JPH03220172A - Thiocarboxylic acid ester compound and its production - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is H or methyl; R<2> and R<3> are H or alkyl; R<4> is 2-5C alkylene; R<5> is aryl). EXAMPLE:2-Phenylethylthioethyl thiomethacrylate. USE:An optical material which is a liquid at ordinary temperature, capable of dissolving a monomer that is a solid at ordinary temperature for high refractive index resins and capable of providing resins having a high refractive index with low dispersibility and excellent in transparency, impact and weather resistance, lightweight properties, etc. PREPARATION:A compound expressed by formula II and a compound expressed by formula III (R<6> is OH, Cl or alkoxy) are subjected to dehydrating condensation in the presence of an acid catalyst (e.g. hydrochloric acid) in a solvent such sa benzene at 0-120 deg.C to afford the compound expressed by formula I. Water formed as a by-product is preferably removed by using a Dean-Stark water separator, etc., or by the coexistence of a dehydrating agent in the reaction system, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to polymerizable thiocarboxylic acid ester compounds which are particularly useful as optical materials, and which are also useful in paints, inks, adhesives, photosensitive resins, etc. This relates to a manufacturing method.

[Prior art]

Conventionally, various studies have been conducted on synthetic resins to replace inorganic glass, but there are many drawbacks, and no one with fully satisfactory properties has yet been obtained. For example, polymers made from monomers whose main components are methyl methacrylate and diethylene glycol bis(allyl carbonate) are used as optical resins and lenses, but their refractive index is approximately 1.5.
As low as 0.

Various high refractive index resins have been proposed to improve this drawback. For example, high refractive index resins such as polycarbonate and polysulfone have been proposed. Although these resins have a high refractive index of about 1.60, they have problems such as low light transmittance, lack of optical homogeneity, and coloring.

For this reason, various crosslinkable monomers for high refractive index resins have been proposed. For example, resins containing a large number of halogen atoms, such as phenyl methacrylate, in which phenyl groups are substituted with halogen atoms, have been proposed in JP-A-61-28901. In addition, α
- A composition for a high refractive index resin containing naphthyl methacrylate as a main component has been proposed. Most of these monomers for high refractive index resins are solid at room temperature because they contain halogen atoms and condensed aromatic rings. Therefore, these monomers are dissolved in a liquid monomer at room temperature and polymerized.

As the above liquid monomer, the following formula %formula% (R' represents an alkyl group.) The methacrylic acid ester shown is known.

However, the resin made by polymerizing this monomer does not have a very high refractive index and, like general resins, has insufficient scratch resistance on the surface, so it cannot be used for optical materials such as lenses. , it is necessary to form a hard coat film consisting of an organic silicone film on the surface. However, since this resin is made of methacrylic acid ester,
Even if the method normally applied to allyl diglycol carbonate resin, that is, the method of forming an organic silicone film after surface treatment with an alkaline solution, is applied, the adhesion between the resin and the film is insufficient and it cannot be put to practical use. It was difficult.

[Problem to be solved by the invention]

The problem to be solved by the present invention is to provide a monomer that is liquid at room temperature and suitable for dissolving monomers that are solid at room temperature for high refractive index resins, which has a high refractive index, low dispersion, and is transparent. The object of the present invention is to provide a monomer that provides a resin with excellent impact resistance, weather resistance, and light weight.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present inventors have conducted intensive research and found that a thiocarboxylic acid ester compound having a specific structure is an excellent compound having the above-mentioned properties. The invention was completed.

That is, the present invention provides - ship storage (1) This is a thiocarboxylic acid ester compound represented by

In the above-mentioned -Shipage CII, R2 and R3 may be the same or different hydrogen atoms or alkyl groups, respectively, but from the viewpoint of utilizing the polymer obtained by polymerization of the compound of the present invention as an optical material, A hydrogen atom or a methyl group is preferred.

In the above-Funazura [I], the alkylene group represented by R4 has 2 to 5 carbon atoms. When the number of carbon atoms is 6 or more, it is not preferable because the heat resistance of the resin obtained by polymerizing the thiocarboxylic acid ester compound of the present invention decreases. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a propylene group, and an I,2-dimethylethylene group. In the present invention, considering the refractive index and heat resistance of the resulting resin, the number of carbon atoms in the alkylene group is 2 to 2.
4 is particularly preferred.

In the above-shipped stock (1), R5 is substituted or unsubstituted 7
It is a reel group. The number of carbon atoms in the above-mentioned oryl group is not particularly limited, but from the viewpoint of the viscosity of the compound of the present invention and the refractive index of the polymer obtained by polymerization, the number of carbon atoms is 6 to 10. It is preferable. Examples include phenyl group, tolyl group, xylyl group, naphthyl group, etc.
A phenyl group is particularly suitable.

The substituent for the oryl group represented by R5 is not particularly limited, and examples include a halogen atom, an alkoxy group, an alkylthio group, a phenyl group, and a phenylthio group. Typical examples of these substituted aryl groups include halogenoaryl groups such as chlorophenyl, bromophenyl, dichlorophenyl, dibromophenyl, and tribromophenyl; methylthiophenyl, di(methylthiophenyl); ) phenyl group, phenylthiophenyl group, biphenyl group, etc.

The thiocarboxylic acid ester compound shown in (4) above of the present invention can be identified and confirmed by the following means.

(a) By measuring the infrared absorption spectrum (IR), absorption based on CH bond at 3150 to 2800 cm-', absorption based on terminal double bond at 1650 to 1620 cm-1, and further absorption at around 1660 to 1690 C1ll-' Strong absorption of carbonyl groups based on thioester bonds is observed.

(a) Compounds can be easily identified by measuring IH-nuclear magnetic resonance spectra ('H-NMR). In particular, when R1 is a methyl group in Shipura (I), there is a peak based on the methyl group at around 61.9 ppm, and a peak based on the terminal vinylidene proton at around δ5, 7 and 66, 1 ppm, respectively, at 3:1. :1 ratio, a pattern characteristic of methacrylic acid esters is observed. When R is a hydrogen atom, three hydrogen atoms are observed at 65.6 to 7 ppm in a pattern unique to acrylic esters. Furthermore, in the thioether chain, hydrogen on the carbon atom bonded to the sulfur atom exhibits a peak around 62.9 ppm in a pattern depending on the bonding state. Furthermore, when either R2 or R3 is a methyl group, 61.1
A double line is observed near ppm. Also, 67-68.
A peak attributed to an alkylene group is observed at 5 ppm, and a peak attributed to an alkylene group is observed at δ~4 ppm. If other hydrogen atoms are present, they will exhibit a spectral pattern depending on their bonding mode. The compound can be easily identified from the above information.

(1) The weight percent of oxygen can be calculated by determining the weight percent of each of carbon, hydrogen, sulfur, and halogen through elemental analysis, and subtracting the sum of the weight percent of each recognized element from 100. The compositional formula of can be determined.

- Shipman The thiocarboxylic acid ester compound represented by N) may be obtained by any method, but is generally produced by the method described below.

The following formula (II) A compound represented by the following formula (n[] This is a method of reacting with the compound shown in

(A) Method using carboxylic acid By dehydrating and condensing a compound represented by general formula (II) and a carboxylic acid in which R6 is a hydroxyl group among the compounds represented by general formula (III) in the presence of an acid catalyst, - The thiocarboxylic acid ester compound in shipyard [I] can be produced. Although the molar ratio of the two raw materials may be appropriately determined as necessary, it is common to use an excess of one of the compounds. In this reaction, examples of the acid used as a catalyst include mineral acids such as hydrochloric acid and sulfuric acid, aromatic sulfonic acids, and Lewis acids such as boron fluoride etherate.

In this reaction, water is produced as a by-product, but since the reaction is an equilibrium reaction, a Dean-Stark water separator is generally used, or a dehydrating agent such as anhydrous sodium sulfate or molecular sieve is placed in a Soxhlet extractor. It is preferable to remove water from the system by refluxing the solvent or allowing a dehydrating agent such as N,N-dicyclohexylcarbodiimide to coexist in the reaction system. The solvent is preferably an aromatic hydrocarbon such as benzene or toluene, or a halogenated aliphatic hydrocarbon such as chloroform or dichloromethane.

The reaction temperature varies depending on the type of solvent, but in general,
0°C to 120°C is preferred. Although the reaction time cannot be absolutely limited depending on the type of raw materials, it is particularly preferably selected from the range of 30 minutes to 20 hours, and more preferably 1 hour to 6 hours. The method for isolating and purifying the target product, ie, the compound represented by Funazura (1) above, from the reaction system is not particularly limited, and any known method can be employed.

(a) Method using carboxylic acid chloride - A compound represented by Shipura (It) and a carboxylic acid chloride in which R6 is a chlorine atom among the compounds represented by the general formula C[[] are combined in the presence of a base. The thiocarboxylic acid ester compound of general formula (1) can be produced by dehydrochlorination.

The molar ratio of both raw materials is usually (-Compound represented by Funagura (11))/(-Compound represented by Funagura (III))
=0.8 to 1.5, but it is particularly preferable to use equal amounts.

In this reaction, hydrogen chloride is produced as a by-product. Generally, in order to remove this hydrogen chloride from the reaction system, it is preferable to coexist a base as a hydrogen chloride scavenger in the reaction system or to pass an inert gas such as nitrogen gas into the reaction system.

The base used as the hydrogen chloride scavenger is not particularly limited, and any known base can be used. Examples of bases that are generally preferably used include trialkylamines such as trimethylamine, triethylamine, and tripropylamine, pyridine, tetramethylurea, sodium hydroxide, and sodium carbonate. The amount of base used is preferably 1 mol or more per 1 mol of carboxylic acid chloride.

In the reaction in the present invention, it is generally preferable to use an organic solvent. Examples of solvents preferably used include aliphatic or aromatic hydrocarbons or halogenated hydrocarbons such as benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride, and ethylene chloride. ; Ethers such as diethyl ether, dioxane, tetrahydrofuran, etc. 11; N,
N-dimethylformamide, N.

Examples include N,N-dialkylamides such as N-diethylformamide; dimethyl sulfoxide, and the like.

The temperature in the reaction can be selected from a wide range, generally from -20°C to 100°C, preferably from 0°C to 50°C. Although the reaction time varies depending on the type of raw materials, it is usually selected from the range of 5 minutes to 24 hours, preferably 10 minutes to 4 hours. Further, it is preferable to stir the reaction mixture during the reaction.

The method for isolating and purifying the target product, ie, the compound represented by -Funezo (I) above, from the reaction system is not particularly limited, and any known method can be employed.

(1) Method using carboxylic acid ester - Funagura (II)
The thiocarboxylic acid ester compound of -Funazo (1) is transesterified using a compound represented by the formula (I) and a carboxylic acid ester in which R6 is an alkoxy group among the compounds represented by the general formula (I It can be manufactured.

In this reaction, it is preferable to use an acid or a base as a catalyst. Examples of acids suitably used as catalysts include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, etc.
Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and alkoxides such as sodium methoxide and potassium t-butoxide.

In this reaction, alcohol (R'H) is produced. Since this reaction is an equilibrium reaction, it is preferable to remove this alcohol from the reaction system by a method such as distillation or azeotropy. For this reason, it is preferable to use a carboxylic acid ester represented by general formula (III) as a raw material in which R6 has an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms.

This reaction is generally carried out without a solvent, but if the raw material is solid, it is preferable to use a solvent with a boiling point higher than that of the by-product alcohol.

Examples of solvents preferably used include aromatic hydrocarbons or halogen-substituted aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene; N,N-dimethylformamide, N,
Examples include N,N-dialkylamides such as N-diethylformamide; dimethyl sulfoxide, and the like.

The temperature in the reaction varies depending on the type of alcohol produced by the reaction, but is generally preferably a temperature at which the alcohol produced by the reaction is distilled off. The reaction time varies depending on the type of raw material, but is usually 30 minutes to 24 hours, preferably 2 hours to
You can choose from a range of 8 hours. Further, it is preferable to stir the reaction mixture during the reaction.

The method for isolating and purifying the target product, ie, the compound represented by Funazura (1) above, from the reaction system is not particularly limited, and any known method can be employed.

The thiocarboxylic acid ester compound shown in the above-mentioned (1) of the present invention is a liquid monomer and has a high refractive index,
Produces a low dispersion, colorless and transparent polymer with low specific gravity and excellent impact resistance.

The compound can be polymerized alone or can be copolymerized with other monomers.

Monomers copolymerizable with the thiocarboxylic acid ester compound are selected depending on the purpose and can be used without particular limitations.

In particular, since the thiocarboxylic acid ester compound of the present invention is liquid, the monomer may be solid. Examples of copolymerizable monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fulmic acid;
Methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2.6.6- Tetrabromobisphenol A dimethacrylate, 2,2-bis(4
-methacryloyloxyethoxyphenyl)propane,
Acrylic acid and methacrylic acid ester compounds such as 2,2-bis(3゜5-dibromo-4-methacryloyloxyethoxyphenyl)propane and trifluoromethyl methacrylate; methyl thiomethacrylate, benzyl thiomethacrylate, phenyl thiomethacrylate, Thioacrylic acid and thiomethacrylic acid ester compounds such as benzyl thioacrylate; Fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, diphenyl fumarate; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, epoxysuccinic acid Allyl compounds such as diallyl, diallyl malate, allyl cinnamate, allyl isocyanate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate; styrene, chlorostyrene, methylstyrene, vinylnaphthalene, isopropenylnaphthalene, bromostyrene , aromatic vinyl compounds such as dipromostyrene, etc. These monomers can be used alone or in combination of two or more.

The mixing ratio of these copolymerizable monomers to the thiocarboxylic acid ester in+ represented by the general formula [I] is as follows:
Although it cannot be absolutely limited depending on each compound, the amount of the copolymerizable monomer is 5 to 500 parts by weight, more preferably 10 to 500 parts by weight, per 100 parts by weight of the thiocarboxylic acid ester compound.
It is preferable to use 200 parts by weight, and the diocarboxylic acid ester of the present invention can be obtained by homopolymerization or copolymerization with a monomer having one polymerizable group among the copolymerizable monomers listed in L. The high refractive index resin is a thermoplastic resin.

For this reason, when the special muco resin is used for applications that require beading processing, etc., it is preferable to copolymerize using a monomer having two or more polymerizable groups as the copolymerizable monomer. .

The polymerization method for obtaining a polymer from a monomer composition containing the thiocarboxylic acid ester compound of general formula II) alone or other copolymerizable monomers is not particularly limited, and known radical polymerization methods can be employed. Polymerization initiation means can be carried out by using radical polymerization initiators such as various peroxides and azo compounds, by irradiation with ultraviolet rays, α rays, β rays, γ rays, etc., or by using a combination of both. To illustrate typical polymerization methods,
The above-mentioned monomer or monomer composition containing a radical polymerization initiator is injected between the molds held by elastomer gaskets or spacers, cured in an air oven, and then taken out. Polymerization is employed.

The radical polymerization initiator is not particularly limited and any known one can be used, but representative examples include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide. Diacyl peroxides such as oxand; Peroxy esters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxybuodecanate, t-butylperoxybenzoate; diisopropyl peroxybenzoate; carbonates such as carbonate, di-2-ethylhexyl peroxydicarbonate, di-5ec-butyl peroxydicarbonate; azo compounds such as azobis-isobutyronitrile; The amount of the radical polymerization initiator used varies depending on the polymerization conditions, the type of initiator, and the composition of the monomers mentioned above, and cannot be generally limited, but is generally 0.00 parts by weight per 100 parts by weight of the total monomers. It is suitable to use it in a range of 0.001 to 10 parts by weight, preferably 0.001 to 5 parts by weight.

Among the polymerization conditions, temperature particularly affects the properties of the high refractive index resin obtained. Since this temperature condition is influenced by the type and amount of initiator and the type of monomer, it is generally not possible to limit it, but polymerization is initiated at a relatively low temperature when fishing on a boat.
It is preferable to carry out so-called tapered two-stage polymerization in which the temperature is slowly raised and the polymer is cured at a moderate temperature when the polymerization is completed. Like temperature, polymerization time also varies depending on various factors, so it is preferable to determine the optimal time according to these conditions in advance. It is preferable to choose.

Of course, during the polymerization, various stabilizers and additives such as release agents, ultraviolet absorbers, antioxidants, color inhibitors, antistatic agents, fluorescent dyes, dyes, and pigments may be selected and used as necessary. You can.

In addition, since the thiocarboxylic acid ester compound of the present invention has one polymerizable group in the molecule, it is possible to perform prepolymerization to obtain a prepolymer and then perform polymerization molding, or to polymerize into pellets and then injection molding. It is also possible to mold the optical material into a desired optical material using methods such as extrusion molding and extrusion molding.

A known polymerization method can be used to obtain the prepolymer or pellets. That is, methods such as bulk polymerization, polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and precipitation polymerization can be applied.

Furthermore, the high refractive index resin obtained by the above method can be subjected to the following treatments depending on its use. In other words, dyeing using dyes such as disperse dyes, hard coating agents mainly composed of solan coupling agents and sol of oxides such as silicon, zirconium, antimony, and aluminum, and hard coatings mainly composed of organic polymers. Hard coating treatment with agent, SiO□, TiOz, ZrO
，! It is also possible to perform processing and secondary treatments such as antireflection treatment and antistatic treatment by vapor deposition of a thin film of a metal oxide, coating of a thin film of an organic polymer, etc.

〔effect〕

The thiocarboxylic acid ester compound of the present invention is liquid at room temperature and can be suitably used as a monomer for dissolving a monomer for high refractive index resin that is solid at room temperature.

In addition, the polymer obtained by polymerizing the thiocarboxylic acid ester compound of the present invention has excellent impact resistance and weather resistance, and has a refractive index of 1.57 or more, low dispersion, and excellent transparency and light weight. ing. Therefore, the homopolymer of the thiocarboxylic acid ester compound of the present invention or the high refractive index resin obtained by copolymerizing the compound with a monomer copolymerizable with the compound is useful as an organic glass, for example, as an eyeglass lens, It is most suitable as an optical lens such as an optical equipment lens, and can also be suitably used for applications such as prisms, optical disk substrates, and optical fibers.

〔Example〕

EXAMPLES Hereinafter, in order to specifically explain the present invention, Examples will be given and explained, but the present invention is not limited to these Examples.

The thiocarboxylic acid ester compound obtained in the present invention was identified by the following analysis method.

(1) IR spectrum Using IR-440 model manufactured by Shimadzu Corporation, the sample was
Measurements were made using a thin film using temporary scissors.

(21'H-NMR spectrum JEOL side layer) Using PMX-60SI type (60 MHz), the sample was diluted to CDC1, and the measurement was performed using tetramethylsilane as an internal standard.

(3) Elemental analysis ■ Carbon and hydrogen were analyzed using a CHN coder MT-2 manufactured by Yanagimoto Seisakusho, and sulfur was measured using a flask combustion method.

(4) Refractive index (nDzo) The refractive index at 20° C. was measured using an Asohe refractometer (model 3T) manufactured by Atago.

Further, various physical properties of the high refractive index resins obtained in the examples were measured by the following test methods.

+11 Refractive index (n, zo), Atsube number (v) The refractive index and Atsube number at 20° C. were measured using an Atsube refractometer (Model 3T) manufactured by Atago ■. Bromonaphthalin was used as the contact liquid.

(2) Appearance Measured visually.

(3) Place the sample in a long-life xenon fade meter (FAC-25AX-HC type) manufactured by Weather Resistance Suga Test Instruments, and
After being exposed to xenon light for 00 hours, the degree of coloring of the sample was visually observed, and samples with a lower degree of coloring than polystyrene were evaluated with ○, those with the same degree of coloring were △, and those with high coloring were evaluated with ×.

(4) Impact resistance 127cm on a disk-shaped sample plate with a thickness of 2mm and a diameter of 65mm.
A steel ball of a predetermined weight was allowed to fall naturally from a height of 0, and the weight of the steel ball that would prevent the sample plate from being damaged was measured. The results were evaluated as A to E according to the criteria shown in Table 1.

Table 1 (5) Adhesion of hard coat film A plate-shaped resin sample was thoroughly washed with methanol and air-dried to a clear state, and then immersed in a 10% aqueous sodium hydroxide solution for 10 minutes.

Next, the sample was pretreated by washing with water and drying.

-4, 20 parts by weight of bis(T-triethoxysilylpropyl) carbonate, 10 parts by weight of T-glycidoxypropyltrimethoxysilane, 30 parts by weight of colloidal silica (methanol sol manufactured by Nissan Chemical Co., Ltd.), methyl cellosolve 3
0 parts by weight, 10 parts by weight of 0.05N hydrochloric acid, and 0.25 parts by weight of ammonium perchlorate were thoroughly mixed to prepare a hard coat liquid. The pretreated sample was immersed in this hard coat solution, thoroughly air-dried at room temperature, and then heated to 80°C for 30 minutes.
The coating was cured by heating for a period of time. The adhesion of the obtained film was evaluated by the following test method. Use a cutter knife with a sharp tip to cut 100 lun x l crane squares on the surface of the sample.
After applying each piece, commercially available cellophane tape was applied and then quickly peeled off, and the state of peeling of the film was visually observed.
Evaluation was made based on the number of squares remaining without peeling.

In addition, some of the monomers used in the following examples are represented by the following symbols. However, the number in [ ] is the refractive index of the homopolymer.

Br3PMA: 2. 4. 6 t”ribromophenyl methacrylate (1,625) czst: chlorostyrene (0 body, m
mixture) (1,610) VDF: 2-vinyldibenzofuran [1
,679) Br2St: dibromostyrene C1,6
57) BBMEPP: 2,2-bis(3,5-
Dibromo-4-methacryloyloxyethoxyphenyl)propane (1,600) BMEPP: 2,2-bis(4-methacryloyloxyethoxyphenyl)propane [1,558] BTM: Benzylthiomethacrylate (
1,620) DEGM: diethylene glycol dimethacrylate [1,508) SL: styrene (1,590) Example 1 In a three-hole flask equipped with a thermometer, stirrer and dropping a, 2-phenylethylthioethyl was added. Thiol 19.9
g (0,10 mo#) and 7.9 g of pyridine (0,10 mo#)
moff) and 100 drops of anhydrous chloroform, and cooled to 0°C.
It was cooled to Methacrylic acid chloride 10 while stirring
．． 5 g (0.10 mojN) was gradually added dropwise. At this time, the reaction temperature was maintained at 0 to 5 °C, and after the completion of the dropwise addition, an additional 20 mojN was added dropwise.
The mixture was stirred at ℃ for 1 hour. Then, pour the reaction mixture into water,
After washing the organic layer with a dilute aqueous sodium carbonate solution, it was washed with water. After drying the mN with anhydrous magnesium sulfate and distilling off the solvent under reduced pressure, the obtained oil was distilled under reduced pressure to obtain the target 2-phenylethyl 1,000 nityl thiomethacrylate with a boiling point of 134-138°C (0 ,04關Hg
) was obtained as a colorless transparent liquid in an amount of 18.7 g. The refractive index of this material was 1.579. The IR chart of this product is shown in FIG. A strong carbonyl group was observed at 1670an-', and absorption based on a terminal double bond was observed at 1640cm+-'. Further, a chart of 'H-NMR (CDCA, in solvent, based on tetramethylsilane, ppm) is shown in FIG. At 61.93, three peaks derived from the hydrogen fc) of the methyl group appear as a doublet with a coupling constant of 2 Hz, and 62
．． Hydrogen (d), (e), i of methylene group in 3 to 63.3
f), [8 peaks derived from gl are a multiplet, one peak derived from hydrogen (a) of the vinylidene group is a multiplet around 65.56, and a vinylidene group is around δ6.05. One peak derived from the hydrogen (b) of the phenyl group was measured as a multiplet, and five peaks derived from the hydrogen (fh) of the phenyl group were measured as a multiplet near δ7.1.

In addition, the elemental analysis values (the values in parentheses are calculated values) are C:
63.32% (63.11%), H: 6.99% (6
, 81%), S: 23.93% (24,07%
), which was in good agreement with the calculated value.

Examples 2 to 8 The thiocarboxylic acid ester compounds shown in Table 2 were obtained in exactly the same manner as in Example 1 using various raw materials. The properties of the obtained thiocarboxylic acid ester compound are also listed in Table 2.

Example 9 1 part by weight of t-butylperoxy-2-ethylhexanate as a radical polymerization initiator was added to 100 parts by weight of the thiocarboxylic acid ester compounds produced in Examples 1 to 8 and mixed well. This mixed solution was poured into a mold consisting of a glass plate and a gasket made of ethylene-vinyl acetate copolymer, and cast polymerization was performed. Polymerization was carried out using an air oven, and the temperature was gradually raised from 30°C to 90''C over 18 hours, and the temperature was maintained at 90°C for 2 hours. After the polymerization was completed, the mold was taken out of the air oven and left to cool. The polymer was removed from the glass mold.The various physical properties of the obtained polymer were measured and are shown in Table 3.

Comparative Examples 1-2 Methyl thiomethacrylate and methacrylic acid 2 as brush strokes
- The same procedure as Example 9 was carried out except that methylthioethyl was used. Various physical properties of the obtained polymer are also listed in Table 3.

Example 10 The same procedure as Example 9 was carried out except that a composition consisting of the thiocarboxylic acid ester compound shown in Table 4 and a monomer copolymerizable therewith was used. The physical properties of the obtained polymer were
Shown in the table.

[Brief explanation of drawings]

1 and 2 show the infrared absorption spectrum and the 'H-nuclear magnetic resonance spectrum of the thiocarboxylic acid ester compound of the present invention obtained in Example 1, respectively.

Claims (2)

[Claims] (1) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R^1 is a hydrogen atom or a methyl group, and R^2 and R^3 are the same or different hydrogen atoms or alkyl groups, respectively. , R^4 is an alkylene group having 2 to 5 carbon atoms, and R^5 is a substituted or unsubstituted aryl group. A thiocarboxylic acid ester compound represented by (2) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R^2 and R^3 are the same or different hydrogen atoms or alkyl groups, respectively, and R^4 is an alkylene having 2 to 5 carbon atoms. R^5 is a substituted or unsubstituted aryl group. There are compounds represented by the following formula ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [However, R^1 is a hydrogen atom or a methyl group, and R^6
is a hydroxyl group, a chlorine atom or an alkoxy group. ] The method for producing a thiocarboxylic acid ester compound according to claim (1), which comprises reacting with a compound represented by the following.