JP2014019862A - (meth)acrylate compound, and polymerizable composition and resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a balanced optical resin with an improved physical property balance of the refractive index, the heat resistance, the impact resistance, etc.SOLUTION: The resin comprises one or more (meth)acrylate compounds selected from (meth)acrylate compounds having two or more (meth)acrylate groups in each molecule and represented by the general formula (1) etc. [In the general formula, Rrepresents an organic residue other than an aromatic ring, or a single bond, Rrepresents a hydrogen atom or a methyl group, and n represents an integer larger than or equal to 1].

Description

  The present invention relates to a (meth) acrylate compound, a polymerizable composition using the same, and a resin.

In recent years, plastic lenses are rapidly spreading as optical elements such as spectacle lenses and camera lenses because they are lighter and less crackable than inorganic lenses and can be dyed.
Also, in recent years, there has been an increasing demand for lenses that are thinner and therefore lighter while guaranteeing the same optical properties as lenses made from known organic polymers.

  Currently, as a resin widely used as an optical element such as a plastic lens, a resin obtained by radical polymerization of diethylene glycol bis allyl carbonate (hereinafter sometimes abbreviated as DAC) is known. Yes. This resin has various features such as excellent impact resistance, light weight, excellent dyeability, and good workability such as machinability and abrasiveness. .

However, this resin has a refractive index: n _D = 1.50, which is smaller than that of an inorganic lens (refractive index: n _D = 1.52). It is necessary to increase the center thickness, edge thickness, and curvature of the material, and it is inevitable that the thickness will be increased overall. Therefore, a lens resin having a higher refractive index is desired.

  A polyurethane-based lens is known as a lens having a higher refractive index than a lens made of DAC resin. As this polyurethane lens, for example, Patent Document 1 proposes a polyurethane lens made of a polymer of xylylene diisocyanate and a polythiol compound, and is widely used as an optical lens such as a spectacle lens. In Patent Document 2 and Patent Document 3, a polyurethane lens having a high refractive index, light weight and excellent impact resistance is proposed by a combination of a specific polythiol compound and an isocyanate compound.

JP-A-63-46213 Japanese Patent Laid-Open No. 2-270859 JP 2001-342252 A JP-A-9-132563

  However, the lenses produced from the resins described in Patent Documents 1 to 3 described above have room for improvement in terms of scratch resistance and ease of scratching the lens surface. In addition, in order to obtain an optically homogeneous lens, the polymerization time becomes long and the workability may become complicated. For this reason, further improvements are desired in these respects.

  The present invention provides a (meth) acrylate compound that can be produced in a short polymerization time and provides a resin having good optical properties, particularly a high refractive index and excellent scratch resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have developed a novel (meth) acrylate compound, a polymerizable composition containing the compound, and obtained by polymerizing the polymerizable composition. The present invention has succeeded in solving the above-mentioned problems all at once, and has completed the present invention.

〔上記一般式（１）中、Ｒ₁は芳香環を除く有機残基、または単結合を示す。Ｒ₂は水素原子またはメチル基を示し、ｎは１以上の整数を示す。〕または、一般式（２）

〔上記一般式（２）中、Ｚは−ＣＨ₂−基または−ＣＨ₂−Ｓ−ＣＨ₂−基を示し、Ｒ₂は水素原子またはメチル基を示す。〕で表され、分子内に２個以上の（メタ）アクリレート基を有する化合物から選ばれる１種以上の（メタ）アクリレート化合物、
［２］ 前記一般式（１）中のＲ₁が、脂肪族、脂環族、複素環、鎖中に硫黄原子を有する脂肪族、鎖中に硫黄原子を有する脂環族および鎖中に硫黄原子を有する複素環から選ばれる有機残基であるか、または単結合である、［１］に記載の（メタ）アクリレート化合物、
［３］ 前記一般式（１）中のＲ₁が、直鎖状もしくは分岐状の脂肪族、直鎖状もしくは分岐状の脂環族、鎖中に硫黄原子を有する直鎖状もしくは分岐状の脂肪族、および鎖中に硫黄原子を有する直鎖状もしくは分岐状の脂環族から選ばれる有機残基であるか、または単結合である、［１］または［２］に記載の（メタ）アクリレート化合物、
［４］ 前記一般式（１）中のｎが１〜４の整数である、［１］乃至［３］いずれか一項に記載の（メタ）アクリレート化合物、
［５］ 一般式（１）

〔上記一般式（１）中、Ｒ₁は芳香環を除く有機残基、または単結合を示す。Ｒ₂は水素原子またはメチル基を示し、ｎは１以上の整数を示す。〕および／または、下記一般式（２）

〔上記一般式（２）中、Ｚは−ＣＨ₂−基または−ＣＨ₂−Ｓ−ＣＨ₂−基を示し、Ｒ₂は水素原子またはメチル基を示す。〕で表され、分子内に２個以上の（メタ）アクリレート基を有する化合物から選ばれる１種以上の化合物を含んでなる重合性組成物、
［６］ 前記一般式（１）および／または前記一般式（２）で表される（メタ）アクリレート化合物と、これと共重合可能な単量体あるいはポリチオール化合物の少なくとも１種とを含有する、［５］に記載の重合性組成物、
［７］ ［５］または［６］に記載の重合性組成物を重合してなる樹脂、
［８］ ［７］に記載の樹脂よりなる光学素子、ならびに
［９］ ［８］に記載の光学素子よりなるレンズを提供するものである。 That is, the present invention
[1] The following general formula (1)

[In the general formula (1), R ₁ represents an organic residue other than an aromatic ring or a single bond. R ₂ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more. Or general formula (2)

[In the above general formula (2), Z represents a —CH ₂ — group or —CH ₂ —S—CH ₂ — group, and R ₂ represents a hydrogen atom or a methyl group. One or more (meth) acrylate compounds selected from compounds having two or more (meth) acrylate groups in the molecule,
[2] R ₁ in the general formula (1) is aliphatic, alicyclic, heterocyclic, aliphatic having a sulfur atom in the chain, alicyclic having a sulfur atom in the chain, and sulfur in the chain. (Meth) acrylate compound according to [1], which is an organic residue selected from a heterocyclic ring having an atom or a single bond;
[3] R ₁ in the general formula (1) is linear or branched aliphatic, linear or branched alicyclic, linear or branched having a sulfur atom in the chain. (Meth) according to [1] or [2], which is an organic residue selected from an aliphatic group and a linear or branched alicyclic group having a sulfur atom in the chain, or a single bond. Acrylate compounds,
[4] The (meth) acrylate compound according to any one of [1] to [3], wherein n in the general formula (1) is an integer of 1 to 4.
[5] General formula (1)

[In the general formula (1), R ₁ represents an organic residue other than an aromatic ring or a single bond. R ₂ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more. And / or the following general formula (2)

[In the above general formula (2), Z represents a —CH ₂ — group or —CH ₂ —S—CH ₂ — group, and R ₂ represents a hydrogen atom or a methyl group. A polymerizable composition comprising one or more compounds selected from compounds having two or more (meth) acrylate groups in the molecule,
[6] containing a (meth) acrylate compound represented by the general formula (1) and / or the general formula (2) and at least one monomer or polythiol compound copolymerizable therewith, The polymerizable composition as described in [5],
[7] A resin obtained by polymerizing the polymerizable composition according to [5] or [6],
[8] An optical element made of the resin according to [7] and a lens made of the optical element according to [9] [8] are provided.

  According to the present invention, it is possible to provide a (meth) acrylate compound capable of producing a resin in a short polymerization time and giving a resin having good optical characteristics, particularly a high refractive index and excellent scratch resistance. Become.

1 is a diagram showing ¹ H-NMR measurement results of a (meth) acrylate compound obtained in Example 1. FIG. 2 is a diagram showing the FT-IR measurement result of the (meth) acrylate compound obtained in Example 1. FIG.

Hereinafter, the present invention will be described in more detail.
The (meth) acrylate compound according to the present invention is a compound represented by the following general formula (1) or the following general formula (2).

[In the general formula (1), R ₁ represents an organic residue other than an aromatic ring or a single bond. R ₂ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more. ]

[In the above general formula (2), Z represents a —CH ₂ — group or —CH ₂ —S—CH ₂ — group, and R ₂ represents a hydrogen atom or a methyl group. ]

In general formula (1), R ₁ represents an organic residue other than an aromatic ring, or a single bond. Specifically, R ₁ is a 1 to 6 valent organic group or a single bond, and more specifically, a 1 to 4 valent organic group or a single bond.

R ₁ is preferably selected from an aliphatic group, an alicyclic group, a heterocyclic ring, an aliphatic group having a sulfur atom in the chain, an alicyclic group having a sulfur atom in the chain, and a heterocyclic ring having a sulfur atom in the chain. An organic residue or a single bond, more preferably an organic residue selected from aliphatic, alicyclic, aliphatic having a sulfur atom in the chain, and alicyclic having a sulfur atom in the chain. Or a single bond, more preferably a linear or branched aliphatic, linear or branched alicyclic, linear or branched having a sulfur atom in the chain It is an organic residue selected from an aliphatic group and a linear or branched alicyclic group having a sulfur atom in the chain, or a single bond.

The number of carbon atoms of R ₁ is preferably 0 (single bond) to 15 from the viewpoint of various physical properties such as refractive index, impact resistance, and heat resistance of a resin obtained by polymerizing the polymerizable composition. Yes, more preferably 0 (single bond) to 12, and still more preferably 2 to 12.
The number of sulfur atoms in R ₁ is preferably 0 to 6, more preferably from the viewpoint of various physical properties such as refractive index, impact resistance, and heat resistance of a resin obtained by polymerizing the polymerizable composition. 0-4, and more preferably 0-3.

Specific examples of R ₁ are not particularly limited, and examples thereof include the following groups.

[Wherein, “− ^* ” represents a bond that is bonded to the thio group of the (meth) acryloylthiomethylthio group of the general formula (1). ]

R ₁ may or may not have a (meth) acrylate group, but the (meth) acrylate compound represented by the general formula (1) has two or more (meth) acrylate groups in the molecule. Therefore, when n in the general formula (1) is ₁ , R _{1 in the} general formula (1) has at least one (meth) acrylate group.

In the general formula (1), R ₂ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
In the general formula (1), n represents an integer of 1 or more, and from the viewpoint of various physical properties such as refractive index, impact resistance, and heat resistance of a resin obtained by polymerizing the polymerizable composition, The integer of 1-6 is represented, More preferably, the integer of 1-5 is represented, More preferably, the integer of 1-4 is represented, More preferably, the integer of 2-4 is represented.

  The (meth) acrylate compound represented by the general formula (1) includes a compound having a disulfide bond, a compound having a dithioacetal skeleton, and a compound having a sulfur-containing alicyclic skeleton. From the viewpoint of balance of other physical properties, a compound having a dithioacetal skeleton and a compound having a sulfur-containing alicyclic skeleton are preferable, and a compound having a dithioacetal skeleton is more preferable.

Next, general formula (2) will be described.
In the (meth) acrylate compound represented by the general formula (2) of the present invention, Z represents a —CH ₂ — group or —CH ₂ —S—CH ₂ — group, and R ₂ represents a hydrogen atom or a methyl group. . R ₂ preferably represents a hydrogen atom.

Although it does not specifically limit as a specific example of the (meth) acrylate compound represented by General formula (1) and General formula (2), The compound shown below can be mentioned.
In the following formulae, R ₂ represents a hydrogen atom or a methyl group.

Next, the method for producing the compound in the present invention will be described with specific examples.
First, the (meth) acrylate compound represented by the general formula (1) can be produced using, for example, a polythiol compound represented by the following general formula (A) as a starting material.

[In the general formula (A), R ₁ represents the same meaning as R ₁ in the general formula (1). ]

The compound represented by the general formula (A) is characterized by having a mercaptomethylthio group, and when n is 1, R ₁ is an organic compound excluding an aromatic ring having at least one mercapto group. R ₁ represents a residue, and when n is 2 or more, R ₁ may or may not contain a mercapto group. That is, the compound represented by the general formula (A) has at least two mercapto groups in the molecule.

Moreover, in general formula (A), n represents the above integer, and from the viewpoint of various physical properties such as refractive index, impact resistance, and heat resistance of a resin obtained by polymerizing the polymerizable composition, preferably 1 to The integer of 6 is represented, More preferably, the integer of 1-5 is represented, More preferably, the integer of 2-4 is represented.
Wherein, R ₁ is the same as R ₁ in the general formula (1), more specifically, a linear or branched aliphatic organic residue, a linear or branched cycloaliphatic organic It represents a residue, a linear or branched heterocyclic organic residue, or a single bond.
The linear or branched aliphatic organic residue may have a sulfide bond or a polysulfide bond due to a sulfur atom in the chain.
The alicyclic organic residue is a group in which a mercaptomethylthio group is bonded to a carbon atom constituting the ring, and may have a sulfide bond or a polysulfide bond due to a sulfur atom outside the ring.
The heterocyclic organic residue is one in which a mercaptomethylthio group is bonded to a substitutable atom constituting the ring, and may have a sulfide bond or a polysulfide bond due to a sulfur atom outside or in the ring.

  The polythiol compound represented by the general formula (A) can be obtained, for example, by the method described in JP-A No. 2001-342252 (Patent Document 3), that is, acetal compound is allowed to act on an acetal compound in the presence of an acid catalyst. Thereafter, it can be easily produced by deacetylation of the product by alcoholysis.

  Moreover, the (meth) acrylate compound represented by General formula (2) which concerns on this invention can be manufactured by using the polythiol compound represented, for example by the following general formula (B) as a starting material.

[In the general formula (B), Z represents the same meaning as Z in the general formula (2). ]

  In the present invention, the (meth) acrylate compound represented by the general formula (1) and / or the general formula (2) is produced from, for example, a compound represented by the general formula (A) and / or the general formula (B). An example of its manufacture is given below.

That is, 1 to 1.5 times mol of (meth) acrylic acid halide with respect to the number of moles of thiol group (mercapto group) of the polythiol compound represented by formula (A) and / or formula (B) [for example, (Meth) acrylic acid chloride] can be produced by a method of reacting at -20 ° C to 60 ° C. Alternatively, 1 to 1.5 times moles of β-halogenopropionyl halide (for example, β) relative to the number of moles of the thiol group (mercapto group) of the polythiol compound represented by formula (A) and / or formula (B) -Chloropropionyl chloride) or β-halogeno-α-methylpropionyl halide (eg β-chloro-α-methylpropionyl chloride) is reacted at −20 ° C. to 80 ° C., and then general formula (A) and / or general It can manufacture by making 1-2 times mole base react with -20 degreeC-60 degreeC with respect to the number-of-moles of the thiol group (mercapto group) of the polythiol compound shown by Formula (B).
In the above reaction, a base can be allowed to coexist as a hydrogen halide scavenger in the reaction system in order to remove hydrogen halide (for example, hydrogen chloride) generated during the reaction. The base as the hydrogen halide scavenger is not particularly limited. For example, trialkylamines such as trimethylamine and triethylamine, organic bases such as pyridine, or sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, hydroxide Examples thereof include inorganic bases such as sodium and potassium hydroxide.

  The base to be acted on after reacting β-halogenopropionyl halide or β-halogeno-α-methylpropionyl halide is preferably a trialkylamine such as trimethylamine or triethylamine.

  Further, in order to obtain a high-purity (meth) acrylate compound with high yield, in the reaction with β-chloropropionyl halide or β-chloro-α-methylpropionyl halide, without coexisting a hydrogen halide scavenger, It is also possible to react directly while removing the generated hydrogen halide out of the system.

Moreover, you may use an organic solvent as needed in each reaction which manufactures the compound represented by general formula (A) and / or general formula (B). Although the organic solvent to be used is not specifically limited, the organic solvent which does not have the reactivity with the raw material required for reaction can be used. Examples of the organic solvent include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, petroleum ether;
Halogenated hydrocarbon solvents such as chloroform, dichloromethane, 1,2-dichloroethane;
Ether solvents such as diethyl ether, dioxane, tetrahydrofuran;
Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone;
Examples include amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide.

  Specific examples of the polythiol compound represented by the general formula (A) include 1,2,5-trimercapto-4-thiapentane, 3,3-dimercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-dimercaptomethyl-1,9-dimercapto-2, 5,8-trithianonane, 3,7-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 4,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethyl-1,6-dimercapto-2,5-dithiahexane, 3-mercaptomethylthio-1,5-dimercapto 2-thiapentane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,4,8,11-tetramercapto-2,6,10 -Trithiaundecane, 1,4,9,12-tetramercapto-2,6,7,11-tetrathiadecane, 2,3-dithia-1,4-butanedithiol, 2,3,5,6-tetrathia -1,7-heptanedithiol, 2,3,5,6,8,9-hexathia-1,10-decanedithiol, 4,5-bis (mercaptomethylthio) -1,3-dithiolane, 4,6-bis (Mercaptomethylthio) -1,3-dithiane, 2-bis (mercaptomethylthio) methyl-1,3-dithietane, 2- [2,2-bis (mercaptomethylthio) ethyl Polythiol compounds such as 1,3-dithietane and the like, but not limited to these exemplified compounds.

  The (meth) acrylate compound in this invention is obtained by the above. The obtained compound can be polymerized in a short time and is suitably used as a raw material for optical materials.

  The polymerizable composition in the present invention contains a (meth) acrylate compound represented by the general formula (1) and / or the general formula (2).

Moreover, the polymerizable composition in the present invention includes at least one of a (meth) acrylate compound represented by the general formula (1) and / or the general formula (2), and a monomer or polythiol compound copolymerizable therewith. 1 type may be contained.
In the case of a polymerizable composition containing another monomer or polythiol compound, the (meth) acrylate compound represented by the general formula (1) and / or the general formula (2) From the viewpoint of various physical properties such as refractive index, impact resistance and heat resistance of the resin obtained by polymerizing the polymerizable composition when the total amount of the monomer or polythiol compound is 100% by weight, for example, a total of 20% by weight. % Or more, preferably 40% by weight or more, more preferably 60% by weight or more.

The monomer or polythiol compound copolymerizable with the (meth) acrylate compound of the present invention is used for adjusting optical properties such as refractive index, adjusting various physical properties such as impact resistance and specific gravity, and the viscosity of the monomer. In order to adjust other handling, it is selected according to the purpose, and is not particularly limited.
These copolymerizable monomers or polythiol compounds can be used alone or in admixture of two or more.

Examples of the copolymerizable monomer include benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxymethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and glycidyl (meth) ) Acrylate, thioglycidyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol bisglycidyl (meth) Acrylate, bisphenol-A-di (meth) acrylate, 2,2-bis [4- (meth) acryloxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloxyethoxyethoxyphenyl] propane, bisphenol -F-di (meth) acrylate, 1,1-bis [4- (meth) acryloxyethoxyphenyl] methane, 1,1-bis [4- (meth) acryloxyethoxyethoxyphenyl] methane, trimethylolpropane tri (Meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, methylthio (meth) acrylate, phenylthio (meth) acrylate, benzylthio (meth) acrylate, xylylene Chioruji (meth) acrylate, 1,2-ethanedithiol di (meth) (meth) acrylate compounds such as acrylate;
(Meth) acryloylthioethane, (meth) acryloylthiomethylbenzene, 1,2-bis [(meth) acryloylthio] ethane, 1,3-bis [(meth) acryloylthio] propane, 1,4-bis [( Meth) acryloylthio] butane, 1,6-bis [(meth) acryloylthio] hexane, bis [2- (meth) acryloylthioethyl] ether, bis [2- (meth) acryloylthioethyl] sulfide, bis [2 -(Meth) acryloylthioethylthio] methane, 1,2-bis [2- (meth) acryloylthioethylthio] -3- (meth) acryloylthiopropane, thioglycidylthio (meth) acrylate, glycidylthio (meth) Acrylate, 1,2-bis [(meth) acryloylthio] benzene, 1,3-bis [(me ) Acryloylthio] benzene, 1,4-bis [(meth) acryloylthio] benzene, 1,2-bis [(meth) acryloylthiomethyl] benzene, 1,3-bis [(meth) acryloylthiomethyl] benzene, 1,4-bis [(meth) acryloylthiomethyl] benzene, 1,2-bis [2- (meth) acryloylthioethylthiomethyl] benzene, 1,3-bis [2- (meth) acryloylthioethylthiomethyl Thio (meth) acrylate compounds such as benzene, 1,4-bis [2- (meth) acryloylthioethylthiomethyl] benzene;
Allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, diallyl sulfide, diallyl disulfide;
Vinyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m-dioxane);
Although diisopropenylbenzene etc. can be mentioned, it is not limited only to these exemplary compounds.

Examples of the polythiol compound include methanedithiol, ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 1,2,3-propane. Trithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2, 3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1- Propanol (3-mercaptopropionate , Diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate), Trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), tetrakis (me Kaputomechiru) aliphatic such as methane polythiol compound;
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-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,3 5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mer Ptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (4′-methoxyphenyl) propane-2,2-dithiol Aromatic polythiols such as 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (4′-mercaptophenyl) pentane;
1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1 , 2,4-Tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) ) Aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as benzene, 1,3,5-tris (mercaptoethylthio) benzene, and their nuclear alkylated products;
Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (2-mercapto) Ethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2, 3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 4, 8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-di Lucaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis (2-mercaptoethylthiomethyl) ) Methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide and the like, and Esters of these thioglycolic acid and mercaptopropionic acid;
Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl Sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis 2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4 Dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodi Propionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester) ), 4,4-dithio Dibutyl acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithiodiglycolic acid bis (2 , 3-dimercaptopropyl ester), dithiodipropionate bis (2,3-dimercaptopropyl ester) and other aliphatic polythiol compounds containing sulfur atoms in addition to mercapto groups;
In addition to mercapto groups such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole, a heterocyclic compound containing a sulfur atom can be given, and further, it can be represented by the general formula (A). The polythiol compound to be used can also be preferably used. The polythiol compounds represented by the general formula (A) can be used alone or in combination of two or more.

The resin in the present invention is obtained by polymerizing the polymerizable composition, and is obtained by polymerizing the (meth) acrylate compound of the present invention alone, or other copolymers of the (meth) acrylate compound. Copolymerized with various monomers or polythiol compounds.
In the present invention, the polymerization method for obtaining the resin is not particularly limited, and a known radical polymerization method can be employed.

  In this case, the polymerization initiation means includes the use of various thermal polymerization initiators such as peroxides and azo compounds, irradiation with ultraviolet rays, visible rays, α rays, β rays, γ rays, electron beams, or the like. Can be used in combination.

As the thermal polymerization initiator, known ones can be used, and typical ones include benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-t-butylperoxyazelate, t-butylperoxy- 2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, bis (4- and peroxides such as t-butylcyclohexyl) peroxydicarbonate and t-butylperoxyisopropyl carbonate, and azo compounds such as azobisisobutyronitrile.
When the polymerization is started by irradiation with ultraviolet (Ultra Violet: UV) or the like, a known UV polymerization initiator or the like can also be used.

  Typical examples of the UV polymerization initiator include benzophenone, 4,4′-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, methyl 2-benzoylbenzoate, 4-benzoyl- 4′-methyldiphenyl sulfide, 4-phenylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, isoamyl 4-N, N-dimethylaminobenzoate, ethyl 4-N, N-dimethylaminobenzoate, 4-N, N-dimethyl Methyl aminobenzoate, 4-N, N-dimethylaminobenzoic acid (2′-butyloxyethyl), benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, oligo [2-hydroxy-2-methyl-1- [4- (1-Vinyl Phenyl] propanone], diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, 2,2-dimethoxy-2-phenylacetophenone 2,2-methyl-2-hydroxyacetophenone, methylbenzoyl formate, ethyl- (2 , 4,6-trimethylbenzoyl) phenylphosphinate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyloxythioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- [4 ′-(2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis [4- (2′-hydroxy-2′-methyl-propionyl) phenyl ] Methane, phenylglyoxylic acid methyls 2-methyl-1- (4′-methylthiophenyl) -2-N-morpholinopropan-1-one, 2-benzyl-1-N, N-dimethylamino-1- (4′-N-morpho Linophenyl) -butan-1-one, 2-N, N-dimethylamino-2- (4′-methylbenzyl) -1- (1′-N-morpholinophenyl) -butan-1-one, bis ( 2,4,6-trimethylbenzoyl) phenylphosphine hydride, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

  A typical polymerization method for obtaining the resin (for example, plastic lens) of the present invention includes cast polymerization.

That is, a polymerization composition of the present invention (also referred to as a monomer mixture) containing a thermal polymerization initiator and / or a UV polymerization initiator is injected between molds held by a gasket or a tape.
At this time, it is preferable to perform treatment such as defoaming as necessary for improving the quality of the cast polymerized product.

  Next, the polymer can be taken out by irradiating with ultraviolet rays or the like, or heating in an oven, or curing in combination.

The polymerization method, polymerization conditions, and the like for obtaining the resin of the present invention cannot be generally limited by the type and amount of the initiator used and the type and ratio of the monomer.
For example, when irradiating with ultraviolet rays, the monomer mixture may be cooled to prevent overheating of the monomer mixture, and when heated in an oven, the temperature should be controlled to select the optimum temperature condition. There is also.
When heating in an oven, generally, a method of gradually heating from a low temperature and maintaining at a high temperature to complete the polymerization is employed.
In addition, the polymerization time can not be generally limited because it is affected by the type and amount of the initiator used and the type and ratio of the monomer.
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, a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye, a filler, etc. Various substances may be added.

  Further, the taken out resin may be subjected to a treatment such as annealing as necessary.

  The resin obtained using the (meth) acrylate compound of the present invention has a high refractive index and low dispersion, and is excellent in optical properties. Moreover, the obtained resin has the characteristic also excellent in abrasion resistance. In addition, for example, it is possible to obtain a resin excellent in heat resistance and weather resistance.

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 various kinds of lenses such as spectacle lenses and camera lenses, other optical element materials, and transparent resins. Can be used for applications.
In particular, it is suitable as a material for optical elements such as eyeglass lenses and camera lenses.

  Furthermore, in the lens using the resin in the present invention, if necessary, such as antireflection, imparting high hardness, improving wear resistance, improving chemical resistance, imparting antifouling property, imparting antifogging property, or imparting fashionability, etc. In order to make improvements, physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coat treatment, dyeing treatment, and light control treatment can be performed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example at all.

The physical properties of the resin obtained by polymerization were evaluated by the following methods.
Refractive index (nd), Abbe number (νd): measured at 25 ° C. using an Abbe refractometer.
Scratch resistance: The surface of the resin was rubbed with # 0000 steel wool to examine the difficulty of scratching the surface, and judged according to the following criteria.
○: No damage even when rubbed strongly. △: Some damage when rubbed strongly.

Production Example 1 Synthesis of 1,1,3,3-tetrakis (mercaptomethylthio) propane A 2 liter flask with a bottomed cock equipped with a stirring blade, a thermometer, a distillation column and a capillary for introducing nitrogen was 164.2 g (1 mol) of 1,3,3-tetramethoxypropane was added, and 488.8 g (4 mol) of acetylthiomethylthiol and 7.6 g (0.04 mol) of paratoluenesulfonic acid were added thereto, and a vacuum of 1 kPa or less was added. The temperature was maintained and the mixture was heated to 55-60 ° C. with stirring.
Heating was continued for about 5 hours until the distillation of methanol stopped.
After cooling, release the vacuum, attach a condenser instead of a distillation column, add 400 mL of methanol and 400 mL of chloroform, heat to 60 ° C. to perform alcoholysis, and then obtain 1,1,3,3-tetrakis of the target compound. (Mercaptomethylthio) propane (hereinafter sometimes abbreviated as TMMTP) was produced.

An appropriate amount of water and chloroform were added for liquid separation, and the chloroform layer was washed with water several times.
The solvent was removed to remove chloroform and low-boiling components, followed by filtration with a 3 μm Teflon (registered trademark) filter to obtain 340.0 g of TMMTP.

When the IR spectrum of TMMTP obtained with FTIR-8300 manufactured by Shimadzu Corporation was measured, absorption specific to a mercapto group was observed at 2538.1 cm ⁻¹ .
Mass spectrum is m / z = 356 (M +), elemental analysis is C = 23.5% (23.6%), H = 4.6% (4.5%), S = 71.9% (71 0.9%) (calculated values in parentheses).

Production Example 2 Synthesis of 1,1,2,2-tetrakis (mercaptomethylthio) ethane A 2 liter flask with a bottomed cock equipped with a stirring blade, a thermometer, a distillation column and a capillary for introducing nitrogen was 150.2 g (1 mol) of 1,2,2-tetramethoxyethane was added, and 488.8 g (4 mol) of acetylthiomethylthiol and 7.6 g (0.04 mol) of paratoluenesulfonic acid were added thereto, and the vacuum was 1 kPa or less. The temperature was maintained and the mixture was heated to 55-60 ° C. with stirring.
Heating was continued for about 5 hours until the distillation of methanol stopped.
After cooling, the vacuum is released, 400 mL of methanol and 400 mL of chloroform are added, and the mixture is heated to 60 ° C. for alcoholysis. The target compound 1,1,2,2-tetrakis (mercaptomethylthio) ethane (hereinafter abbreviated as TMMTE). May be generated).

An appropriate amount of water and chloroform were added for liquid separation, and the chloroform layer was washed with water several times.
After removing the solvent to remove chloroform and low-boiling components, the solution was filtered through a 3 μm Teflon (registered trademark) filter to obtain 321.1 g of TMMTE.

When the IR spectrum of TMMTE obtained with FTIR-8300 manufactured by Shimadzu Corporation was measured, absorption specific to a mercapto group was observed at 2522.7 cm ⁻¹ .
Mass spectrum is m / z = 342, elemental analysis is C = 20.8% (21.0%), H = 4.2% (4.1%), S = 75.0% (74.9%) (The value in parentheses is the calculated value).

(Production Example 3) Synthesis of 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane A 2 liter flask with a bottomed cock equipped with a stirring blade, a thermometer, a distillation column and a capillary for introducing nitrogen, Add 82.1 g (0.5 mol) of 1-acetylthio-2,2-dimethoxyethane, add 244.4 g (2 mol) of acetylthiomethylthiol and 3.8 g (0.02 mol) of paratoluenesulfonic acid, and add 1 kPa The following vacuum degree was maintained and it heated at 55-60 degreeC, stirring.
Heating was continued for about 5 hours until the distillation of methanol stopped.
After cooling, the vacuum was released, and a condenser was attached instead of a distillation column. Then, 300 mL of methanol and 300 mL of chloroform were added, and the mixture was heated to 60 ° C. for alcoholysis. The target compound 3-mercaptomethyl-1,5- Dimercapto-2,4-dithiapentane (hereinafter sometimes abbreviated as MDMDP) was produced.

An appropriate amount of water and chloroform were added for liquid separation, and the chloroform layer was washed with water several times.
The solvent was removed to remove chloroform and low-boiling components, followed by filtration with a 3 μm Teflon (registered trademark) filter to obtain 100.6 g of MDMDP.

The IR spectrum of MDMDP obtained with FTIR-8300 manufactured by Shimadzu Corporation was measured, and absorption specific to the mercapto group was observed at 2540.1 cm ⁻¹ .
Mass spectrum is m / z = 218, elemental analysis is C = 21.9% (22.0%), H = 4.6% (4.6%), S = 73.5% (73.4%) (The value in parentheses is the calculated value).

(Example 1) Production of 1,1,3,3-tetrakis (acryloylthiomethylthio) propane A 500 mL flask equipped with a stirring blade, a thermometer, a condenser, a nitrogen introduction pipe and an exhaust pipe, and two dropping funnels Was charged with 17.9 g (0.05 mol) of 1,1,3,3-tetrakis (mercaptomethylthio) propane and 130 g of toluene. β-chloropropionyl chloride 27.9 g (0.22 mol) and toluene 20 g were charged into one dropping funnel, and triethylamine 22.2 g (0.22 mol) and toluene 10 g were charged into the other dropping funnel. The flask was immersed in a water bath, and β-chloropropionyl chloride and triethylamine were simultaneously dropped into the flask from two dropping funnels. At this time, the internal temperature was adjusted by adding ice to the water bath so that the internal temperature of the flask did not exceed 25 ° C. The dropping time from the dropping funnel to the reaction mixture required 55 minutes for the toluene solution of β-chloropropionyl chloride and 70 minutes for the toluene solution of triethylamine.

Thereafter, the suspension in the flask (becomes suspended due to the formation of triethylemine hydrochloride) was stirred overnight at room temperature.
Next, the suspension in the flask was filtered to remove triethylamine hydrochloride, and the triethylamine hydrochloride was washed with 200 mL of toluene.
Toluene was distilled off from the filtrate and washings under reduced pressure to obtain 33.8 g of a colorless oil. This oily substance was purified by silica gel column chromatography (eluent: toluene) to obtain 11.3 g of colorless oily 1,1,3,3-tetrakis (β-chloropropionylthiomethylthio) propane.

  Next, 5.17 g (7.2 mmol) of 1,1,3,3-tetrakis (β-chloropropionylthiomethylthio) propane and 40 g of dichloromethane were charged into a 100 mL flask, and 3.15 g (0.03 mol) of triethylamine was added. ) And 20 g of dichloromethane were added dropwise over 2 hours and 20 minutes, and the reaction mixture was further stirred at room temperature for 50 minutes. The internal temperature of the flask was adjusted with a water bath so as to be in the range of 25 ° C to 26 ° C.

After completion of the reaction, the reaction solution was neutralized and washed with 200 mL of 1% hydrochloric acid, and further washed twice with 200 mL of distilled water. From the organic layer obtained after the separation, dichloromethane was distilled off under reduced pressure to obtain a colorless oil. Furthermore, air was passed through the capillary through the oily substance, and the solvent was removed overnight to obtain 4.5 g of the desired 1,1,3,3-tetrakis (acryloylthiomethylthio) propane as a colorless oily substance.
1 and 2 are diagrams showing the ¹ H-NMR measurement result and the FT-IR measurement result of the compound obtained in this example, respectively.

  Mass spectrum is m / z = 572, elemental analysis is C = 39.7% (39.8%), H = 4.2% (4.2%), S = 44.7% (44.8%) (The value in parentheses is the calculated value).

¹ H-NMR (in CDCl ₃ , TMS standard)
σ = 2.32 (t, 2H,> CH—C H ₂ —CH <)
4.23 (m, 8H, -S- C H 2 -S-)
4.37 (m, 2H,> C H -CH 2 -C H <)
5.76 (m, 4H, -CH = C H 2)
6.36 (m, 8H, -C H = C H ₂ )

(Example 2) Production of 1,1,2,2, -tetrakis (acryloylthiomethylthio) ethane 500 mL flask equipped with a stirring blade, thermometer, condenser, nitrogen introduction pipe and exhaust pipe, and two dropping funnels Was charged with 17.1 g (0.05 mol) of 1,1,2,2-tetrakis (mercaptomethylthio) ethane and 120 g of toluene. β-chloropropionyl chloride 27.9 g (0.22 mol) and toluene 20 g were charged into one dropping funnel, and triethylamine 22.2 g (0.22 mol) and toluene 10 g were charged into the other dropping funnel. The flask was immersed in a water bath, and β-chloropropionyl chloride and triethylamine were simultaneously dropped into the flask from two dropping funnels. At this time, the internal temperature was adjusted by adding ice to the water bath so that the internal temperature of the flask did not exceed 25 ° C. The dropping time from the dropping funnel to the reaction mixture required 61 minutes for the toluene solution of β-chloropropionyl chloride and 65 minutes for the toluene solution of triethylamine.

Thereafter, the suspension in the flask (becomes suspended due to the formation of triethylemine hydrochloride) was stirred overnight at room temperature.
Next, the suspension in the flask was filtered to remove triethylamine hydrochloride, and the triethylamine hydrochloride was washed with 200 mL of toluene.
Toluene was distilled off from the filtrate and washings under reduced pressure to obtain 32.6 g of a colorless oil. The oil was purified by silica gel column chromatography (eluent: toluene) to obtain 12.5 g of colorless oily 1,1,2,2, -tetrakis (β-chloropropionylthiomethylthio) ethane.

  Next, 5.07 g (7.2 mmol) of 1,1,2,2, -tetrakis (β-chloropropionylthiomethylthio) ethane and 40 g of dichloromethane were charged into a 100 mL flask, and 3.15 g (0.03 mol) of triethylamine was added. ) And 20 g of dichloromethane were added dropwise over 1 hour 30 minutes, and the reaction mixture was further stirred at room temperature for 60 minutes. The internal temperature of the flask was adjusted with a water bath so as to be in the range of 25 ° C to 26 ° C.

  After completion of the reaction, the reaction solution was neutralized and washed with 200 mL of 1% hydrochloric acid, and further washed twice with 200 mL of distilled water. From the organic layer obtained after the separation, dichloromethane was distilled off under reduced pressure to obtain a colorless oil. Further, air was passed through the capillary into the oily substance, and the solvent was removed overnight to obtain 4.1 g of the desired 1,1,2,2-tetrakis (acryloylthiomethylthio) ethane as a colorless oily substance.

  Mass spectrum is m / z = 558, elemental analysis is C = 38.6% (38.7%), H = 3.9% (4.0%), S = 45.8% (45.9%) (The value in parentheses is the calculated value).

(Example 3) Production of 3-acryloylthiomethyl-1,5-bis (acryloylthio) -2,4-dithiapentane A stirring blade, a thermometer, a condenser, a nitrogen introduction pipe and an exhaust pipe, and two dropping funnels were installed. A 500 mL flask was charged with 10.92 g (0.05 mol) of 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane and 120 g of toluene. 20.95 g (0.165 mol) of β-chloropropionyl chloride and 20 g of toluene were charged into one dropping funnel, and 16.66 g (0.165 mol) of triethylamine and 10 g of toluene were charged into the other dropping funnel. The flask was immersed in a water bath, and β-chloropropionyl chloride and triethylamine were simultaneously dropped into the flask from two dropping funnels. At this time, the internal temperature was adjusted by adding ice to the water bath so that the internal temperature of the flask did not exceed 25 ° C. The dripping time from the dropping funnel to the reaction mixture required 64 minutes for the toluene solution of β-chloropropionyl chloride and 69 minutes for the toluene solution of triethylamine.

Thereafter, the suspension in the flask (becomes suspended due to the formation of triethylemine hydrochloride) was stirred overnight at room temperature.
Next, the suspension in the flask was filtered to remove triethylamine hydrochloride, and the triethylamine hydrochloride was washed with 200 mL of toluene.
Toluene was distilled off from the filtrate and washings under reduced pressure to obtain 18.62 g of a colorless oil. This oily substance was purified by silica gel column chromatography (eluent: toluene), and colorless oily 3-β-chloropropionylthiomethyl-1,5-bis (β-chloropropionylthio) -2,4-dithiapentane7. 2 g was obtained.

  Next, 4.89 g (10 mmol) of 3-β-chloropropionylthiomethyl-1,5-bis (β-chloropropionylthio) -2,4-dithiapentane and 50 g of dichloromethane were charged into a 100 mL flask, and triethylamine 3 A solution consisting of .33 g (33 mmol) and 20 g of dichloromethane was added dropwise over 2 hours and the reaction mixture was further stirred at room temperature for 60 minutes. The internal temperature of the flask was adjusted with a water bath so as to be in the range of 25 ° C to 26 ° C.

  After completion of the reaction, the reaction solution was neutralized and washed with 200 mL of 1% hydrochloric acid, and further washed twice with 200 mL of distilled water. From the organic layer obtained after the separation, dichloromethane was distilled off under reduced pressure to obtain a colorless oil. Further, air is passed through the capillary into the oily substance, and the solvent is removed overnight. The desired 3-acryloylthiomethyl-1,5-bis (acryloylthio) -2,4-dithiapentane is obtained as a colorless oily substance. 3.73 g was obtained.

  Mass spectrum is m / z = 380, elemental analysis is C = 40.8% (41.0%), H = 4.2% (4.2%), S = 42.0% (42.1%) (The value in parentheses is the calculated value).

(Example 4) Production of 1,3-bis (methacryloylthio) -2-thiapropane In a 500 mL flask equipped with a stirring blade, a thermometer, a condenser, a nitrogen introduction pipe and an exhaust pipe, and two dropping funnels, 12.6 g (0.1 mol) of 3-dimercapto-2-thiapropane and 140 g of toluene were charged. β-Chloro-α-methylpropionyl chloride (31.02 g, 0.22 mol) and toluene (20 g) were charged into one dropping funnel, and triethylamine (22.2 g, 0.22 mol) and toluene (20 g) were charged into the other dropping funnel. I entered. The flask was immersed in a water bath, and β-chloro-α-methylpropionyl chloride and triethylamine were simultaneously dropped into the flask from two dropping funnels. At this time, the internal temperature was adjusted by adding ice to the water bath so that the internal temperature of the flask did not exceed 25 ° C. The dropping time from the dropping funnel to the reaction mixture required 59 minutes for the toluene solution of β-chloro-α-methylpropionyl chloride and 62 minutes for the toluene solution of triethylamine.

Thereafter, the suspension in the flask (becomes suspended due to the formation of triethylemine hydrochloride) was stirred overnight at room temperature.
Next, the suspension in the flask was filtered to remove triethylamine hydrochloride, and the triethylamine hydrochloride was washed with 200 mL of toluene.
Toluene was distilled off from the filtrate and washings under reduced pressure to obtain 10.2 g of a colorless oil. This oily matter was purified by silica gel column chromatography (eluent: toluene) to obtain 7.2 g of colorless oily 1,3-bis (β-chloro-α-methylpropionylthio) -2-thiapropane.

  Next, 3.35 g (10 mmol) of 1,3-bis (β-chloro-α-methylpropionylthio) -2-thiapropane and 30 g of dichloromethane were charged into a 100 mL flask, and 2.22 g (22 mmol) of triethylamine and dichloromethane were charged. A solution consisting of 20 g was added dropwise over 2 hours and the reaction mixture was further stirred at room temperature for 60 minutes. The internal temperature of the flask was adjusted with a water bath so as to be in the range of 25 ° C to 26 ° C.

  After completion of the reaction, the reaction solution was neutralized and washed with 200 mL of 1% hydrochloric acid, and further washed twice with 200 mL of distilled water. From the organic layer obtained after the separation, dichloromethane was distilled off under reduced pressure to obtain a colorless oil. Furthermore, air was passed through the capillary through the oily substance, and the solvent was removed overnight to obtain 2.33 g of the objective 1,3-bis (methacryloylthio) -2-thiapropane as a colorless oily substance.

  Mass spectrum is m / z = 262, elemental analysis is C = 45.7% (45.8%), H = 5.3% (5.4%), S = 36.6% (36.7%) (The value in parentheses is the calculated value).

(Example 5) (Resinification)
According to Table 1, a monomer and a photopolymerization initiator were mixed, and degassed for 2 hours under light-shielding and reduced pressure (<30 mmHg) to obtain a composition for polymerization.

  In Table 1, Drocure-1173 is a photopolymerization initiator (BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one).

The composition obtained is injected into a cavity formed by a glass plate and tape, and inside a UV conveyor (Fusion UV Systems Japan, electrodeless discharge lamp H bulb, 120 W / cm, conveyor speed 6 m / min) Was passed through 3 times (accumulated light amount 2700 mJ / cm ² ) and cured.

After cooling, the tape and the glass plate were peeled off to obtain a transparent resin molded body.
When the obtained resin molding was measured with an Abbe refractometer, n _D = 1.68 and Abbe number 32 as shown in Table 2. Table 2 shows the measurement results of the refractive index and Abbe number of the obtained resin molding.
Moreover, the obtained resin molding was excellent in scratch resistance, and the evaluation was “◯”.

(Comparative Example 1)
For comparison, instead of the acrylate compound obtained in Example 1, 1,4-bis (2′-acryloylthioethylthio) which is an acrylate compound described in JP-A-9-132563 (Patent Document 4) About -1,5-bis (acryloylthio) -3-thiapentane, resinification was performed by an operation according to Example 5 to obtain a transparent resin molded product.
The obtained resin molding had a refractive index n _D of 1.642 and an Abbe number of 33.

  From a comparison between Example 5 and Comparative Example 1, it can be seen that the resin prepared from the (meth) acrylate compound of the present invention can be polymerized in a short time and has high optical properties, particularly a high refractive index. .

Claims (9)

The following general formula (1)

[In the general formula (1), R ₁ represents an organic residue other than an aromatic ring or a single bond. R ₂ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more. Or general formula (2)

[In the above general formula (2), Z represents a —CH ₂ — group or —CH ₂ —S—CH ₂ — group, and R ₂ represents a hydrogen atom or a methyl group. And one or more (meth) acrylate compounds selected from compounds having two or more (meth) acrylate groups in the molecule. R ₁ in the general formula (1) is aliphatic, alicyclic, heterocyclic, aliphatic having a sulfur atom in the chain, alicyclic having a sulfur atom in the chain, and having a sulfur atom in the chain. The (meth) acrylate compound according to claim 1, which is an organic residue selected from a heterocyclic ring or a single bond. R ₁ in the general formula (1) is linear or branched aliphatic, linear or branched alicyclic, linear or branched aliphatic having a sulfur atom in the chain, The (meth) acrylate compound according to claim 1 or 2, which is an organic residue selected from a linear or branched alicyclic group having a sulfur atom in the chain, or a single bond.   The (meth) acrylate compound as described in any one of Claims 1 thru | or 3 whose n in the said General formula (1) is an integer of 1-4. The following general formula (1)

[In the general formula (1), R ₁ represents an organic residue other than an aromatic ring or a single bond. R ₂ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more. And / or the following general formula (2)

[In the above general formula (2), Z represents a —CH ₂ — group or —CH ₂ —S—CH ₂ — group, and R ₂ represents a hydrogen atom or a methyl group. ] And a polymerizable composition comprising one or more compounds selected from compounds having two or more (meth) acrylate groups in the molecule.   The (meth) acrylate compound represented by the general formula (1) and / or the general formula (2), and at least one monomer or polythiol compound copolymerizable therewith is contained. The polymerizable composition described in 1.   A resin obtained by polymerizing the polymerizable composition according to claim 5.   An optical element made of the resin according to claim 7.   A lens comprising the optical element according to claim 8.

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