JP2017190326A - (meth) acrylate and method for producing the same, and (co) polymer thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel (meth) acrylate for dilution having a low viscosity and a high refractive index, a homopolymer of which has high heat resistance.SOLUTION: The present invention relates to a (meth) acrylate represented by the following formula (1), a homopolymer of the (meth) acrylate or a copolymer of the (meth) acrylate and another monomer (in the formula, Ris an alkyl group having carbon atoms of one or more and four or less, and Ris a hydrogen atom or a methyl group).SELECTED DRAWING: None

Description

  The present invention relates to a novel (meth) acrylic acid ester and a method for producing the same. The present invention also relates to a homopolymer or copolymer of the (meth) acrylic acid ester.

For transparent optical members such as camera lenses, eyeglass lenses, optical fibers, and prism sheets, a resin having better processability is used instead of glass. Among these, polymers of monomers such as styrene and (meth) acrylic acid esters are particularly widely used because of their excellent transparency. As the demands for smaller, lighter, and thinner transparent optical members increase, it is becoming essential to increase the refractive index of transparent optical members. On the other hand, in applications such as mobile phones and automobiles, transparent optical members have been used so far. The above heat resistance is required. In order to realize a polymer having a high refractive index and a high heat resistance, it is desirable that each component of the monomer contained as a raw material has a high refractive index and a high heat resistance of the homopolymer.
Di (meth) acrylic acid esters having a plurality of aromatic rings have been proposed as monomers having a high refractive index and a high heat resistance of the homopolymer. For example, dimethacrylic acid ester having a bisphenol skeleton (Patent Document 1) and diacrylic acid ester having a fluorene skeleton (Patent Documents 2 to 4) are known. However, since such di (meth) acrylic acid ester having a plurality of aromatic rings is a solid at room temperature or a liquid having a very high viscosity, in order to treat it as a monomer solution containing a polymerization initiator, It is necessary to dilute with the monomer.
It is desirable that the monomer for dilution has a low viscosity, a high refractive index, and a high heat resistance of the homopolymer. As such a monomer, acrylate-o-phenylphenoxyethyl acrylate has been proposed (Patent Document 5). However, acrylic acid-o-phenylphenoxyethyl has a high viscosity, and its homopolymer has a low glass transition temperature.
In addition, naphthylmethyl (meth) acrylate has been proposed (Patent Document 6). However, as a result of confirmation by the present inventors, a monomer solution containing naphthylmethyl (meth) acrylate has a tendency to increase in viscosity, and a copolymer thereof tends to decrease in transparency.
Recently, 4- (methylthio) benzyl methacrylate has been proposed as a high refractive index monomer (Non-patent Document 1). However, the present inventors have confirmed that the glass transition temperature of the homopolymer of methacrylic acid-4- (methylthio) benzyl is low.
Therefore, low viscosity, high refractive index and high heat resistance of the homopolymer, (meth) acrylic acid ester for dilution, and (meth) acrylic acid ester which can be suitably used as a transparent optical member (Co) polymers are strongly desired.

Japanese Patent Laid-Open No. 55-13747 JP-A-4-325508 JP 2007-84815 A International Publication Number WO2005 / 033061 JP 2008-94987 A JP 08-26349 A

Polymer Journal, 42, 249-255, 2010.

  Accordingly, the present invention provides a novel (meth) acrylic acid ester for dilution, a (co) polymer of the (meth) acrylic acid ester, and a low viscosity, high refractive index and high heat resistance of the homopolymer. The main purpose is to provide.

In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, they have found that the above object can be achieved by a specific novel compound, and have completed the present invention.
The present invention relates to a (meth) acrylic acid ester represented by the following formula (1).
In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms. R ² represents a hydrogen atom or a methyl group.
Moreover, this invention relates to the homopolymer of said (meth) acrylic acid ester, or the copolymer of the (meth) acrylic acid ester and another monomer.

  According to the present invention, there are provided a novel (meth) acrylic acid ester for dilution and a (co) polymer of the (meth) acrylic acid ester having a low viscosity, a high refractive index and a high heat resistance of the homopolymer. can do.

It is the spectrum of the ¹ H one-dimensional mode of the ¹ H-NMR of the methacrylic acid-1- [4- (methylthio) phenyl] ethyl obtained in Example 1. It is the spectrum of ¹³ C one-dimensional mode of ¹³ C-NMR of methacrylic acid-1- [4- (methylthio) phenyl] ethyl obtained in Example 1. 1 is a GC-MS mass spectrum of methacrylic acid-1- [4- (methylthio) phenyl] ethyl obtained in Example 1. It is the spectrum of 1H one-dimensional mode of 1H-NMR of acrylic acid-1- [4- (methylthio) phenyl] ethyl obtained in Example 4. 13 is a 13C one-dimensional mode spectrum of 13C-NMR of acrylic acid-1- [4- (methylthio) phenyl] ethyl obtained in Example 4. FIG. 4 is a GC-MS mass spectrum of acrylic acid-1- [4- (methylthio) phenyl] ethyl obtained in Example 4. 1 is a 1H one-dimensional mode spectrum of 1H-NMR of methacrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 5. FIG. 13 is a 13C one-dimensional mode spectrum of 13C-NMR of methacrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 5. FIG. 2 is a GC-MS mass spectrum of methacrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 5. FIG. 1 is a 1H one-dimensional mode spectrum of 1H-NMR of acrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 6. FIG. 13 is a 13C one-dimensional mode spectrum of 13C-NMR of acrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 6. FIG. 4 is a GC-MS mass spectrum of acrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 6.

  In this specification, acrylic acid and methacrylic acid are combined into “(meth) acrylic acid”, acrylic acid ester and methacrylic acid ester are combined into “(meth) acrylic acid ester”, acryloyl group and methacryloyl group are combined into “( "Meth) acryloyl group". Further, the radical polymerizable monomer is referred to as “monomer”, homopolymerization and copolymerization are referred to as “polymerization”, and the homopolymer and copolymer are referred to as “(co) polymer”.

(I) (Meth) acrylic acid ester of the present invention The present invention relates to a (meth) acrylic acid ester represented by the formula (1).
In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms. When the carbon number is 1 or more, the heat resistance of the (co) polymer is improved. When the number of carbon atoms is 4 or less, the monomer has sufficient polymerizability. In view of ease of production and physical properties, R ¹ is preferably a methyl group having 1 carbon atom or an ethyl group having 2 carbon atoms. R ² represents a hydrogen atom or a methyl group. In consideration of the viscosity, refractive index, and ease of photopolymerization, R ² is preferably a hydrogen atom, and in view of the heat resistance of the (co) polymer, R ² is preferably a methyl group.
Examples of the (meth) acrylic acid ester of the present invention represented by the formula (1) include (meth) acrylic acid-1- [2- (methylthio) phenyl] ethyl, (meth) acrylic acid-1- [3- (Methylthio) phenyl] ethyl, (meth) acrylic acid-1- [4- (methylthio) phenyl] ethyl, (meth) acrylic acid-1- [2- (methylthio) phenyl] propyl, (meth) acrylic acid-1 -[3- (methylthio) phenyl] propyl, (meth) acrylic acid-1- [4- (methylthio) phenyl] propyl, (meth) acrylic acid-1- [2- (methylthio) phenyl] butyl, (meth) Acrylic acid-1- [3- (methylthio) phenyl] butyl, (meth) acrylic acid-1- [4- (methylthio) phenyl] butyl, (meth) acrylic acid-2-methyl- -[2- (methylthio) phenyl] propyl, (meth) acrylic acid-2-methyl-1- [3- (methylthio) phenyl] propyl, (meth) acrylic acid-2-methyl-1- [4- (methylthio) ) Phenyl] propyl, (meth) acrylic acid-1- [2- (methylthio) phenyl] pentyl, (meth) acrylic acid-1- [3- (methylthio) phenyl] pentyl, (meth) acrylic acid-1- [ 4- (methylthio) phenyl] pentyl, (meth) acrylic acid-2-methyl-1- [2- (methylthio) phenyl] butyl, (meth) acrylic acid-2-methyl-1- [3- (methylthio) phenyl ] Butyl, (meth) acrylic acid-2-methyl-1- [4- (methylthio) phenyl] butyl, (meth) acrylic acid-2,2-dimethyl-1- [2- (methyl) E) Phenyl] propyl, (meth) acrylic acid-2,2-dimethyl-1- [3- (methylthio) phenyl] propyl, (meth) acrylic acid-2,2-dimethyl-1- [4- (methylthio) Phenyl] propyl and the like.

(B) Production of (meth) acrylic acid ester As a production method of the (meth) acrylic acid ester of the present invention, a compound represented by formula (2) (hereinafter referred to as “compound of formula (2)”) is carbon. A compound represented by the formula (3) (hereinafter referred to as “compound of the formula (3)”) produced by the action of an organometallic compound having an alkyl group of 1 to 4 is a (meth) acrylic acid derivative. The method of esterifying is mentioned.
In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms.

Examples of the compound of the formula (2) include 2- (methylthio) benzaldehyde, 3- (methylthio) benzaldehyde, and 4- (methylthio) benzaldehyde.
In order to produce the compound of the formula (3) from the compound of the formula (2), it is preferable that an organometallic compound having an alkyl group having 1 to 4 carbon atoms is allowed to act on the compound of the formula (2). Examples of the organometallic compound having an alkyl group having 1 to 4 carbon atoms that acts on the compound of formula (2) include methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, butyl lithium, s-butyl lithium, t- Alkyl lithium compounds such as butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, isopropyl magnesium bromide, isopropyl magnesium chloride, butyl magnesium chloride, s-butyl magnesium bromide, Alkylmagnesium compounds such as s-butylmagnesium chloride and t-butylmagnesium chloride , Alkyl zinc compounds, such as methyl zinc chloride, alkyl titanium compounds such as dimethyl titanium dichloride and the like. Of these, alkylmagnesium compounds are particularly preferred because they are readily available and easy to handle. When the alkylmagnesium compound is allowed to act on the compound of the formula (2), the reaction temperature is preferably −10 to 50 ° C. from the viewpoint of the reaction rate, and the molar ratio of the compound of the formula (2): the alkylmagnesium compound is 1: 0. 1-2.0 are preferable and 1: 0.4-1.8 are more preferable. As the reaction solvent, diethyl ether, tetrahydrofuran, toluene, a mixed solvent thereof or the like is preferable from the viewpoint of solubility of the alkylmagnesium compound, and tetrahydrofuran is particularly preferable because it is easily available and easy to handle.

Examples of the compound of the formula (3) thus produced include 1- [2- (methylthio) phenyl] ethanol, 1- [3- (methylthio) phenyl] ethanol, 1- [4- (methylthio) Phenyl] ethanol, 1- [2- (methylthio) phenyl] propal, 1- [3- (methylthio) phenyl] propal, 1- [4- (methylthio) phenyl] propal, 1- [2- (methylthio) ) Phenyl] butanol, 1- [3- (methylthio) phenyl] butanol, 1- [4- (methylthio) phenyl] butanol, 2-methyl-1- [2- (methylthio) phenyl] propal, 2-methyl- 1- [3- (methylthio) phenyl] propal, 2-methyl-1- [4- (methylthio) phenyl] propal, 1- [2- (methylthio) ) Phenyl] pentanol, 1- [3- (methylthio) phenyl] pentanol, 1- [4- (methylthio) phenyl] pentanol, 2-methyl-1- [2- (methylthio) phenyl] butanol, -2 -Methyl-1- [3- (methylthio) phenyl] butanol, 2-methyl-1- [4- (methylthio) phenyl] butanol, 2,2-dimethyl-1- [2- (methylthio) phenyl] propanol, 2 , 2-dimethyl-1- [3- (methylthio) phenyl] propanol, 2,2-dimethyl-1- [4- (methylthio) phenyl] propanol, and the like.
In order to produce the (meth) acrylic acid ester of the present invention from the compound of the formula (3), it is preferable to esterify the compound of the formula (3) with a (meth) acrylic acid derivative.

  Examples of (meth) acrylic acid derivatives used in esterification include (meth) acrylic acid halide, (meth) acrylic anhydride, (meth) acrylic acid, (meth) acrylic acid ester, etc. In view of recoverability of reaction raw materials and by-products and waste disposal, esterification with (meth) acrylic acid ester, that is, transesterification is particularly preferable.

  When performing the transesterification reaction, a catalyst for the transesterification reaction is used. Examples of the transesterification catalyst used at this time include hydroxides of alkali metals such as lithium, sodium and potassium, oxides of alkaline earth metals such as carbonates, hydrogen carbonates, magnesium and calcium, and hydroxides. , Carbonate, lithium methoxide, sodium methoxide, sodium ethoxide, alkali metal alkoxides such as potassium t-butoxy, alkali metal amides such as lithium amide, sodium amide, potassium amide, titanium tetramethoxide, titanium tetraiso Propoxide, Titanium tetrabutoxide, Zirconium tetraethoxide, Zirconium tetraisopropoxide, Zirconium tetrabutoxide and other group 4A metal alkoxides, Titanium oxydiacetylacetonate, Zirconium tetraacetylacetonate 4A genus metal acetylacetonate etc., dibutyltin oxide, dialkyltin oxide, and the like, such as dioctyl tin oxide. Among them, 4A group metal alkoxide and 4A group metal acetylacetonate are particularly preferable because they are highly active, easily available, and easy to handle.

  When 4A group metal alkoxide or 4A group metal acetylacetonate is used as a catalyst for transesterification reaction, the compound of formula (3): (meth) acrylic, considering the reaction rate and recovery of unreacted raw materials and by-products The molar ratio of acid ester: catalyst is preferably 1: 1.5-20: 0.0001-0.05, more preferably 1: 2.0-6: 0.0005-0.03. Examples of the (meth) acrylic acid ester used in this case include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic acid-i-propyl, and (meth) acrylic. Examples include butyl acid, (meth) acrylic acid-i-butyl, (meth) acrylic acid-s-butyl, and (meth) acrylic acid-t-butyl. Among these, methyl (meth) acrylate is particularly preferable in view of recoverability of alcohol as a by-product and availability. The reaction temperature is preferably −30 to 180 ° C. in consideration of the reaction rate, and more preferably 60 to 150 ° C. in consideration of accelerating the reaction rate excluding by-product alcohol.

  In order to prevent polymerization of the obtained (meth) acrylic acid ester of the present invention under high temperature conditions, it is preferable to react in the presence of a polymerization inhibitor, and to react while bubbling oxygen-containing gas. Is preferred. It is more preferable to use both a polymerization inhibitor and oxygen bubbling because polymerization can be prevented more strongly.

Examples of the polymerization inhibitor include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 4,4′-thiobis (6 Phenolic compounds such as -t-butyl-m-cresol); amine compounds such as N, N'-bis (2-naphthyl) -1,4-phenylenediamine; 4-hydroxy-2,2,6,6 -Tetramethylpiperidine-N-oxyl, 4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, N-oxyl compounds such as 4,4 ′-[1,2-phenylenebis (carbonyloxy)] bis [2,2,6,6-tetramethylpiperidine-N-oxyl] And the like. Among these, in order to prevent polymerization during the reaction, an N-oxyl polymerization inhibitor or the like is preferable. When the catalyst is deactivated and removed by purification after the reaction, for example, 4-methoxyphenol, 2, Phenol compounds such as 6-di-t-butyl-4-methylphenol are preferred.
One of these polymerization inhibitors can be used alone, or two or more thereof can be used in combination. The amount of the polymerization inhibitor used in the present invention (the total amount when two or more polymerization inhibitors are used in combination) can be appropriately selected according to the reaction conditions and the like.

  Further, the type of gas used for bubbling is not limited, and a gas containing oxygen is preferable because it exhibits a polymerization preventing effect. Among them, air is more preferable because it is inexpensive and exhibits a polymerization preventing effect. The flow rate at the time of bubbling is not limited, and can be appropriately selected according to reaction conditions and the like.

The (meth) acrylic acid ester of the present invention can be purified using a known method such as silica gel column chromatography or vacuum distillation.
In addition, also in the vacuum distillation in refining, in order to prevent superposition | polymerization by high temperature, the said polymerization inhibitor can be used or the gas containing oxygen can be bubbled. The polymerization inhibitor used for preventing polymerization during distillation is preferably an N-oxyl polymerization inhibitor, and among them, 4,4 ′-[1,2-phenylenebis (carbonyloxy)] having a high boiling point. Bis [2,2,6,6-tetramethylpiperidine-N-oxyl] is particularly preferred because it can avoid mixing into the distillate.

  The (meth) acrylic acid ester of the present invention obtained as described above has a viscosity that is lower or substantially the same as that of a conventional high refractive index monomer for dilution, and the refractive index is substantially the same. And the glass transition temperature of the homopolymer is high.

(C) (Co) polymer A (co) polymer can be obtained by polymerizing the (meth) acrylic acid ester of the present invention obtained as described above.
The method for producing the (co) polymer is not particularly limited, and examples thereof include bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, and precipitation polymerization. Among them, a method of carrying out the polymerization reaction by holding a monomer solution in which a monomer and a polymerization initiator are mixed in advance at a constant temperature, which is a kind of bulk polymerization, is preferable because it is simple.

  When producing a copolymer using the (meth) acrylic acid ester of the present invention, the type of monomer other than the (meth) acrylic acid ester of the present invention is not particularly limited, and the desired type of copolymer It can be selected as appropriate according to the conditions.

  Examples of monomers other than (meth) acrylic acid esters include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid-i. -Propyl, butyl (meth) acrylate, -i-butyl (meth) acrylate, -s-butyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, (meth) Hexyl acrylate, (meth) acrylate-2-ethylhexyl, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, ( (Meth) acrylic acid lauryl, (meth) acrylic acid tridecyl, (meth) acrylic acid cetyl, (meth) acrylic acid stearyl, Isostearyl (meth) acrylate, behenyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, (meth) acrylic acid Nonylphenoxypolyethylene glycol, cyclohexyl (meth) acrylate, (3,3,5-trimethylcyclohexyl), (meth) acrylic acid-4-t-butylcyclohexyl, (meth) acrylic acid dicyclopentenyl, ( Dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxyethylene (meth) acrylate Glycol, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( (Meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, (meth) acrylic acid-4-hydroxybutyl, glycidyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane 2- (meth) acryloyloxyethyl acid phosphate, a reaction product of 6-hexanolide addition polymer of (meth) acrylic acid-2-hydroxyethyl and phosphoric anhydride, (meth) acrylic acid-2-ethylhexyl diethylene glycol, Acryloylmorpholine, aqua Monofunctional monomers such as rilonitrile, acrylamide, dimethylacrylamide, styrene, α-methylstyrene, and vinyl acetate; ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, di (meth) acrylic acid 1,3-propylene glycol, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylic acid-1,3-butylene glycol, di (meth) acrylic acid-1,4 -Butylene glycol, poly (butylene glycol) di (meth) acrylate, di (meth) acrylic acid-3-methyl-1,5-pentanediol, di (meth) acrylic acid-1,6-hexanediol, di (meth) Acrylic acid-1,9-nonanediol, di (meth) acrylic acid-1,1 -Decanediol, di (meth) acrylic acid-1,4-cyclohexanedimethanol, di (meth) acrylic acid tricyclodecane dimethylol, di (meth) acrylic acid polycarbonate diol, di (meth) acrylic acid polyester diol, epsilon -Caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate, 2,2-bis [4-((meth) acryloyloxy) phenyl] propane, 2,2-bis [4-((meth) acryloyloxypolyethoxy) ) Phenyl] propane, 2,2-bis [4-((meth) acryloyloxypolypropoxy) phenyl] propane, 1,1-bis [4-((meth) acryloyloxy) phenyl] methane, 1,1-bis [4-((meth) acryloyloxypolyethoxy) phenyl] methane, 1, -Bis [4-((meth) acryloyloxy) phenyl] ethane, 2,2-bis [4-((meth) acryloyloxy) phenyl] butane, 1,1-bis [4-((meth) acryloyloxy) Phenyl] cyclohexane, 1,1-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] cyclohexane, 1,1-bis [4-((meth) acryloyloxy) phenyl] -1-phenylethane, 1 , 1-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] -1-phenylethane, 9,9-bis [4-((meth) acryloyloxy) phenyl] fluorene, 9,9-bis [ 4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4-((meth) acryloyloxy) phenyl] sulfur Bis [4- (2- (meth) acryloyloxyethoxy) phenyl] sulfide bis [4-((meth) acryloyloxy) phenyl] sulfone, bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] Bifunctional monomer such as sulfone, bis [4-((meth) acryloylthio) phenyl] sulfide, bis [4- (2- (meth) acryloylthioethoxy) phenyl] sulfide, butadiene; tri (meth) Trifunctional such as trimethylolpropane acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, tris (2- (meth) acryloyloxyethyl) isocyanurate Monomer; Ditrimethylotetra (meth) acrylate Tetrafunctional monomers such as propane propane and tetra (meth) acrylate pentaerythritol; pentafunctional monomers such as dipentaerythritol penta (meth) acrylate; hexafunctional such as dipentaerythritol hexa (meth) acrylate And the like. These monomers may be used individually by 1 type, and may use 2 or more types together.

  When a copolymer is produced, a copolymer having a high refractive index and high heat resistance can be produced by using a monomer having a high refractive index and a high heat resistance of the homopolymer. A monomer having a high refractive index and a high heat resistance of the homopolymer used here is a bifunctional or higher monomer having a plurality of aromatic rings, for example, 2,2-bis [4-(( (Meth) acryloyloxy) phenyl] propane, 2,2-bis [4-((meth) acryloyloxypolyethoxy) phenyl] propane, 2,2-bis [4-((meth) acryloyloxypolypropoxy) phenyl] propane 1,1-bis [4-((meth) acryloyloxy) phenyl] methane, 1,1-bis [4-((meth) acryloyloxypolyethoxy) phenyl] methane, 1,1-bis [4- ( (Meth) acryloyloxy) phenyl] ethane, 2,2-bis [4-((meth) acryloyloxy) phenyl] butane, 1,1-bis [4-((meth) acryloyloxy) ) Phenyl] cyclohexane, 1,1-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] cyclohexane, 1,1-bis [4-((meth) acryloyloxy) phenyl] -1-phenylethane, 1,1-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] -1-phenylethane, 9,9-bis [4-((meth) acryloyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4-((meth) acryloyloxy) phenyl] sulfide, bis [4- (2- (meth) acryloyloxyethoxy) phenyl] sulfide, Bis [4-((meth) acryloyloxy) phenyl] sulfone, bis [4- (2- (meth) acrylic Yl) phenyl] sulfone, bis [4 - ((meth) acryloylthio) phenyl] sulfide, bis [4- (2- (meth) acryloylthio) phenyl] sulfide, and the like. Among these, 9,9-bis [4- (2- (meth)) is a 9,9-bis [4- (meta)] because it can efficiently produce a copolymer having a high refractive index and high heat resistance, is easily available, and is easy to handle. Acrylyloxyethoxy) phenyl] fluorene is particularly preferred.

  The content of the bifunctional or higher monomer having a plurality of aromatic rings is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and more preferably 30 to 70 parts by mass in 100 parts by mass of the total amount of monomer components. Is more preferable. If the content of the bifunctional or higher monomer having a plurality of aromatic rings is 10 parts by mass or more, the refractive index and heat resistance of the copolymer can be increased, and if the content is 90 parts by mass or less. For example, the viscosity of the monomer solution can be lowered.

  When a copolymer having a high refractive index and a high heat resistance is produced using the (meth) acrylic acid ester of the present invention and a monomer having two or more functional rings and a plurality of aromatic rings, the (meth) of the present invention The content of the acrylic ester is preferably 10 to 90 parts by mass in 100 parts by mass of the total amount of the monomer components. If the content of the (meth) acrylic acid ester of the present invention is 10 parts by mass or more, the viscosity of the monomer solution can be lowered, and if the content is 90 parts by mass or less, the refraction of the copolymer The rate and heat resistance can be increased.

  In the total amount of monomer components of 100 parts by mass, the total amount of the (meth) acrylic acid ester of the present invention and the bifunctional or more monomer having a plurality of aromatic rings is preferably 70 parts by mass or more. More preferably, it is 80 parts by mass or more. If the total amount of the (meth) acrylic acid ester of the present invention and the bifunctional or more monomer having a plurality of aromatic rings is 70 parts by mass or more, the refractive index and heat resistance of the copolymer may be increased. it can.

When producing a copolymer having a high refractive index and a high heat resistance, in addition to the (meth) acrylic acid ester of the present invention and a monomer having two or more functional and plural aromatic rings, further viscosity of the monomer solution In order to suppress the reduction, the coloration of the copolymer, and the weight loss during the heating of the copolymer, another monomer may be contained.
As such a monomer, the viscosity of the monomer solution can be greatly reduced while maintaining the high refractive index and high heat resistance of the copolymer, so that phenyl (meth) acrylate, (meth) Preferred are benzyl acrylate, phenoxyethyl (meth) acrylate, and the like.

The polymerization initiator used for the polymerization is not particularly limited, and can be appropriately selected according to the type of monomer, reaction conditions, and the like. Examples of the polymerization initiator include radical polymerization initiators, and are classified into photopolymerization initiators, thermal polymerization initiators, peroxides used for redox polymerization, and the like, depending on the mode of polymerization initiation.
The photopolymerization initiator is a radical polymerization initiator used for photopolymerization. Examples of the photopolymerization initiator include benzophenone-type compounds such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone; t-butylanthraquinone, 2-ethylanthraquinone Anthraquinone type compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, benzyl Dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methylpropi Nyl) benzyl] phenyl} -2-methylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and other alkylphenone type compounds; diethylthioxanthone, isopropylthioxanthone, etc. 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- And acylphosphine oxide type compounds such as phenylphosphine oxide; phenylglyoxylate type compounds such as phenylglyoxylic acid methyl ester. Among them, alkylphenone type compounds are preferable in that coloring of the (co) polymer can be suppressed. Among them, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone Is particularly preferred. Further, an acylphosphine oxide type compound is preferable in that it can be easily polymerized to the inside of the (co) polymer, and among them, 2,4,6-trimethylbenzoyl is preferable in that coloring of the (co) polymer can be suppressed. Diphenylphosphine oxide is particularly preferred. These photopolymerization initiators may be used alone or in combination of two or more.

The thermal polymerization initiator is a radical polymerization initiator used for thermal polymerization. Examples of the thermal polymerization initiator include organic peroxides and azo compounds.
Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide; 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) ) Peroxyketals such as cyclohexane and 1,1-di (t-butylperoxy) cyclohexane; 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, [2- (4-methylcyclohexyl) ) Propan-2-yl] hydroperoxide such as hydroperoxide; dialkyl peroxide such as dicumyl peroxide and di-t-butyl peroxide; diacyl peroxide such as dilauroyl peroxide and dibenzoyl peroxide; (4-t-butylcyclohexyl) peroxydicarbo Peroxydicarbonates such as nate, di (2-ethylhexyl) peroxydicarbonate; t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxybenzoate, 1, And peroxyesters such as 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate.

  Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1 1, 1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate and the like.

These thermal polymerization initiators may be used alone or in combination of two or more.
As the thermal polymerization initiator, an organic peroxide is preferable because bubbles are not easily generated in the (co) polymer. Considering the balance between the polymerization time of the monomer solution and the pot life, the 10-hour half-life temperature of the organic peroxide is preferably in the range of 35 ° C to 80 ° C, and preferably in the range of 40 to 75 ° C. More preferably, it is further in the range of 45 ° C to 70 ° C. If the 10-hour half-life temperature is 35 ° C. or higher, the monomer solution is difficult to gel at room temperature, and the pot life is improved. On the other hand, if the 10-hour half-life temperature is 80 ° C. or less, the polymerization time of the monomer solution can be shortened. Examples of such organic peroxides include 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (10 hour half-life temperature 65 ° C.), t-butylperoxy-2-ethylhexa Noate (10-hour half-life temperature 72 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (10-hour half-life temperature 41 ° C.) and the like.

The redox polymerization initiator is a radical polymerization initiator used for redox polymerization, and is a polymerization initiator using a peroxide and a reducing agent in combination. Examples of the peroxide used for redox polymerization include dibenzoyl peroxide and hydroperoxide. These peroxides may be used alone or in combination of two or more. In the case where the above-described peroxide is used as a redox polymerization initiator, an example of a combination with a reducing agent is as follows.
(1) Dibenzoyl peroxide (peroxide) and aroma such as N, N-dimethylaniline, 4-dimethylaminotoluene, 1,1 ′-[(4-methylphenyl) imino] bis (2-propanol) Combination with group III tertiary amines (reducing agents).
(2) A combination of hydroperoxide (peroxide) and metal soap (reducing agent).
(3) A combination of hydroperoxide (peroxide) and thioureas (reducing agent).

  The content of the polymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and 0.1 to 3 parts by mass with respect to 100 parts by mass of the total amount of the monomer components. Further preferred. If content of a polymerization initiator is 0.01 mass part or more, the polymerizability of a monomer solution will improve. On the other hand, when the content of the polymerization initiator is 10 parts by mass or less, the transparency of the (co) polymer is improved.

The monomer solution preferably further contains an antioxidant. When the monomer solution contains an antioxidant, coloring due to oxidation of the (co) polymer can be suppressed. Further, when the (co) polymer passes through a heat treatment step such as solder reflow, coloring due to heating during passage can be suppressed.
Examples of the antioxidant include 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, and octadecyl-3- (3 ′, 5′-di-t-butyl-4. '-Hydroxyphenyl) propionate, tetrakis- [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, triethylene glycol bis [3- (3-t-butyl Phenolic antioxidants such as -5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; Phenyl phosphite, trisisodecyl phosphite, tristridecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite Phosphorous antioxidants of: dihexyl sulfide, dilauryl 3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, disteryl 3,3′-thio And sulfur-based antioxidants such as dipropionate and pentaerythritol tetrakis (β-laurylthiopropionate). Of these, sulfur-based antioxidants and phosphorus-based antioxidants are preferred because of their high solubility in monomer solutions and high effects of suppressing the coloration of (co) polymers. These antioxidants may be used alone or in combination of two or more.
The content of the antioxidant is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 4 parts by mass, and 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the monomer components. Further preferred. If the content of the antioxidant is 0.01 parts by mass or more, the coloration due to oxidation of the (co) polymer and the coloration due to heating during reflow tend to be further suppressed, and the content of the antioxidant is 5 masses. If it is at most parts, the transparency of the (co) polymer tends to be higher.

  The monomer solution can also contain a chain transfer agent in order to control the molecular weight of the (co) polymer. Examples of the chain transfer agent include mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan, and α-methylstyrene dimer.

  As long as the monomer solution is within the range not impairing the effects of the present invention, the (meth) acrylic acid ester of the present invention, a bifunctional or more monomer having a plurality of aromatic rings, other monomers, polymerization You may contain other components (henceforth "other components") other than an initiator, antioxidant, and a chain transfer agent.

  Examples of other components include various additions such as acrylic polymers, rubber, silica fine particles, plasticizers, ultraviolet absorbers, antifoaming agents, thixotropic agents, polymerization inhibitors, mold release agents, fillers, phosphors, and pigments. Agents.

  As a method for producing a monomer solution, for example, the (meth) acrylic acid ester of the present invention, a monomer having two or more functional aromatic rings, other monomers, a polymerization initiator, an antioxidant, Examples thereof include a method of stirring and mixing other components at room temperature, a method of heating and mixing these components, and the like.

  In the case of using a thermal polymerization initiator as a polymerization initiator, in consideration of the stability of the monomer solution, the (meth) acrylic acid ester of the present invention, a bifunctional or higher-functional monomer having multiple aromatic rings, Accordingly, it is preferable to heat and mix other monomer components, antioxidants, and other components and then cool, add a thermal polymerization initiator at room temperature, and stir and mix to obtain a monomer solution.

  In the case of producing a monomer solution by heating and mixing, the compatibility is good and the mixture can be mixed more uniformly. Therefore, it is preferable to mix under heating at 40 to 100 ° C. The mixing stirring time is 0.1 to 5 It is preferably in the time range.

The viscosity of the monomer solution is preferably in the range of 100 to 50,000 mPa · s, measured using a single cylindrical rotary viscometer at 23 ° C., and in the range of 500 to 30,000 mPa · s. More preferably, it is in the range of 1000 to 10,000 mPa · s. If the viscosity of the monomer solution is within the above range, good moldability can be obtained. In particular, if the viscosity of the monomer solution is 100 mPa · s or more, resin leakage from the dispenser or the mold can be suppressed, and if it is 50,000 mPa · s or less, the penetration into the mold or the time of liquid transfer can be suppressed. Workability will be good.
The (co) polymer of the present invention is obtained by polymerizing the monomer solution described above.

Examples of a method for obtaining a (co) polymer include a method of obtaining a (co) polymer having a predetermined shape by placing a monomer solution in a predetermined shape and polymerizing the monomer solution. Examples of a method for obtaining a (co) polymer having a predetermined shape in this way include, for example, a coating method for applying a monomer solution, a potting molding method, a casting molding method, a printing molding method, and a liquid resin injection molding method. (LIM method), transfer molding method, and the like.
In addition, as a method for polymerizing the monomer solution, any of photopolymerization, thermal polymerization, and redox polymerization can be employed depending on the type of polymerization initiator contained in the monomer solution.

When the monomer solution is polymerized by photopolymerization to obtain a (co) polymer, the wavelength of light irradiated to the monomer solution is not particularly limited, but it is preferable to irradiate ultraviolet rays having a wavelength of 200 to 400 nm. Specific examples of the ultraviolet light source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, and a UV-LED lamp.
After photopolymerization of the monomer solution, it is preferable to further perform aftercuring. Thereby, the amount of unreacted (meth) acryloyl groups remaining in the (co) polymer can be reduced, and the strength of the (co) polymer can be further increased. As conditions for after cure, 0.1 to 24 hours are preferable at 70 to 150 ° C, and 0.2 to 10 hours are more preferable at 80 to 130 ° C.

  When a monomer solution is polymerized by thermal polymerization to obtain a (co) polymer, the polymerization conditions are not particularly limited, but the polymerization temperature is 40 in that it is easy to obtain a (co) polymer with suppressed coloring. -200 degreeC is preferable and 60-150 degreeC is more preferable.

  The polymerization time (heating time) in the case of molding by injecting a monomer solution into a preheated mold, such as the LIM method or transfer molding method, varies depending on the polymerization temperature. For example, the polymerization temperature is 100 ° C. In this case, it is preferably 1 to 180 seconds, more preferably 1 to 120 seconds, and further preferably 1 to 60 seconds. On the other hand, the polymerization time when heating after injecting the monomer solution into the mold at room temperature as in the casting molding method varies depending on the polymerization temperature. For example, when the polymerization temperature is 70 ° C., 5 minutes to 5 hours is preferable. 10 minutes to 3 hours is more preferable.

  After the monomer solution is thermally polymerized, after-curing is preferably further performed. The after-curing conditions are preferably 50 to 150 ° C. for 0.1 to 10 hours, more preferably 70 to 130 ° C. for 0.2 to 5 hours.

  When a monomer solution is polymerized by redox polymerization to obtain a (co) polymer, it can be polymerized at room temperature of 5 to 40 ° C. by using a redox polymerization initiator. Since the amount of unreacted (meth) acryloyl groups remaining in the obtained (co) polymer can be reduced and the strength of the (co) polymer can be further increased, the polymerization temperature is 15 to 40 ° C. Is preferred.

  Since the monomer solution is difficult to gel and can be handled stably, a method in which a reducing agent is dissolved in the monomer solution in advance and the polymerization is performed by adding a peroxide thereto is preferable.

When the (co) polymer is 1 mm thick, the total light transmittance is preferably 85% or more and the haze is 2.0% or less, the total light transmittance is 88% or more, and the haze is 1. More preferably, the total light transmittance is 90% or more and the haze is 1% or less. If the (co) polymer has a total light transmittance of 90% or more and a haze of 1% or less, it can be applied to a wide range of transparent optical members.
The refractive index of the (co) polymer is preferably 1.57 or more, more preferably 1.59 or more, and more preferably 1.60 or more, as measured with a sodium D line (589 nm) at 25 ° C. More preferably. When the refractive index of the (co) polymer is 1.60 or more, various optical designs are possible when applied to a transparent optical member.

  As the heat resistance of the (co) polymer, the glass transition point of the (co) polymer is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and further preferably 110 ° C. or higher. If the glass transition point of the (co) polymer is 100 ° C. or higher, the shape of the (co) polymer is stable even in a standard high temperature and high humidity test environment of 85 ° C. and 85% RH. Reliability improves when applied.

  The monomer solution which is the raw material of the (co) polymer of the present invention described above is the above-described (meth) acrylic acid ester of the present invention, a bifunctional or higher monomer having a plurality of aromatic rings, and a polymerization initiator. By including, it has a viscosity suitable for moldability. The (co) polymer of the present invention has high transparency, high refractive index, and high glass transition point. By containing the antioxidant, the (co) polymer can suppress coloring due to oxidation of the (co) polymer and heating due to reflow.

  When the (co) polymer of the present invention is applied to a transparent optical member, the transparent optical member is produced by molding the (co) polymer of the present invention. The molding may be performed after the monomer solution is polymerized or may be performed simultaneously with the polymerization. Examples of the molding method include a coating method, potting molding method, casting molding method, printing molding method, LIM method, transfer molding method, and the like. The polymerization method at the time of molding is preferably photopolymerization or thermal polymerization in that the transparency of the optical member is good.

  As a transparent optical member considered to be applicable to the (co) polymer of the present invention, for example, a light emitting diode module, a mobile phone, a smartphone, a tablet terminal, a personal computer, a camera, an organic electroluminescence (organic EL) device, Films, sheets, lenses, optical waveguides, sealants, fillers, adhesives, reflectors, adhesives, wavelengths used in flat panel displays, touch panels, electronic paper, photodiodes, phototransistors, solar cells, projectors, etc. Conversion material etc. are mentioned. The (co) polymer of the present invention has high transparency, a high refractive index, and a high glass transition point, and thus is particularly useful as a lens such as a camera lens. Moreover, since coloring by heating at the time of reflow can be suppressed by adding an antioxidant, it is also useful as a transparent optical member such as a lens that passes through the reflow process.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
Data in Examples and Comparative Examples were measured by the following methods.

(A) Purity The purity of each compound was calculated from the peak area in the measurement of a gas chromatograph (hereinafter referred to as “GC”. Apparatus: Agilent Technologies, Inc., Agilent 6890GC, column: DB-1) by the following formula.
Purity (%) = (A / B) × 100
Here, A represents the total peak area of the target product, and B represents the total total peak area.

(B) Actual yield The actual yield was calculated by the following formula.
Actual yield (%) = (C / D) × 100
Here, C represents the number of moles of the target product obtained, and D represents the number of moles of the reference raw material.

(C) Confirmation of Structure The structure of each compound is determined by proton nuclear magnetic resonance spectroscopy (hereinafter referred to as “ ¹ H-NMR”) and carbon nuclear magnetic resonance spectroscopy (hereinafter referred to as “ ¹³ C-NMR”). Identified. The conditions are as follows.
Apparatus: JEOL Ltd. ECS-400 FT-NMR
Frequency: 400MHz
Sample: 20 mg of each compound dissolved in 1 g of deuterated solvent Measurement mode: ¹ H one-dimensional mode
Irradiation pulse width: 3.04 microseconds (45 degree pulse)
Pulse repetition time 5.000 seconds
(FID capture time 2.184 seconds,
Wait time 2.816 seconds)
Cumulative count: 8 times
¹³ C one-dimensional mode
Irradiation pulse width: 10.83 microseconds (90 degree pulse)
Pulse repetition time ・ ・ ・ 3.04333 seconds
(FID acquisition time: 1.04333 seconds,
Waiting time ... 2 seconds)
Integration count 1024 times

(D) Molecular Weight The molecular weight of each compound is gas chromatograph mass spectrometry (hereinafter referred to as “GC-MS”. Apparatus: Agilent Technologies, Inc., Agilent 5975GC-MS, column: UA-5, ionization method: electron impact (EI) Ionization).

(E) Viscosity The viscosity of each monomer for dilution was measured at 10 ° C., 15 ° C., 20 ° C., 25 ° C., and 30 ° C. using a conical plate type rotary viscometer. The monomer solution obtained by stirring and mixing each monomer for dilution, a monomer having two or more functional aromatic rings, other monomers, and a polymerization initiator has a single viscosity. It measured at 23 degreeC using the cylindrical rotary viscometer.

(F) Total light transmittance and haze The monomer solution was aftercured after photopolymerization to obtain a (co) polymer having a diameter of about 50 mm and a thickness of about 1 mm. The total light transmittance and haze of the (co) polymer were measured using a haze meter (manufactured by Murakami Color Research Laboratory, model HM-150).

(G) Refractive index The monomer solution was aftercured after photopolymerization to obtain a (co) polymer having a thickness of about 100 μm. The refractive index (sodium D line (589 nm), 25 ° C.) of the (co) polymer was measured with a multiwavelength Abbe refractometer (DR-M2 manufactured by Atago Co., Ltd.). Note that methylene sulfur iodide (manufactured by Atago Co., Ltd.) was used as the measurement intermediate solution.

(H) Glass transition temperature The monomer solution was aftercured after photopolymerization to obtain a (co) polymer of about 4 mm × 35 mm × thickness 1 mm. The dynamic viscoelasticity and loss tangent of the (co) polymer were measured, and the temperature at which the loss tangent (tan δ) showed the maximum value was defined as the glass transition temperature of the (co) polymer. For the measurement, a dynamic viscoelasticity measuring device (manufactured by TA Instruments Japan Co., Ltd., RSA-II) was used, and the measurement conditions were a tensile mode and a measurement frequency of 10 Hz.

  The following examples and comparative examples illustrate the production of the (meth) acrylic acid ester of the present invention and its physical properties.

Example 1
In a nitrogen atmosphere, 327.9 g of a methylmagnesium bromide-12 mass% tetrahydrofuran solution [manufactured by Tokyo Chemical Industry Co., Ltd., 0.33 mol] was charged into a 500 ml three-necked flask equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermometer. The inner liquid of the flask was stirred. It cooled until the internal liquid of a flask became 0 degreeC. 4- (Methylthio) benzaldehyde 28.26 g [manufactured by Tokyo Chemical Industry Co., Ltd., 0.22 mol] was gradually dropped into the flask over 1 hour. After dropping, the cooling was stopped and the internal solution in the flask was returned to room temperature, and then stirred for 2 hours. The internal liquid of the flask was again cooled to 0 ° C., and 100 ml of a saturated aqueous ammonium chloride solution was gradually added dropwise. The organic layer was separated by a liquid separation operation, and the aqueous layer was extracted twice with 90 g of tetrahydrofuran. The combined organic layers were washed with 100 ml of 5% by weight aqueous potassium carbonate solution, concentrated using a rotary evaporator, and tetrahydrofuran was distilled off. As a result, white solid 1- [4- (methylthio) phenyl] -1-hydroxyethyl 25 .24 g [0.15 mol] was obtained. The actual yield based on 4- (methylthio) benzaldehyde was 68.2%.

  Methyl methacrylate 60.07 g [0.60 mol, manufactured by Mitsubishi Rayon Co., Ltd., trade name Acryester M], 1- [4- (methylthio) phenyl] -1-hydroxyethyl 25.24 g [0.15 mol], polymerization prevention 4,4 ′-[1,2-phenylenebis (carbonyloxy)] bis [2,2,6,6-tetramethylpiperidine-N-oxyl] 0.03 g was mixed as an agent, and the cooling tube, Dean Stark The solution was put into a 100 ml three-necked flask equipped with a device, a stir bar, an air introduction tube, and a thermometer. While introducing air, the liquid in the flask was stirred and the flask was heated in an oil bath. Methyl methacrylate and water were extracted azeotropically at an internal temperature of 100 to 110 ° C. After analyzing the water content of the internal liquid of the flask and confirming that the water content was 100 ppm or less, 0.10 g of titanium tetrabutoxide [manufactured by Kanto Chemical Co., Ltd., 0.0003 mol] was added as a catalyst. Thereafter, the reaction was carried out at an internal temperature of 100 to 120 ° C. for 8 hours while extracting methyl methacrylate and methanol by azeotropy. After completion of the reaction, the reaction mixture was cooled and concentrated using a rotary evaporator, and excess methyl methacrylate was distilled off. The residue was purified by distillation under reduced pressure. As a result, 29.05 g [0.12 mol] of transparent liquid-1- [4- (methylthio) phenyl] ethyl methacrylate having a boiling point of 140 ° C./0.67 hPa and a purity of 99.7% was obtained. Got. The actual yield based on 1- [4- (methylthio) phenyl] -1-hydroxyethyl was 81.7%.

The resulting methacrylic acid-1- [4- (methylthio) phenyl] ethyl The ¹ H one-dimensional mode of the ¹ H-NMR (molecular weight 236) spectrum (solvent: heavy methanol) in Figure ^1, the 13 C-NMR The spectrum of ¹³ C one-dimensional mode (solvent: deuterated acetonitrile) is shown in FIG. 2, and the mass spectrum of GC-MS is shown in FIG.

  Table 1 shows the viscosity of methacrylic acid-1- [4- (methylthio) phenyl] ethyl measured at various temperatures using a conical plate type rotational viscometer.

(Comparative Example 1)
Table 1 shows the viscosity of acrylic acid-o-phenylphenoxyethyl [manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-LEN-10] measured at various temperatures using a conical plate type rotational viscometer.

(Comparative Example 2)
Methyl methacrylate (1-naphthyl) methyl was synthesized by the method described in Patent Document 6 (Japanese Patent Application Laid-Open No. 08-263737).

  Table 1 shows the viscosity of methyl (1-naphthyl) methacrylate measured at various temperatures using a conical plate type rotary viscometer.

(Comparative Example 3)
4- (Methylthio) benzyl methacrylate was synthesized by the method described in Non-Patent Document 1 (Polymer Journal, Vol. 42, pages 249 to 255, 2010).

  Table 1 shows the viscosity of 4- (methylthio) benzyl methacrylate measured at various temperatures using a conical plate type rotational viscometer.

(Example 2)
In a reaction vessel equipped with a condenser, 100 parts of methacrylic acid-1- [4- (methylthio) phenyl] ethyl produced in Example 1 and 3 parts of 1-hydroxycyclohexyl phenyl ketone [manufactured by BASF Corporation, Irgacure 184] In addition, a monomer solution was obtained by stirring at 70 ° C. for 2 hours.

The obtained monomer solution was sandwiched between two glass plates using a 1 mm-thick silicone sheet as a gasket, irradiated with ultraviolet light with an integrated light quantity of 1000 mJ / cm ² with a high-pressure mercury lamp, and then heated at 100 ° C. for 30 minutes. After cooling, the plate glass was removed to obtain a molded product made of a homopolymer having a diameter of about 50 mm and a thickness of about 1 mm.

  Similarly, a 1 mm thick silicone sheet obtained by cutting out a rectangular shape of about 4 mm × 35 mm was used as a gasket to obtain a molded product made of a homopolymer of about 4 mm × 35 mm × thickness 1 mm. In the same manner, a molded article made of a homopolymer having a thickness of about 100 μm was obtained by using a polyester tape having a thickness of about 100 μm.

  Using the obtained molded product comprising a homopolymer, the total light transmittance, haze, refractive index, and glass transition point were measured. The results are shown in Table 2.

(Comparative Examples 4-6)
A monomer solution was prepared in the same manner as in Example 2 except that 1- [4- (methylthio) phenyl] ethyl methacrylate was changed to various monomers shown in Table 2, and a homopolymer A molded product consisting of was obtained and various measurements were performed. The results are shown in Table 2.

(Example 3)
In a reaction vessel equipped with a condenser, 15 parts of methacrylic acid-1- [4- (methylthio) phenyl] ethyl and 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene produced in Example 1 were used. 70 parts [manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF], 15 parts of benzyl methacrylate [manufactured by Mitsubishi Rayon Co., Ltd., trade name acrylate BZ], 3 parts of 1-hydroxycyclohexyl phenyl ketone [manufactured by BASF Corporation] , Irgacure 184] was added, and the mixture was stirred at 70 ° C. for 2 hours to obtain a monomer solution. Table 2 shows the viscosity of the monomer solution measured at 23 ° C. using a single cylindrical rotary viscometer.

The obtained monomer solution was sandwiched between two glass plates using a 1 mm-thick silicone sheet as a gasket, irradiated with ultraviolet light with an integrated light quantity of 1000 mJ / cm ² with a high-pressure mercury lamp, and then heated at 100 ° C. for 30 minutes. After cooling, the plate glass was removed to obtain a molded product made of a copolymer having a diameter of about 50 mm and a thickness of about 1 mm.

  Similarly, a 1 mm thick silicone sheet obtained by cutting out a rectangular shape of about 4 mm × 35 mm was used as a gasket, thereby obtaining a molded product made of a copolymer of about 4 mm × 35 mm × thickness 1 mm. In the same manner, a molded article made of a copolymer having a thickness of about 100 μm was obtained by using a polyester tape having a thickness of about 100 μm.

  Using the molded product obtained from the copolymer, total light transmittance, haze, refractive index, and glass transition point were measured. The results are shown in Table 2.

(Comparative Examples 7-9)
A monomer solution was prepared in the same manner as in Example 3 except that 1- [4- (methylthio) phenyl] ethyl methacrylate was changed to various monomers shown in Table 2, and a copolymer was prepared. A molded product consisting of was obtained and various measurements were performed. The results are shown in Table 2.

Example 4
1- [4- (methylthio) phenyl] -1 in the same manner as in Example 1 except that 51.65 g of methyl acrylate (manufactured by Mitsubishi Chemical Co., Ltd., 0.60 mol) was used instead of methyl methacrylate. -Transesterification with 25.24 g [0.15 mol] of hydroxyethyl was carried out. At this time, methyl acrylate and water were extracted azeotropically at an internal temperature of 80 to 90 ° C., and after the addition of the catalyst, the reaction was carried out for 12 hours while extracting methyl acrylate and methanol azeotropically at an internal temperature of 80 to 100 ° C. . The residue obtained after the reaction was purified by distillation under reduced pressure to obtain 23.17 g of transparent liquid-1- [4- (methylthio) phenyl] ethyl acrylate having a boiling point of 138 ° C./0.37 hPa and a purity of 99.1%. [0.10 mol] was obtained. The actual yield based on 1- [4- (methylthio) phenyl] -1-hydroxyethyl was 68.9%.

The resulting acrylic acid-1- [4- (methylthio) phenyl] ethyl spectra of the ¹ H one-dimensional mode of the ¹ H-NMR (molecular weight 222) (solvent: heavy methanol) in FIG. ^4, the 13 C-NMR The spectrum of ¹³ C one-dimensional mode (solvent: deuterated acetonitrile) is shown in FIG. 5, and the mass spectrum of GC-MS is shown in FIG.

  Table 1 shows the viscosity of acrylic acid-1- [4- (methylthio) phenyl] ethyl acrylate measured at various temperatures using a conical plate type rotational viscometer.

(Example 5)
Except for using 250.0 g of an ethyl magnesium bromide-13 mass% tetrahydrofuran solution [manufactured by Tokyo Chemical Industry Co., Ltd., 0.24 mol] instead of the methyl magnesium bromide-12 mass% tetrahydrofuran solution, When 24.74 g of 4- (methylthio) benzaldehyde [manufactured by Tokyo Chemical Industry Co., Ltd., 0.16 mol] was allowed to act, white solid 1- [4- (methylthio) phenyl] -1-hydroxypropyl 19.37 g [0. 11 mol] was obtained. The actual yield based on 4- (methylthio) benzaldehyde was 65.4%.
Methyl methacrylate 42.56 g [0.43 mol, manufactured by Mitsubishi Rayon Co., Ltd., trade name Acryester M], 1- [4- (methylthio) phenyl] -1-hydroxypropyl 19.37 g [0.11 mol], polymerization prevention 4,4 ′-[1,2-phenylenebis (carbonyloxy)] bis [2,2,6,6-tetramethylpiperidine-N-oxyl] 0.02 g was mixed as an agent, and the cooling tube, Dean Stark The solution was put into a 100 ml three-necked flask equipped with a device, a stir bar, an air introduction tube, and a thermometer. While introducing air, the liquid in the flask was stirred and the flask was heated in an oil bath. Methyl methacrylate and water were extracted azeotropically at an internal temperature of 100 to 110 ° C. After analyzing the water content of the internal liquid of the flask and confirming that the water content was 100 ppm or less, 0.07 g of titanium tetra-n-butoxide [manufactured by Kanto Chemical Co., Inc., 0.0002 mol] was added as a catalyst. Thereafter, the reaction was carried out at an internal temperature of 100 to 120 ° C. for 16 hours while extracting methyl methacrylate and methanol by azeotropy. After completion of the reaction, the reaction mixture was cooled and concentrated using a rotary evaporator, and excess methyl methacrylate was distilled off. The residue was purified by distillation under reduced pressure. As a result, 20.48 g [0.08 mol] of transparent liquid-1- [4- (methylthio) phenyl] propyl methacrylate having a boiling point of 144 ° C./0.53 hPa and a purity of 98.2% was obtained. Got. The actual yield based on 1- [4- (methylthio) phenyl] -1-hydroxypropyl was 75.6%.
The resulting methacrylic acid-1- [4- (methylthio) phenyl] propyl of the ¹ H one-dimensional mode of the ¹ H-NMR (molecular weight 250) spectrum: FIG. 7 (solvent heavy ^methanol) of the 13 C-NMR A spectrum of ¹³ C one-dimensional mode (solvent: deuterated acetonitrile) is shown in FIG. 8, and a mass spectrum of GC-MS is shown in FIG.

  Table 1 shows the viscosity of methacrylic acid-1- [4- (methylthio) phenyl] propyl measured at various temperatures using a conical plate type rotational viscometer.

(Example 6)
1- [4- (methylthio) phenyl] -1 in the same manner as in Example 5 except that 36.60 g of methyl acrylate (0.43 mol, manufactured by Mitsubishi Chemical Corporation) was used instead of methyl methacrylate. -An esterification reaction with 19.37 g [0.11 mol] of hydroxypropyl was carried out. At this time, methyl acrylate and water were extracted azeotropically at an internal temperature of 80 to 90 ° C., and after the addition of the catalyst, the reaction was performed for 24 hours while extracting methyl acrylate and methanol azeotropically at an internal temperature of 80 to 100 ° C. . The residue obtained after the reaction was purified by distillation under reduced pressure. As a result, 17.85 g of transparent liquid-1- [4- (methylthio) phenyl] propyl acrylate having a boiling point of 136 ° C./0.67 hPa and a purity of 97.8% was obtained. [0.07 mol] was obtained. The actual yield based on 1- [4- (methylthio) phenyl] -1-hydroxypropyl was 69.5%.
The resulting acrylic acid-1- [4- (methylthio) phenyl] propyl spectra of the ¹ H one-dimensional mode of the ¹ H-NMR (molecular weight 236): Figure 10 (solvent heavy ^methanol) of the 13 C-NMR The spectrum of ¹³ C one-dimensional mode (solvent: deuterated acetonitrile) is shown in FIG. 11, and the mass spectrum of GC-MS is shown in FIG.

  Table 1 shows the viscosity of acrylic acid-1- [4- (methylthio) phenyl] propyl acrylate measured at various temperatures using a conical plate type rotational viscometer.

  The present invention relates to a novel (meth) acrylic acid ester for dilution having a low viscosity, a high refractive index, and a high heat resistance of the homopolymer, and the (co) polymer is suitable as a transparent optical member. Can be used.

Claims (4)

(Meth) acrylic acid ester represented by the following formula (1).
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms. R ² represents a hydrogen atom or a methyl group.) A compound represented by the following formula (3) is produced by allowing an organometallic compound having an alkyl group having 1 to 4 carbon atoms to act on the compound represented by the following formula (2), and the compound is represented by a (meth) acrylic acid derivative. The method for producing a (meth) acrylic acid ester according to claim 1, wherein the esterification is carried out.
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms.)   The homopolymer of the (meth) acrylic acid ester according to claim 1. A copolymer of the (meth) acrylic acid ester according to claim 1 and another monomer.