JP6911422B2 - Methacrylic acid ester, its production method, and its (co) polymer - Google Patents

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 a copolymer of the (meth) acrylic acid ester.

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

Japanese Unexamined Patent Publication No. 55-13747 Japanese Unexamined Patent Publication No. 4-325508 Japanese Unexamined Patent Publication No. 2007-84415 International Publication No. WO2005 / 033061 Japanese Unexamined Patent Publication No. 2008-94987 Japanese Unexamined Patent Publication No. 08-263949

Polymer Journal, Vol. 42, pp. 249-255, 2010.

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

式中、Ｒ^１は炭素数１以上４以下のアルキル基を示す。Ｒ^２は水素原子又はメチル基を示す。
また、本発明は上記の（メタ）アクリル酸エステルの単独重合体又はその（メタ）アクリル酸エステルと他の単量体との共重合体に関する。 As a result of diligent studies in order to solve the above problems, the present inventors 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 or more carbon atoms and 4 or less carbon atoms. R ² represents a hydrogen atom or a methyl group.
The present invention also relates to a homopolymer of the above (meth) acrylic acid ester or a copolymer of the (meth) acrylic acid ester and another monomer.

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

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. ^{3 is a spectrum of 13} C 1-dimensional mode of ¹³ C-NMR of -1- [4- (methylthio) phenyl] ethyl methacrylate obtained in Example 1. 6 is a mass spectrum of GC-MS of -1- [4- (methylthio) phenyl] ethyl methacrylate obtained in Example 1. It is a spectrum of 1H one-dimensional mode of 1H-NMR of acrylic acid-1- [4- (methylthio) phenyl] ethyl obtained in Example 4. It is a spectrum of 13C one-dimensional mode of 13C-NMR of acrylic acid-1- [4- (methylthio) phenyl] ethyl obtained in Example 4. 6 is a mass spectrum of GC-MS of -1- [4- (methylthio) phenyl] ethyl acrylic acid obtained in Example 4. It is a spectrum of 1H one-dimensional mode of 1H-NMR of methacrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 5. It is a spectrum of 13C one-dimensional mode of 13C-NMR of methacrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 5. It is a mass spectrum of GC-MS of methacrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 5. 6 is a 1H one-dimensional mode spectrum of 1H-NMR of acrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 6. It is a spectrum of 13C one-dimensional mode of 13C-NMR of acrylic acid-1- [4- (methylthio) phenyl] propyl obtained in Example 6. 6 is a mass spectrum of GC-MS of -1- [4- (methylthio) phenyl] propyl acrylic acid obtained in Example 6.

In the present specification, acrylic acid and methacrylic acid are combined as "(meth) acrylic acid", acrylic acid ester and methacrylic acid ester are combined as "(meth) acrylic acid ester", and acryloyl group and methacrylic acid group are combined as "((meth) acrylic acid ester". Meta) Acryloyl group ". Further, the radically polymerizable monomer is described as "monomer", the homopolymerization and the copolymer are collectively referred to as "polymerization", and the homopolymer and the copolymer are collectively referred to as "(co) polymer".

(A) (Meta) 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 or more carbon atoms and 4 or less carbon atoms. When the number of carbon atoms 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 polymerizable property. Considering ease of production and physical properties, R ¹ is preferably a methyl group having 1 carbon atom and an ethyl group having 2 carbon atoms. R ² represents a hydrogen atom or a methyl group. Considering the viscosity, refractive index, and ease of photopolymerizability, R ² is preferably a hydrogen atom, and considering 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 and (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) acrylate-2-methyl-1- [2- (methylthio) ) Phenyl] propyl, -2-methyl-1- [3- (methylthio) phenyl] propyl (meth) acrylate, -2-methyl-1- [4- (methylthio) phenyl] propyl (meth) acrylate, ( Meta) Acrylic Acid-1- [2- (Methylthio) Phenyl] Pentyl, (Meta) Acrylic Acid-1- [3- (Methylthio) Phenyl] Pentyl, (Meta) Acrylic Acid-1- [4- (Methylthio) Phenyl ] Pentyl, -2-methyl-1- [2- (methylthio) phenyl] butyl (meth) acrylate, -2-methyl-1- [3- (methylthio) phenyl] butyl (meth) acrylate, (meth) -2-Methyl acrylate-1- [4- (methylthio) phenyl] butyl, (meth) acrylate-2,2-dimethyl-1- [2- (methylthio) phenyl] propyl, (meth) acrylate-2 , 2-Dimethyl-1- [3- (methylthio) phenyl] propyl, (meth) acrylic acid-2,2-dimethyl-1- [4- (methylthio) phenyl] propyl and the like.

式中、Ｒ^１は炭素数１以上４以下のアルキル基を示す。 (B) Production of (meth) acrylic acid ester As a method for producing the (meth) acrylic acid ester of the present invention, a compound represented by the formula (2) (hereinafter referred to as "compound of the formula (2)") is carbonized. A compound represented by the formula (3) (hereinafter referred to as "compound of the formula (3)") produced by reacting an organic metal compound having an alkyl group having a number of 1 or more and 4 or less is a (meth) acrylic acid derivative. Examples thereof include a method of esterification.

In the formula, R ¹ represents an alkyl group having 1 or more carbon atoms and 4 or less 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 to act on the compound of the formula (2) with an organometallic compound having an alkyl group having 1 or more and 4 or less carbon atoms. Examples of the organic metal compound having an alkyl group having 1 or more and 4 or less carbon atoms that acts on the compound of the formula (2) include methyllithium, ethyllithium, propyllithium, isopropyllithium, butyllithium, s-butyllithium, and t-. Alkyl lithium compounds such as butyllithium, methyllithium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, isopropylmagnesium bromide, isopropylmagnesium chloride, butylmagnesium chloride, s-butylmagnesium bromide, Examples thereof include alkylmagnesium compounds such as s-butylmagnesium chloride and t-butylmagnesium chloride, alkylzinc compounds such as methylzinc chloride, and alkyltitanium compounds such as dimethyltitanium dichloride. Among them, alkylmagnesium compounds are particularly preferable because they are easily 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 to 2.0 is preferable, and 1: 0.4 to 1.8 is more preferable. As the reaction solvent, diethyl ether, tetrahydrofuran, toluene or 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) produced in this manner include 1- [2- (methylthio) phenyl] ethanol, 1- [3- (methylthio) phenyl] ethanol, and 1- [4- (methylthio). Phenyl] ethanol, 1- [2- (methylthio) phenyl] propal, 1- [3- (methylthio) phenyl] propal, 1- [4- (methylthio) phenyl] propal, 1- [2- (methylthio) phenyl ) 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] Propearl, 2-Methyl-1- [4- (Methylthio) Phenyl] Propearl, 1- [2- (Methylthio) Phenyl] Pentanol, 1- [3- (Methylthio) Phenyl] ) 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)) Examples thereof include phenyl] propanol and 2,2-dimethyl-1- [4- (methylthio) phenyl] propanol.
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 the (meth) acrylic acid derivative used in esterification include (meth) acrylic acid halide, (meth) acrylic acid anhydride, (meth) acrylic acid, (meth) acrylic acid ester, and the like, but not yet. Considering the recoverability of reaction raw materials and by-products and waste treatment, esterification with (meth) acrylic acid ester, that is, transesterification reaction is particularly preferable.

When performing a transesterification reaction, a catalyst for transesterification reaction is used. Examples of the ester exchange reaction catalyst used in this case 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. Alkali metal alkoxides such as substances, carbonates, lithium methoxydos, sodium methoxydos, sodium ethoxides and potassium-t-butoxy, alkali metal amides such as lithium amides, sodium amides and potassium amides, titanium tetramethoxydes and titanium tetraisos. 4A metal alkoxides such as propoxide, titanium tetrabutoxide, zirconium tetraethoxydo, zirconite tetraisopropoxide, zirconium tetrabutoxide, 4A metal acetylacetonate such as titaniumoxydiacetylacetonate and zirconium tetraacetylacetonate, dibutyltin Examples thereof include dialkyltin oxides such as oxides and dioctyltin oxides. Among them, 4A metal alkoxides and 4A metal acetylacetonates are particularly preferable because they have high activity, are easily available, and are easy to handle.

When a 4A metal alkoxide or a 4A metal acetylacetonate is used as a catalyst for a transesterification reaction, the compound of formula (3): (meth) acrylic is considered in consideration of the reaction rate and the recovery of unreacted raw materials and by-products. The molar ratio of the acid ester: catalyst is preferably 1: 1.5 to 20: 0.0001 to 0.05, more preferably 1: 2.0 to 6: 0.0005 to 0.03. Examples of the (meth) acrylic acid ester used in this case include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, -i-propyl (meth) acrylate, and (meth) acrylic. Examples thereof include butyl acid acid, -i-butyl (meth) acrylate, -s-butyl (meth) acrylate, and -t-butyl (meth) acrylate. Among them, methyl (meth) acrylate is particularly preferable in consideration of recoverability and availability of by-produced alcohol. 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 by removing the by-produced alcohol.

In order to prevent the obtained (meth) acrylic acid ester of the present invention from polymerizing under high temperature conditions, it is preferable to react in the presence of a polymerization inhibitor, and the reaction is carried out while bubbling a gas containing oxygen. Is preferable. It is more preferable to use both the polymerization inhibitor and the oxygen bubbling because the 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, and 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 -Tetramethylpiperidin-N-oxyl, 4-acetamide-2,2,6,6-tetramethylpiperidin-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidin-N-oxyl, Examples thereof include N-oxyl compounds such as 4,4'-[1,2-phenylenebis (carbonyloxy)] bis [2,2,6,6-tetramethylpiperidin-N-oxyl]. Among them, an N-oxyl-based polymerization inhibitor or the like is preferable in order to prevent polymerization during the reaction, and when the catalyst is deactivated and removed by purification after the reaction, for example, 4-methoxyphenol 2, Phenolic compounds such as 6-di-t-butyl-4-methylphenol are preferred.
One type of these polymerization inhibitors may be used alone, or two or more types may be used in combination. The amount of the polymerization inhibitor used in the present invention (when two or more kinds of polymerization inhibitors are used in combination, the total amount thereof) can be appropriately selected depending on 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. Of these, air is more preferable because it is inexpensive and exhibits a polymerization preventing effect. The flow velocity at the time of bubbling is not limited, and can be appropriately selected depending on the reaction conditions and the like.

The (meth) acrylic acid ester of the present invention can be purified by using known methods such as silica gel column chromatography and vacuum distillation.
Even during vacuum distillation in purification, the above-mentioned polymerization inhibitor can be used or a gas containing oxygen can be bubbled in order to prevent polymerization at a high temperature. As the polymerization inhibitor used to prevent polymerization during distillation, an N-oxyl-based polymerization inhibitor is preferable, and among them, a high boiling point of 4,4'-[1,2-phenylenebis (carbonyloxy)] Bis [2,2,6,6-tetramethylpiperidin-N-oxyl] is particularly preferable because it can avoid contamination with the distillate.

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

(C) (Co) polymer By polymerizing the (meth) acrylic acid ester of the present invention obtained as described above, a (co) polymer can be obtained.
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 a polymerization reaction by holding a monomer solution in which a monomer and a polymerization initiator are mixed in advance, which is a kind of bulk polymerization, at a constant temperature is preferable because it is simple.

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

Examples of the monomer other than the (meth) acrylic acid ester include (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, 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, -2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) Lauryl acrylate, (meth) tridecyl acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, phenyl (meth) acrylate, (meth) Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, -3,3, (meth) acrylate 5-trimethylcyclohexyl, (meth) acrylate-4-t-butylcyclohexyl, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid Dicyclopentanyl, adamantyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, (meth) acrylate Tetrahydrofurfuryl, -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate, -3-hydroxypropyl (meth) acrylate, -2-hydroxybutyl (meth) acrylate, (meth) ) 4-Hydroxybutyl acrylate, glycidyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyl acid phosphate, -2-hydroxyethyl (meth) acrylate Reaction product of 6-hexanolide addition polymer and phosphate anhydride, -2-ethylhexyldiethylene glycol (meth) acrylate, acryloylmorpholin, ac. Monofunctional monomers such as lilonitrile, acrylamide, dimethylacrylamide, styrene, α-methylstyrene, vinyl acetate; ethylene glycol di (meth) acrylic acid, polyethylene glycol di (meth) acrylic acid, di (meth) acrylic acid- 1,3-propylene glycol, di (meth) acrylic acid polypropylene glycol, di (meth) acrylic acid neopentyl glycol, di (meth) acrylic acid-1,3-butylene glycol, di (meth) acrylic acid-1,4 -Butylene glycol, polybutylene glycol di (meth) acrylic acid, 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-1,10-decanediol, di (meth) acrylic acid-1,4-cyclohexanedimethanol, di (meth) acrylic acid tricyclodecanedimethylol , Di (meth) acrylate polycarbonate diol, di (meth) acrylate polyester diol, ε-caprolactone-modified tris ((meth) achromiethyl) 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, 1,1-bis [4-((meth) acryloyloxy) phenyl] ) Phenyl] ethane, 2,2-bis [4-((meth) acryloyloxy) phenyl] butane, 1,1-bis [4-((meth) acryloyloxy) phenyl] cyclohexane, 1,1-bis [4 -(2- (Meta) acryloyloxyethoxy) phenyl] cyclohexane, 1,1-bis [4-((meth) acryloyloxy) phenyl] -1-phenylethane, 1,1-bis [4- (2-( Meta) acryloyloxyethoxy) phenyl] -1-phenylethane, 9,9-bis [4-((meth) acryloyloxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) ) Phenyl] Fluoren, Bis [4-((meth) Acryloyloxy) Phenyl] Sul Fido, bis [4- (2- (meth) acryloyloxyethoxy) phenyl] sulfide bis [4-((meth) acryloyloxy) phenyl] sulfone, bis [4- (2- (meth) acryloyloxyethoxy) phenyl] Bifunctional monomers such as sulfone, bis [4-((meth) acryloylthio) phenyl] sulfide, bis [4- (2- (meth) acryloylthioethoxy) phenyl] sulfide, butadiene; tri (meth) acrylic Trifunctional simples such as trimethylol propanoate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, tris (2- (meth) acryloyloxyethyl) isocyanurate. Quantities; tetrafunctional monomers such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate; pentafunctional monomers such as dipentaerythritol penta (meth) acrylate; hexa ( Meta) Examples thereof include hexafunctional monomers such as dipentaerythritol acrylate. These monomers may be used alone or in combination of two or more.

When producing a copolymer, a copolymer having a high refractive index and high heat resistance can be produced by using a monomer having a high refractive index and high heat resistance of the homopolymer. The monomer used at this time having a high refractive index and high heat resistance of the homopolymer includes a bifunctional or higher monomer having a plurality of aromatic rings, for example, 2,2-bis [4-((((). Meta) 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-( (Meta) 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- (Meta) acryloyloxyethoxy) phenyl] -1-phenylethane, 9,9-bis [4-((meth) acryloyloxy) phenyl] fluorene, 9,9-bis [4- (2-( Meta) acryloyloxyethoxy) phenyl] fluorene, bis [4-((meth) acryloyloxy) phenyl] sulfide, bis [4- (2- (meth) acryloyloxyethoxy) phenyl] sulfide, bis [4-((meth) acryloyloxyethoxy) phenyl] sulfide ) Acryloyloxy) phenyl] sulfone, bis [4- (2- (meth) acryloyloxyethoxy) phenyl] sulfone, bis [4-((meth) acryloylthio) phenyl] sulfide, bis [4- (2- (meth) acryloylthio) phenyl] ) Acryloylthioethoxy) phenyl] sulfide and the like. Among them, 9,9-bis [4- (2- (meth)) is available because it can efficiently produce a copolymer having a high refractive index and high heat resistance, and it is easy to obtain and handle. Acryloyloxyethoxy) phenyl] fluorene is particularly preferred.

The content of the monomer having two or more functionalities and having a plurality of aromatic rings is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and 30 to 70 parts by mass out of 100 parts by mass of the total amount of the monomer components. Is even more preferable. When the content of the monomer having two or more functionalities and 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 the content may be 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 high heat resistance is produced by using the (meth) acrylic acid ester of the present invention and a monomer having two or more functionalities and having a plurality of aromatic rings, the (meth) of the present invention is used. The content of the acrylic acid ester is preferably 10 to 90 parts by mass out of 100 parts by mass of the total amount of the monomer components. When 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 when the content is 90 parts by mass or less, the refractive index of the copolymer The rate and heat resistance can be increased.

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

When producing a copolymer having a high refractive index and high heat resistance, in addition to the (meth) acrylic acid ester of the present invention and a monomer having a plurality of aromatic rings with bifunctionality or higher, the viscosity of the monomer solution is further increased. Still another monomer may be contained in order to reduce the decrease, suppress the coloring of the copolymer, and suppress the weight loss of the copolymer during heating.
As such a monomer, phenyl (meth) acrylate, (meth) can be used because the viscosity of the monomer solution can be significantly reduced while maintaining the high refractive index and high heat resistance of the copolymer. Phenyl acrylate, phenoxyethyl (meth) acrylate and the like are preferable.

The polymerization initiator used for the polymerization is not particularly limited, and can be appropriately selected depending on the type of the monomer, the reaction conditions, and the like. Examples of the polymerization initiator include radical polymerization initiators, which are classified into photopolymerization initiators, thermal polymerization initiators, peroxides used for redox polymerization, and the like according to 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, methyl orthobenzoylbenzoate and 4-phenylbenzophenone; t-butylanthraquinone and 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-hydroxycyclohexylphenyl ketone, benzoin methyl ether, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-1- {4- [4- (2- (2-) Hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and other alkylphenone-type compounds; diethyl Thioxanthone-type compounds such as thioxanthone and isopropylthioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphenyl oxide, bis (2,4,6) -Trimethylbenzoyl) -Acylphosphine oxide type compounds such as phenylphosphinoxide; Phenylglycilate type compounds such as phenylglycoxylic acid methyl ester and the like can be mentioned. Among them, alkylphenone-type compounds are preferable because they can suppress the coloring of the (co) polymer, and among them, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexylphenyl ketone are preferable. Is particularly preferable. Further, the acylphosphine oxide type compound is preferable in that it can sufficiently polymerize to the inside of the (co) polymer, and among them, 2,4,6-trimethylbenzoyl in that the 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 and 1,1-di (t-hexylperoxy). ) Peroxyketals such as cyclohexane, 1,1-di (t-butylperoxy) cyclohexane; 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, [2- (4-methylcyclohexyl) ) Propane-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; Peroxydicarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate; t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmono Examples thereof include peroxyesters such as carbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate.

Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 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 unlikely to be 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, preferably in the range of 40 to 75 ° C. More preferably, it is in the range of 45 ° C. to 70 ° C. When the 10-hour half-life temperature is 35 ° C. or higher, the monomer solution is less likely to gel at room temperature, and the pot life is improved. On the other hand, when the 10-hour half-life temperature is 80 ° C. or lower, 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 of 65 ° C.) and t-butylperoxy-2-ethylhexanoate. Examples thereof include 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-based polymerization initiator is a radical polymerization initiator used for redox-based polymerization, and is a polymerization initiator in which a peroxide and a reducing agent are used 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. When the above-mentioned peroxide is used as a redox-based polymerization initiator, an example of a combination with a reducing agent is as follows.
(1) Dibenzoyl peroxide (peroxide) and aromatics such as N, N-dimethylaniline, 4-dimethylaminotoluene, 1,1'-[(4-methylphenyl) imino] bis (2-propanol) Combination with group tertiary amines (reducing agent).
(2) Combination of hydroperoxide (peroxide) and metal soaps (reducing agent).
(3) 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. More preferred. When the content of the polymerization initiator is 0.01 parts by mass or more, the polymerizable property of the monomer solution is improved. 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, it is possible to suppress the coloration of the (co) polymer due to oxidation. Further, when the (co) polymer passes through a heat treatment step such as solder reflow, coloring due to heating at the time of passing can be suppressed.
Examples of antioxidants 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-hexanediolbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; tri Phosphorus antioxidants such as phenylphosphite, trisisodecylphosphite, tristridecylphosphite, tris (2,4-di-t-butylphenyl) phosphite; dihexyl sulfide, dilaurilu 3,3'-thiodipro Pionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, disterial-3,3'-thiodipropionate, pentaerythritol tetrakis (β-laurylthiopropionate), etc. Examples include sulfur-based antioxidants. Among them, sulfur-based antioxidants and phosphorus-based antioxidants are preferable because they are highly soluble in monomeric solutions and have a high effect of suppressing the coloring 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. More preferred. When 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% by mass. If it is less than a part, the transparency of the (co) polymer tends to be higher.

The monomeric solution can also contain a chain transfer agent 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, α-methylstyrene dimer and the like.

The monomer solution is the (meth) acrylic acid ester of the present invention, a monomer having two or more functional and multiple aromatic rings, other monomers, and polymerization as long as the effect of the present invention is not impaired. It may contain components other than the initiator, the antioxidant, and the chain transfer agent (hereinafter, referred to as “other components”).

Other components include, for example, various additions of acrylic polymers, rubber, silica fine particles, plasticizers, ultraviolet absorbers, defoamers, rockers, polymerization inhibitors, mold release agents, fillers, phosphors, pigments, etc. Agents can be mentioned.

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

When a thermal polymerization initiator is used as the polymerization initiator, the (meth) acrylic acid ester of the present invention, which is bifunctional or higher and has a plurality of aromatic rings, is required in consideration of the stability of the monomer solution. A method is preferable in which the other monomer component, the antioxidant, and the other component are heated and mixed, cooled, the thermal polymerization initiator is added at room temperature, and the mixture is stirred and mixed to obtain a monomer solution.

When a monomer solution is produced 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., and the stirring time for mixing 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, preferably in the range of 500 to 30,000 mPa · s, as measured by a single cylindrical rotary viscometer at 23 ° C. It is more preferably in the range of 1000 to 10,000 mPa · s. When 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 penetrability into the mold and the liquid transfer can be suppressed. Workability is good.
The (co) polymer of the present invention is a polymer of the above-mentioned monomer solution.

Examples of the method for obtaining the (co) polymer include a method in which a monomer solution is provided in a predetermined shape and then polymerized to obtain a (co) polymer having a predetermined shape. Examples of the method for obtaining a (co) polymer having a predetermined shape in this way include a coating method for coating 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 can be mentioned.
Further, as a method for polymerizing the monomer solution, any one of photopolymerization, thermal polymerization and redox polymerization can be adopted depending on the type of the 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 ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, high power metal halide lamps, UV-LED lamps and the like.
After photopolymerizing the monomer solution, it is preferable to further perform aftercure. As a result, 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. The aftercure conditions are preferably 0.1 to 24 hours at 70 to 150 ° C., more preferably 0.2 to 10 hours at 80 to 130 ° C.

When the 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 a (co) polymer with suppressed coloring can be easily obtained. ~ 200 ° C. is preferable, and 60 to 150 ° C. is more preferable.

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

After the monomer solution is thermally polymerized, it is preferable to further perform aftercure. The aftercure conditions are preferably 0.1 to 10 hours at 50 to 150 ° C, more preferably 0.2 to 5 hours at 70 to 130 ° C.

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-based 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 preferable.

Since the monomer solution is difficult to gel and can be handled stably, a method of dissolving the reducing agent in the monomer solution in advance and adding a peroxide to the solution is preferable.

When the (co) polymer has a thickness of 1 mm, the total light transmittance is preferably 85% or more and the haze is 2.0% or less, and the total light transmittance is 88% or more and the haze is 1. It is more preferably 5% or less, and further preferably the total light transmittance is 90% or more and the haze is 1% or less. When the total light transmittance of the (co) polymer is 90% or more and the haze is 1% or less, it can be applied to a transparent optical member for a wide range of applications.
The refractive index of the (co) polymer is preferably 1.57 or more, more preferably 1.59 or more, and 1.60 or more, as measured by the sodium D line (589 nm) at 25 ° C. Is more preferable. 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 for 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 even more preferably 110 ° C. or higher. When 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. Improves reliability when applied.

The monomer solution which is the raw material of the (co) polymer of the present invention described above is the above-mentioned (meth) acrylic acid ester of the present invention, a monomer having two or more functional and multiple aromatic rings, and a polymerization initiator. By including, it has a viscosity suitable for moldability. In addition, the (co) polymer of the present invention has high transparency, a high refractive index, and a high glass transition point. By containing an antioxidant, the (co) polymer can suppress coloring due to oxidation of the (co) polymer and coloring due to heating during 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 carried out after the monomer solution is polymerized, or may be carried out at the same time as the polymerization. Examples of the molding method include a coating method, a potting molding method, a casting molding method, a printing molding method, a LIM method, a 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 improved.

Examples of the transparent optical member to which the (co) polymer of the present invention can be applied include a light emitting diode module, a mobile phone, a smartphone, a tablet terminal, a personal computer, a camera, an organic electroluminescence (organic EL) device, and the like. Films, sheets, lenses, optical waveguides, encapsulants, fillers, adhesives, reflectors, adhesives, wavelengths used in flat panel displays, touch panels, electronic paper, photodiodes, phototransistors, solar cells, projectors, etc. Examples include conversion materials. Since the (co) polymer of the present invention has high transparency, high refractive index and high glass transition point, it is particularly useful as a lens such as a camera lens. Further, by adding an antioxidant, coloring due to heating during reflow can be suppressed, so that 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.
The data in Examples and Comparative Examples were measured by the following methods.

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

(B) Actual yield The actual yield was calculated by the following formula.
Actual yield (%) = (C / D) x 100
Here, C represents the number of moles of the obtained target product, 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.
Equipment: 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,
Waiting time: 2.816 seconds)
Accumulation number: 8 times
¹³ C one-dimensional mode
Irradiation pulse width: 10.83 microseconds (90 degree pulse)
Pulse repetition time: 3.04333 seconds
(FID capture time: 1.04333 seconds,
Waiting time: 2 seconds)
Number of integrations: 1024 times

(D) Molecular Weight The molecular weight of each compound is gas chromatograph mass spectrometry (hereinafter referred to as "GC-MS". Equipment: Azilent Technology Co., Ltd., Azilent 5975GC-MS, Column: UA-5, Ionization method: Electron impact (EI) Ionization).

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

(F) Total light transmittance and haze monomer solution were photopolymerized and then after-cured 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 Technology Laboratory, HM-150 type).

(G) Refractive index The monomer solution was photopolymerized and then aftercured to obtain a (co) polymer having a thickness of about 100 μm. The refractive index of the (co) polymer (sodium D line (589 nm), 25 ° C.) was measured with a multi-wavelength Abbe refractometer (DR-M2, manufactured by Atago Co., Ltd.). Methylene iodide (manufactured by Atago Co., Ltd.) was used as the measurement intermediate solution.

(H) Glass transition temperature The monomer solution was photopolymerized and then aftercured to obtain a (co) polymer having a size of about 4 mm × 35 mm × thickness of 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. A dynamic viscoelasticity measuring device (RSA-II manufactured by TA Instruments Japan Co., Ltd.) was used for the measurement, and the measurement conditions were a tension mode and a measurement frequency of 10 Hz.

The following Examples and Comparative Examples exemplify the production of the (meth) acrylic acid ester of the present invention and its physical properties.

(Example 1)
Under a nitrogen atmosphere, 327.9 g of a methylmagnesium bromide-12 mass% tetrahydrofuran solution [manufactured by Tokyo Kasei Co., Ltd., 0.33 mol] was placed in a 500 ml three-necked flask equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermometer. , The inner solution of the flask was stirred. The liquid in the flask was cooled to 0 ° C. 28.26 g of 4- (methylthio) benzaldehyde [manufactured by Tokyo Kasei Co., Ltd., 0.22 mol] was gradually added dropwise into the flask over 1 hour. After the dropping, the cooling was stopped, the internal solution of the flask was returned to room temperature, and then the mixture was stirred for 2 hours. The internal solution of the flask was cooled to 0 ° C. again, 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 layer was washed with 100 ml of a 5 mass% potassium carbonate aqueous solution, concentrated using a rotary evaporator, and tetrahydrofuran was distilled off. As a result, a white solid 1- [4- (methylthio) phenyl] -1-hydroxyethyl 25 was obtained. .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 inhibitor As an agent, 0.03 g of 4,4'-[1,2-phenylenebis (carbonyloxy)] bis [2,2,6,6-tetramethylpiperidin-N-oxyl] was mixed, and a cooling tube and Dean Stark were mixed. It was placed in a 100 ml three-necked flask equipped with an apparatus, a stir bar, an air introduction tube, and a thermometer. The inner liquid of the flask was stirred while introducing air, and the flask was heated in an oil bath. Methyl methacrylate and water were azeotropically extracted at an internal temperature of 100 to 110 ° C. After analyzing the water content of the liquid in the flask and confirming that the water content was 100 ppm or less, 0.10 g of titanium tetrabutoxide [manufactured by Kanto Chemical Co., Inc., 0.0003 mol] was added as a catalyst. Then, the reaction was carried out at an internal temperature of 100 to 120 ° C. for 8 hours while extracting methyl methacrylate and methanol by azeotrope. After completion of the reaction, the mixture was cooled and concentrated using a rotary evaporator to distill off excess methyl methacrylate. When the residue was distilled and purified under reduced pressure, a transparent liquid methacrylic acid-1- [4- (methylthio) phenyl] ethyl 29.05 g [0.12 mol] 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 the 13C} 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 viscosities of -1- [4- (methylthio) phenyl] ethyl methacrylate measured at various temperatures using a conical flat plate type rotary viscometer.

(Comparative Example 1)
Table 1 shows the viscosities of -o-phenylphenoxyethyl acrylate [NK ester A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.] measured at various temperatures using a conical flat plate type rotary viscometer.

(Comparative Example 2)
Methyl methacrylate (1-naphthyl) was synthesized by the method described in Patent Document 6 (Japanese Unexamined Patent Publication No. 08-263949).

Table 1 shows the viscosities of methyl methacrylate (1-naphthyl) measured at various temperatures using a conical flat 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, pp. 249-255, 2010).

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

(Example 2)
In a reaction vessel equipped with a cooler, 100 parts of ethyl methacrylate-1- [4- (methylthio) phenyl] ethyl and 3 parts of 1-hydroxycyclohexylphenyl ketone produced in Example 1 [Irgacure 184, manufactured by BASF Co., Ltd.] were placed. 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 rays having an integrated light amount 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 cut out from a rectangular shape of about 4 mm × 35 mm was used as a gasket to obtain a molded product made of a homopolymer having a thickness of about 4 mm × 35 mm × 1 mm. Further, in the same method, a molded product 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.

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

(Comparative Examples 4 to 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 was prepared. A molded product made of the above was obtained, and various measurements were carried out. The results are shown in Table 2.

(Example 3)
In a reaction vessel equipped with a cooler, 15 parts of -1- [4- (methylthio) phenyl] ethyl methacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene produced in Example 1 70 parts [manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A-BPEF], 15 parts of benzyl methacrylate [manufactured by Mitsubishi Rayon Co., Ltd., trade name Acryloyl BZ], 3 parts of 1-hydroxycyclohexylphenyl ketone [manufactured by BASF Co., Ltd.] , Irgacure 184] was added, and the mixture was stirred at 70 ° C. for 2 hours to obtain a monomer solution. Table 2 shows the viscosities of the monomer solutions 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 rays having an integrated light amount 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 cut out from a rectangular shape of about 4 mm × 35 mm was used as a gasket to obtain a molded product made of a copolymer having a thickness of about 4 mm × 35 mm × 1 mm. Further, in the same method, a molded product 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 a molded product made of the obtained copolymer, the 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 made of the above was obtained, and various measurements were carried out. 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 Corporation, 0.60 mol] was used instead of methyl methacrylate. A transesterification reaction with 25.24 g [0.15 mol] of −hydroxyethyl was carried out. At this time, methyl acrylate and water were azeotropically extracted at an internal temperature of 80 to 90 ° C., and after the catalyst was added, the reaction was carried out at an internal temperature of 80 to 100 ° C. for 12 hours while extracting methyl acrylate and methanol by azeotrope. .. When the residue obtained after the reaction was distilled and purified under reduced pressure, 23.17 g of clear liquid acrylic acid-1- [4- (methylthio) phenyl] ethyl having a boiling point of 138 ° C./0.37 hPa and a purity of 99.1% was obtained. [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 the 13C} 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 viscosities of -1- [4- (methylthio) phenyl] ethyl acrylate measured at various temperatures using a conical flat plate type rotary viscometer.

(Example 5)
In the same manner as in Example 1, 250.0 g of an ethylmagnesium bromide-13 mass% tetrahydrofuran solution [manufactured by Tokyo Kasei Co., Ltd., 0.24 mol] was used instead of the methyl magnesium bromide-12 mass% tetrahydrofuran solution. When it was allowed to act on 24-74 g [manufactured by Tokyo Kasei Co., Ltd., 0.16 mol] of 4- (methylthio) benzaldehyde, a 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 inhibitor As an agent, 0.02 g of 4,4'-[1,2-phenylenebis (carbonyloxy)] bis [2,2,6,6-tetramethylpiperidin-N-oxyl] was mixed, and a cooling tube and Dean Stark were mixed. It was placed in a 100 ml three-necked flask equipped with an apparatus, a stirrer, an air introduction tube, and a thermometer. The inner liquid of the flask was stirred while introducing air, and the flask was heated in an oil bath. Methyl methacrylate and water were azeotropically extracted at an internal temperature of 100 to 110 ° C. After analyzing the water content of the liquid in 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. Then, the reaction was carried out at an internal temperature of 100 to 120 ° C. for 16 hours while extracting methyl methacrylate and methanol by azeotrope. After completion of the reaction, the mixture was cooled and concentrated using a rotary evaporator to distill off excess methyl methacrylate. When the residue was distilled and purified under reduced pressure, a transparent liquid methacrylic acid-1- [4- (methylthio) phenyl] propyl 20.48 g [0.08 mol] 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 ^{The spectrum of the 13C} one-dimensional mode (solvent: deuterated acetonitrile) is shown in FIG. 8, and the mass spectrum of GC-MS is shown in FIG.

Table 1 shows the viscosities of -1- [4- (methylthio) phenyl] propyl methacrylate measured at various temperatures using a conical flat plate type rotary viscometer.

(Example 6)
1- [4- (Methylthio) phenyl] -1 in the same manner as in Example 5 except that 36.60 g of methyl acrylate [manufactured by Mitsubishi Chemical Corporation, 0.43 mol] 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 azeotropically extracted at an internal temperature of 80 to 90 ° C., and after the catalyst was added, the reaction was carried out at an internal temperature of 80 to 100 ° C. for 24 hours while azeotropic extraction of methyl acrylate and methanol. .. When the residue obtained after the reaction was distilled and purified under reduced pressure, a transparent liquid acrylic acid-1- [4- (methylthio) phenyl] propyl 17.85 g 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 the 13C} 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 viscosities of -1- [4- (methylthio) phenyl] propyl acrylate measured at various temperatures using a conical flat plate type rotary viscometer.

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

Claims (4)

A methacrylic acid ester represented by the following formula (1).

(In the formula, ^{R 1} .R ² showing an ethyl group shows the methylation group.) The first aspect of claim 1, wherein an organic metal compound having an ethyl group is allowed to act on the compound represented by the following formula (2) to produce a compound represented by the following formula (3), and the compound is esterified with a methacrylic acid derivative. Method for producing methacrylic acid ester.

(In the formula, R ¹ represents an ethyl group .) The homopolymer of the methacrylic acid ester according to claim 1. A copolymer of the methacrylic acid ester according to claim 1 and another monomer.

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