CDCl ₃ solvent, based on tetramethylsilane) chart is shown in FIG. 1.

Example 2 Benzaldehyde was added to a reaction flask equipped with a Dean-Stark tube equipped with a stir bar, a thermometer, and a condenser.
2 g (0.20 mol) of 3-chloropropionic acid (2-
70.8 g (0.42 mol) of mercaptoethyl ester, 0.3 g of p-toluenesulfonic acid, toluene 30
0 ml, and under reduced pressure of 80 to 110 mmHg, 5
The pressure was adjusted to reflux at 0 ° C., and the dithioacetalization reaction was performed for 2 hours. After cooling, the mixture was washed with water, and then the organic layer was washed with a 5% aqueous sodium bicarbonate solution, and then further washed with water several times. After the organic layer was dried over anhydrous magnesium sulfate, toluene was distilled off under reduced pressure to obtain 82.1 g (0.19 mol) of a colorless liquid. This was dissolved in 200 ml of acetone, charged into a reaction flask equipped with a stirrer, a thermometer, and a dropping funnel. 43.0 g (0.42 mol) of triethylamine was gradually added dropwise while stirring at 10 ° C or lower. did. After the completion of dropping, at 25 ° C,
Stirred for 10 hours. Then, 200 ml of toluene and water 2
After addition of 00 ml, the reaction product was extracted into an organic layer and separated, and the organic layer was washed with dilute hydrochloric acid, dilute aqueous sodium bicarbonate, and water. After drying over anhydrous magnesium sulfate, the toluene was distilled off under reduced pressure to obtain the desired colorless and transparent compound of the following formula (Chemical Formula 2).
The sulfur-containing O-acrylate compound represented by 1), bis (2
-Acryloyloxyethyl) dithioacetal benzene (66.9 g, 0.190 mol) was obtained.

[0044]

Embedded image The elemental analysis values of this product are shown below. A chart of ¹ H-NMR (based on tetramethylsilane in CDCl ₃ solvent) is shown in FIG. 2.

Example 3 21.2 g (0.20 mol) of the benzaldehyde of Example 2 was replaced with 30.4 g of 4-methylthiobenzaldehyde.
(0.20 mol), a dithioacetalization reaction and an acrylation reaction were carried out in the same manner as in Example 2.
Thus, 76.4 g (0.192 mol) of a colorless and transparent sulfur-containing O-acrylate compound represented by the following structural formula (Formula 22), 4-methylthiobenzaldehyde bis (2-acryloyloxyethyl) dithioacetal, was obtained.

[0046]

Embedded image The elemental analysis values of this product are shown below. A chart of ¹ H-NMR (based on tetramethylsilane in a CDCl ₃ solvent) is shown in FIG. 3.

Example 4 A dithioacetal was prepared in the same manner as in Example 2 except that 21.2 g (0.20 mol) of benzaldehyde in Example 2 was changed to 31.2 g (0.20 mol) of 1-naphthaldehyde. A colorless and transparent sulfur-containing O-acrylate compound represented by the following structural formula (Formula 23), 78.3 g of 1-naphthaldehydebis (2-acryloyloxyethyl) dithioacetal (0.195) Mol).

[0048]

Embedded image The elemental analysis values of this product are shown below. A chart of ¹ H-NMR (based on tetramethylsilane in CDCl ₃ solvent) is shown in FIG. 4.

Example 5 21.2 g (0.20 mol) of the benzaldehyde of Example 2 was replaced with 22.4 g (0.20 mol) of 2-thiophenaldehyde.
Mol), a dithioacetalization reaction and an acrylation reaction were carried out in the same manner as in Example 2 to obtain a colorless and transparent sulfur-containing O-acrylate compound represented by the following structural formula (Formula 24). 54.1 g (0.151 mol) of bis (2-acryloyloxyethyl) dithioacetalthiophene were obtained.

[0050]

Embedded image The elemental analysis values of this product are shown below. A chart of ¹ H-NMR (based on tetramethylsilane in CDCl ₃ solvent) is shown in FIG. 5.

Example 6 21.2 g (0.20 mol) of the benzaldehyde of Example 2 was replaced with 24.0 g (0.20 mol) of phenylacetaldehyde.
Mol), a dithioacetalization reaction and an acrylation reaction were carried out in the same manner as in Example 2 to carry out a colorless and transparent sulfur-containing O-acrylate compound represented by the following structural formula (Formula 25), phenylmethylenebis 65.2 g (0.178 mol) of (2-acryloyloxyethyl) dithioacetal were obtained.

[0052]

Embedded image The elemental analysis values of this product are shown below. A chart of ¹ H-NMR (based on tetramethylsilane in a CDCl ₃ solvent) is shown in FIG. 6.

Example 7 A reaction flask equipped with a stirring rod, a thermometer, and a dropping funnel was placed in a reaction flask.
39.3 g of methylenebis (thioglycolic acid) (0.2
0 mol), 81.0 g (0.48 mol) of 3-chloropropionic acid (2-mercaptoethyl ester), 0.1 g of dimethylaminopyridine and 400 ml of chloroform, and 100 ml of chloroform with stirring in a water bath.
90.8 g of dicyclohexylcarbodiimide dissolved in water
(0.44 mol) was slowly added dropwise. After dropping,
The mixture was further stirred at 25 ° C. for 15 hours. After crushing the excess dicyclohexylcarbodiimide with acetic acid, the formed urea was removed by suction filtration. After chloroform was distilled off under reduced pressure, the residue was dissolved in 300 ml of toluene. The organic layer was washed with a 5% aqueous sodium bicarbonate solution, further washed with water, the organic layer was dried over anhydrous magnesium sulfate, and toluene was distilled off under reduced pressure to obtain 88.6 g of a colorless liquid.
(0.18 mol). This was dissolved in 300 ml of acetone, and charged into a reaction flask equipped with a stirring rod, a thermometer, and a dropping funnel.
37.8 g (0.37 mol) of triethylamine was gradually added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 10 hours. Thereafter, 400 ml of toluene and 300 ml of water were added, and the reaction product was extracted into an organic layer and separated, and then the organic layer was washed with dilute hydrochloric acid, dilute aqueous sodium bicarbonate, and water. After drying over anhydrous magnesium sulfate, the toluene is distilled off under reduced pressure, and the desired colorless and transparent sulfur-containing O-acrylate compound represented by the following structural formula (Chemical Formula 26), methylene bis (acryloyloxyethyl thioester thioglycolate) is obtained.
59.2 g (0.14 mol) were obtained.

[0054]

Embedded image The elemental analysis values of this product are shown below. A chart of ¹ H-NMR (based on tetramethylsilane in CDCl ₃ solvent) is shown in FIG. 7.

Example 8 The methylenebis (thioglycolic acid) of Example 7 39.3
g (0.20 mol) in 30.0 g of thiodiglycolic acid
(0.20 mol), a dehydration esterification reaction and an acrylation reaction were carried out in the same manner as in Example 1 to obtain a colorless and transparent sulfur-containing O-acrylate compound, bis (acryloyloxyethyl thiodiglycolate). 52.7 g (0.14 mol) of thioester) was obtained.

[0056]

Embedded image The elemental analysis values of this product are shown below. A chart of ¹ H-NMR (based on tetramethylsilane in CDCl ₃ solvent) is shown in FIG. 8.

Example 9 Methylene bis (thioglycolic acid) of Example 6 39.3
g (0.20 mol) was changed to 57.3 g (0.20 mol) of methine tris (thioglycolic acid), and the other raw material used was 3-chloropropionic acid (2-mercaptoethyl ester) of 0.72 g. Mol, dicyclohexylcarbodiimide was changed to 0.66 mol, and triethylamine was changed to 0.59 mol in the same manner as in Example 1.
The dehydration esterification reaction and the acrylation reaction were performed to obtain 100.6 g (0.16 mol) of a colorless and transparent sulfur-containing O-acrylate compound, methine tris [thioglycolic acid (acryloyloxyethyl thioester)] (formula 28).

[0058]

Embedded image The elemental analysis values of this product are shown below. A chart of ¹ H-NMR (based on tetramethylsilane in a CDCl ₃ solvent) is shown in FIG. 9.

Example 10 A reaction flask equipped with a stirring rod, a thermometer, and a dropping funnel was placed in a reaction flask.
Bis (isocyanatomethylthio) methane 19.0g
(0.10 mol), dimethyltin dichloride 15m
g, 100 ml of toluene and 33.7 g (0.20 mol) of 3-chloropropionic acid (2-mercaptoethyl ester) were slowly added dropwise while stirring in a water bath. After the completion of the dropwise addition, the mixture was stirred for 2 hours, and then further
Stirred at C for 2 hours. After cooling, the formed crystal was filtered, washed, and dried. White crystal 4
2.5 g (0.08 mol) were obtained. This is acetone 20
The solution was dissolved in 0 ml, charged into a reaction flask equipped with a stirrer, a thermometer, and a dropping funnel, and cooled to 10 ° C. or lower while stirring, and 17.1 g (0.17 mol) of triethylamine was stirred.
Was gradually added dropwise. After completion of the dropwise addition, the mixture was further heated
Stirred for hours. Then, 200 ml of toluene and 200 ml of water
The reaction product was extracted into an organic layer and separated, and the organic layer was washed with dilute hydrochloric acid, dilute aqueous sodium bicarbonate, and water. After drying over anhydrous magnesium sulfate, toluene was distilled off under reduced pressure to obtain 29.7 g (0.065 mol) of the objective sulfur-containing O-acrylate compound (formula 29) as white crystals.

[0060]

Embedded image The elemental analysis values of this product are shown below. _{Composition: C 15 H 22 N 2 O} 6 S 4 C H N S Analysis value (%) 39.8 5.1 6.0 28.5 Calculated (%) 39.6 4.9 6.2 28.2 A chart of ¹ H-NMR (based on tetramethylsilane in a CDCl ₃ solvent) is shown in FIG. 10.

Examples 11 to 19 To 50 g of the compound obtained in Examples 2 to 10, 50 to 100 mg of 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photoinitiator was added. Mix well. After these were sufficiently degassed, they were poured into a mold composed of a glass mold and a gasket. UV light 1
After irradiation for 0 to 60 seconds, polymerization was carried out by heating at 120 ° C. for 1 hour. After the completion of the polymerization, the mixture was gradually cooled, and the molded product was taken out of the mold. Table 1 (Table 1) shows the physical properties of the obtained molded body (lens).

[0062]

[Table 1]

Example 20 To 35 g of the benzaldehyde bis (2-acryloyloxyethyl) dithioacetal obtained in Example 2, 15 g of bis (4-acryloxydiethoxyphenyl) methane and 2-hydroxy- as a photoinitiator were used. 2-methyl-
50 mg of 1-phenylpropan-1-one was added and mixed well. After this was sufficiently degassed, it was poured into a mold composed of a glass mold and a tape. UV rays 10
After irradiation for 2 seconds, the mixture was heated at 120 ° C. for 1 hour to perform polymerization. After the completion of the polymerization, the mixture was gradually cooled and the molded product was taken out of the mold. The evaluation results of the obtained molded body (lens) are shown in Table 2 (Table 2).

Examples 21 to 26 A plastic lens was obtained in the same manner as in Example 20, except that the monomer compositions shown in Table 2 were used. The evaluation results of these plastic lenses are shown in Example 2.
The results are shown in Table 2 together with the evaluation results of 0. From Table 2, the plastic lenses of Examples 20 to 26 are colorless and transparent, have a well-balanced refractive index, Abbe number, and specific gravity, have excellent impact resistance, and are unpleasant when polishing a resin. Had no significant sulfur odor.

Comparative Examples 1 to 3 A plastic lens was obtained in the same manner as in Example 20, except that the monomer compositions shown in Table 2 were used. Table 2 shows the evaluation results of these plastic lenses together with the evaluation results of the examples. From Table 2, the plastic lens of the comparative example was inferior in impact resistance as compared with Examples 20 to 26, and had a sulfur smell when polishing the resin.

[0066]

[Table 2] BSFA; bis (4-acryloxydiethoxyphenyl) methane TEGDMA; tetraethylene glycol dimethacrylate DTAET; 2,5-bis (acryloxyethylthiomethyl) -1,4-dithiane AETE; bis (acryloxyethylthio) ethane XDMET; p-bis (β-methacryloxyethylthio) xylylene BSAM; 2,2-bis (4-methacryloxydiethoxyphenyl) propane DCPA; dimethylol tricyclodecane diacrylate

[0067]

Industrial Applicability The sulfur-containing O- (meth) acrylate compound of the present invention is a novel compound and has improved monomer stability and excellent workability. In addition, the optical resin composition of the present invention can be polymerized in a short time, has good optical properties, particularly has a high refractive index, has excellent impact resistance, and has a low odor during processing. give.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of a sulfur-containing O-acrylate compound obtained in Example 1.

FIG. 2 is a ¹ H-NMR chart of the sulfur-containing O-acrylate compound obtained in Example 2.

FIG. 3 is a ¹ H-NMR chart of the sulfur-containing O-acrylate compound obtained in Example 3.

FIG. 4 is a ¹ H-NMR chart of the sulfur-containing O-acrylate compound obtained in Example 4.

FIG. 5 is a ¹ H-NMR chart of the sulfur-containing O-acrylate compound obtained in Example 5.

FIG. 6 is a ¹ H-NMR chart of the sulfur-containing O-acrylate compound obtained in Example 6.

FIG. 7 is a ¹ H-NMR chart of the sulfur-containing O-acrylate compound obtained in Example 7.

FIG. 8 is a ¹ H-NMR chart of the sulfur-containing O-acrylate compound obtained in Example 8.

FIG. 9 is a ¹ H-NMR chart of the sulfur-containing O-acrylate compound obtained in Example 9.

FIG. 10 is a ¹ H-NMR chart of the sulfur-containing O-acrylate compound obtained in Example 10.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08F 20/38 C08F 20/38 290/04 290/04 G02B 1/04 G02B 1/04 (72) Inventor Masao Imai 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside of Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Kenichi Fujii 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Toatsu Chemicals Co., Ltd.

Claims (11)

[Claims] 1. A sulfur-containing O represented by the following formula (1):
-(Meth) acrylate compounds. Embedded image [Wherein, R represents a hydrogen atom or a methyl group;
3 represents an integer, B represents a methine group, a —C (＝ O) — group or a —NHC (＝ O) — group, and when B is a methine group, n is 2 and m is 1 or 2 And A represents any group represented by the following formula (Formula 2); (In the above formula, m represents 1 or 2, and each ring may be substituted with one or more alkyl, alkylthio, or alkoxy groups having 1 or 2 carbon atoms, and p and q represent 0 or 1. However, when p is 1, m is 1.) When B is a —C (＝ O) — group, n is 1 and m is 2
Or 3, and A represents any group represented by the following formula (Formula 3); (Wherein, r and s represent an integer of 1 to 3) When B is a —NHC (＝ O) — group, n is 1;
Is 2, and A is any group represented by the following formula (Formula 4). (Wherein, r and s represent an integer of 1 to 3). ] 2. The method according to claim 1, wherein the thiol compound represented by the following formula (2) is converted to dithioacetal, thioester or thiourethane, and then dehydrohalogenated. A method for producing a sulfur-containing O- (meth) acrylate compound according to the above. Embedded image (In the formula, X represents a chlorine atom or a bromine atom, R represents a hydrogen atom or a methyl group, and l represents an integer of 1 to 3.) 3. A diacetalization using a compound having at least one aldehyde group in a molecule represented by any one of the following formulas (Formula 6).
The method for producing the sulfur-containing O- (meth) acrylate compound according to the above. Embedded image (In the above formula, m represents 1 or 2, each ring may be substituted by one or more alkyl or alkoxy groups having 1 or 2 carbon atoms, and p and q represent 0 or 1. , P is 1
At the time, m is 1. ) 4. The sulfur-containing O- according to claim 2, wherein the thioesterification is carried out using a compound having at least two carboxyl groups in a molecule represented by any of the following formulas (Formula 7). A method for producing a (meth) acrylate compound. Embedded image (In the above formula, r and s each represent an integer of 1 to 3.) 5. The sulfur-containing O according to claim 2, wherein the thiourethane is formed by using a compound having two isocyanate groups in a molecule represented by any of the following formulas (Formula 8). -A method for producing a (meth) acrylate compound. Embedded image (In the above formula, r and s each represent an integer of 1 to 3.) 6. A composition for an optical resin, comprising the sulfur-containing O- (meth) acrylate compound according to claim 1. 7. The composition for an optical resin according to claim 6, comprising at least one of a monomer and a polythiol compound copolymerizable with the sulfur-containing O- (meth) acrylate compound. 8. The composition for an optical resin according to claim 7, wherein the copolymerizable monomer contains a compound represented by the following formula (3). Embedded image (Wherein, R represents a hydrogen atom or a methyl group, t and u each represent an integer of 0 to 4, and E represents —CH ₂ —, —C (CH ₃ )).
₂ -, - S- or -SO ₂ - represents a. ) 9. An optical resin obtained by polymerizing the composition according to claim 6. Description: 10. A lens comprising the optical resin according to claim 9. 11. A thiol compound represented by the following formula (2): Embedded image (In the formula, X represents a chlorine atom or a bromine atom, R represents a hydrogen atom or a methyl group, and l represents an integer of 1 to 3.)