JP6951233B2 - Compounds, moldings and optical materials - Google Patents

Description

The present invention relates to a polycarbonate resin having a specific repeating unit and an optical material formed by the polycarbonate resin represented by an optical lens.

Optical glass or transparent resin for optics is used as a material for optical elements used in the optical system of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many kinds of materials having various refractive indexes (nD) and Abbe number (νD). However, it has problems that the material cost is high, the molding processability is poor, and the productivity is low. In particular, processing into an aspherical lens used for aberration correction requires extremely advanced technology and high cost, which is a major obstacle in practical use.

On the other hand, optical transparent resins, especially optical lenses made of thermoplastic transparent resins, have the advantage that they can be mass-produced by injection molding and that aspherical lenses can be easily manufactured. It is used as. Examples of the transparent resin for optics include polycarbonate made of bisphenol A, polystyrene, poly-4-methylpentene, polymethylmethacrylate, and amorphous polyolefin.

However, when an optical transparent resin is used as an optical lens, transparency, heat resistance, and low compound refractive index are required in addition to the refractive index and Abbe number, so the place of use is limited by the balance of resin characteristics. There are weaknesses. For example, polystyrene has low heat resistance and high double refraction, poly-4-methylpentene has low heat resistance, polymethylmethacrylate has low glass transition temperature, low heat resistance, and low refractive index. Polycarbonate composed of bisphenol A. Has a weak point such as a large double refraction, so that the place of use is limited, which is not preferable.

On the other hand, when the refractive index of the optical material is generally high, a lens element having the same refractive index can be realized on a surface having a smaller curvature, so that the amount of aberration generated can be reduced. Increasing the refractive index is useful because it makes it possible to reduce the number of lenses, reduce the eccentric sensitivity of the lens, and reduce the thickness of the lens to reduce the size and weight of the lens system.

Patent Document 1 describes a highly transparent polycarbonate using a diol compound having a specific structure in which two hydroxyl group-containing groups are bonded, which contains an aromatic hydrocarbon ring having two or more benzene rings at the 9-position of the fluorene ring. Although a resin or a polyester resin is disclosed, it has a high melt viscosity and leaves a problem in moldability. In Patent Document 2, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, a specific polyorganosiloxane compound, and 2,2-bis (4-hydroxyphenyl) propane are reacted with phosgene. Although the resulting polycarbonate resin with good moldability is disclosed, phosgene, which is highly toxic during production, is used due to the high melt viscosity of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. It leaves the issue of needing to be done.

JP-A-2017-171827 Japanese Unexamined Patent Publication No. 2001-342247

An object to be solved by the present invention is to provide a compound having a low melt viscosity, a high refractive index, and a high glass transition temperature (heat resistance), and to provide an excellent optical material.

The present inventor has conducted diligent studies and found that the above problems can be solved by using a compound having a specific structure.

（式中、Ｍは、下記式（ａ）又は（ｂ）で表される群から選ばれる置換基を表し、
Ｍで表される基中の水素原子はハロゲン原子で置換される場合があり、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、炭素原子数１〜２０の炭化水素基又はハロゲン原子を表し、
Ｘ^１は、単結合又は−Ｒ^９Ｏ−を表し、
Ｘ^２は、単結合又は−ＯＲ^９−を表し、
Ｒ^９は、炭素原子数１〜２０の炭化水素基を表し、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９で表される基の中のメチレン基の１つ又は２つ以上は、酸素原子が隣り合わない条件で、−Ｏ−で置換される場合もあり、
化合物の構造中に、複数存在するＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｘ^１、Ｘ^２及びＭは、それぞれ、同一である場合も、異なる場合もある。）

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５及びＲ^２６は、それぞれ独立に、水素原子、炭素原子数１〜２０の炭化水素基、複素環を含有する炭素原子数２〜２０の基又はハロゲン原子を表し、
Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５及びＲ^２６で表される基中のメチレン基の１つ又は２つ以上は、酸素原子又は硫黄原子が隣り合わない条件で、−Ｏ−又は−Ｓ−で置換される場合があり、
Ｒ^１１とＲ^１２、Ｒ^１２とＲ^１３、Ｒ^１３とＲ^１４、Ｒ^１９とＲ^２０、Ｒ^２０とＲ^２１及びＲ^２１とＲ^２２は結合して環を形成する場合があり、
式中の＊は、これらの式で表される基が、＊部分で、隣接する基と結合することを意味する。） That is, the present invention relates to the following items.
[1] A compound having a repeating unit represented by the following general formula (I).

(In the formula, M represents a substituent selected from the group represented by the following formula (a) or (b).
The hydrogen atom in the group represented by M may be replaced with a halogen atom.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, respectively.
X ¹ represents a single bond or -R ⁹ O-
X ² represents a single bond or a -OR ⁹ - represents,
R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms.
One or more of the methylene groups among the groups represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 have oxygen atoms next to each other.} In some cases, it may be replaced with -O- under no conditions.
^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X ¹ , X ^2, and M, which are present in a plurality in the structure of the compound, are the same, respectively. In some cases, it may be different. )

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R. ²⁶ independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group containing a heterocycle and having 2 to 20 carbon atoms, or a halogen atom.
Represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ^26. One or more of the methylene groups in the group may be replaced with -O- or -S- under the condition that the oxygen atom or the sulfur atom is not adjacent to each other.
R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁹ and R ²⁰ , R ²⁰ and R ²¹ and R ²¹ and R ²² may combine to form a ring.
* In the formulas means that the groups represented by these formulas are bonded to adjacent groups at the * part. )

[2] In the above general formula (I), ^{at least one of R 15} , R ¹⁶ , R ¹⁷ and R ¹⁸ of (a) is a phenyl group or R ²³ , R ²⁴ , R ²⁵ and R ²⁶ of (b). The compound according to [1], wherein at least one of them is a phenyl group.

[3] The compound according to [1] or [2], wherein in the above general formula (I), R ^{15 of} (a) is a phenyl group or ^{at least one of R 23} and R ^{25 of (b) is a phenyl group.} ..

[4] The compound according to any one of [1] to [3], wherein M is (a) in the above general formula (I).

[5] A molded product containing the compound according to any one of [1] to [4].

[6] An optical material made of the molded product according to [5].

According to the present invention, it is possible to provide a compound having a high refractive index, a high glass transition temperature (heat resistance) and a low melt viscosity, and by using the compound, an excellent high refractive index optical lens can be obtained.

Hereinafter, the preferred embodiment of the present invention will be described in detail.
The present invention relates to an optical material (camera lens for smartphones, spectacle lens) having a high refractive index, a low Abbe number, a low double refraction, a high transparency, and a high glass transition temperature (heat resistance) in a well-balanced manner. It is formed from a compound having a repeating unit represented by the general formula (I).

^{The hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to} R ⁸ in the general formula (I) is not particularly limited, but is an alkyl group having 1 to 20 carbon atoms and a carbon atom. An alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms. It is preferably a group or the like. Among these, when used as an optical material, since it has a high refractive index, it has an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arcandyl group having 1 to 10 carbon atoms, and carbon. More preferably, it is a cycloalkyl group having 3 to 10 atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, or the like.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, and isooctyl. , 2-Ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like. Examples of the alkyl group having 1 to 10 carbon atoms include methyl. Ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl and isodecyl, etc. Can be mentioned.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4 , 8,12-Tetradecatrienylallyl and the like. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl and 3-. Examples thereof include pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl and 4-decenyl and the like.

The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and tetradecahydroanthrasenyl, etc. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo. [1.1.1] Pentanyl and the like can be mentioned.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with a cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2- Cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-Cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecyl Examples thereof include butyl, 3-3-adamantylpropyl, decahydronaphthylpropyl and the like. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclo. Heptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, Examples thereof include 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl and 4-cyclohexylbutyl.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, trill, xsilyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl and the like, the alkyl group, the alkenyl group, the carboxyl group, the halogen atom and the like. Substituted phenyl, biphenylyl, naphthyl, anthryl and the like, for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like can be mentioned, and the number of carbon atoms is described above. Examples of the 6 to 10 aryl groups include phenyl, trill, xsilyl, ethylphenyl, naphthyl and the like, and phenyl, biphenylyl and naphthyl substituted with one or more of the above alkyl group, the above alkenyl group, the carboxyl group, a halogen atom and the like. , Anthrill and the like, for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like.

The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 30 carbon atoms in which the hydrogen atom of the alkyl group is substituted with an aryl group. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, naphthylpropyl and the like can be mentioned. The arylalkyl group having 7 to 20 carbon atoms is an aryl group in which the hydrogen atom of the alkyl group is an aryl group. It means a group having 7 to 20 substituted carbon atoms. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like can be mentioned.

The hydrocarbon groups having 1 to 20 carbon atoms represented by ^{R 9} in the general formula (I) include various groups listed as monovalent hydrocarbon groups represented by ^{R 1 to} R ^{8 above.} Corresponding divalent hydrocarbon groups can be mentioned.

One or more of the methylene groups among the groups represented by ^{R 1 to} R ⁹ in the above general formula (I) may be substituted with −O−. In this case, it is a condition that the oxygen atoms are not adjacent to each other, and specifically, it is a condition that -O-O- is not contained.

As the hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 11 to} R ²⁶ in the substituents (a) and (b), the hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 1 to} R ^{8 is mentioned above.} The same as the hydrocarbon group can be mentioned.

^{The group having 2 to 20 carbon atoms containing the heterocycle represented by R 11 to} R ²⁶ in the substituents (a) and (b) is not particularly limited, but for example, pyrrolyl, pyridyl, and the like. Pyridylethyl, pyrimidyl, pyridadyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazil, triazilmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl , Thiazolyl, benzothiazolyl, oxazolidine, benzoxazolyl, isothiazolidine, isooxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidine- Examples thereof include 3-yl and 2,4-dioxyoxazolidine-3-yl, and specific examples including substituents and the like include groups having the following structures.

（上記式中、Ｒは水素原子又は炭素原子数１〜６のアルキル基を表し、Ｚは直接結合又は炭素原子数１〜６のアルキレン基を表す。尚、式中の＊は、これらの式で表される基が、＊部分で、隣接する基と結合することを意味する。）

(In the above formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. * In the formula, these formulas. It means that the group represented by is bonded to an adjacent group at the * part.)

Examples of the alkyl group having 1 to 6 carbon atoms include those having 1 to 6 carbon atoms among those exemplified above as alkyl groups having 1 to 20 carbon atoms.

Examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, and hexylene.

^{R 11} and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁹ and R ²⁰ , R ²⁰ and R ²¹ and R ²¹ and R ^{22 in the} substituents (a) and (b) are bonded. Examples of the ring to be formed include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a pyrrolidine ring, a pyrrol ring, a piperazine ring, a morpholine ring, a thiomorpholin ring, a tetrahydropyridine ring, a lactone ring and a lactam ring. Examples thereof include a to 7-membered ring and a fused ring such as a naphthalene ring and an anthracene ring.

One or more of the methylene groups among the groups represented by ^{R 11 to} R ²⁶ in the above general formula (I) may be substituted with -O- or -S-. In this case, it is a condition that oxygen atoms or sulfur atoms are not adjacent to each other, and specifically, it is a condition that -O-O-, -O-S-, and -S-S- are not included.

Examples of the halogen atom of the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

^{One or more of R 1 to} R ⁹ and R ^{11 to} R ²⁶ of the above general formula (I) having an aryl group is preferable because the obtained compound has a high refractive index, and the aryl group is a phenyl group. In this case, it is more preferable because the diol component which is the raw material of the compound can be easily synthesized. Among them, ^{at least one or more of R 15} , R ¹⁶ , R ¹⁷ and R ¹⁸ of (a) is a phenyl group, or at least one or more of R ²³ , R ²⁴ , R ²⁵ and R ²⁶ of (b). Those having a phenyl group are preferable. In particular, since the synthesis of the diol component is easy, the substitution position of the phenyl group, if the above general formula (I) M is (a), if is preferably R ^15, M is (b), It is preferably R ²³ or R ^25.

The compound of the general formula (I) in which M is (a) is preferable because the diol component as a raw material can be easily synthesized.

The preferred polystyrene-equivalent weight average molecular weight (Mw) of the compound of the present invention is 20,000 to 300,000. More preferably, the polystyrene-equivalent weight average molecular weight (Mw) is 30,000 to 120,000.
It is preferable to use the above-mentioned compound having an average molecular weight because an optical lens having high productivity and excellent strength can be obtained.

The above compound is preferably a compound having a high refractive index because the film thickness of the molded product using the compound can be reduced.

The above compound preferably has excellent heat resistance, and specifically, the glass transition temperature (Tg) is preferably 250 ° C. or higher, and more preferably 280 ° C. or higher.

Since the above compound is excellent in moldability, the melt viscosity is preferably less than 1000 Pa · s, and more preferably less than 800 Pa · s.

The compound of the present invention can be produced by a known melt polycondensation method in which a raw material diol component is reacted with a carbonic acid diester in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst consisting of both of them. .. Only one type of diol component may be used, or two or more types may be used.

As a preferable example of the above diol component, the compound No. A1 to A43 can be mentioned.

Examples of the carbonic acid diester include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable. The carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, with respect to 1 mol of the diol component. Only one type of carbonic acid diester may be used, or two or more types may be used.

Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

Examples of the alkali metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkali metals. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, stearer. Sodium acid, potassium stearate, cesium stearate, lithium stearate, sodium boron hydride, sodium phenylated, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, sodium hydrogen phosphate, hydrogen phosphate Dipotassium, 2 lithium hydrogen phosphate, 2 sodium phenyl phosphate, 2 sodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt, etc. are used. Be done.

Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkaline earth metals. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogencarbonate, calcium hydrogencarbonate, strontium hydrogencarbonate, barium hydrogencarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, acetic acid. Magnesium, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate and the like are used.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxide and salts thereof, amines and the like. Specifically, quaternary ammonium hydroxides having alkyl, aryl, group, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, etc. Tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2-phenylimidazole and benzoimidazole. And other imidazoles, or bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like are used.

As the transesterification catalyst, salts of zinc, tin, zirconium and lead are preferably used, and these can be used alone or in combination.
Examples of the ester exchange catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II), tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltin dilaurate, and dibutyltin. Examples thereof include oxide, dibutyltin dimethoxyde, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II) and lead acetate (IV).

These catalysts are used in a ratio of ^10-9 to ^10-3 mol, preferably ^10-7 to ^10-4 mol, relative to a total of 1 mol of the diol component.

In the melt polycondensation method, melt polycondensation is carried out by a transesterification reaction while heating under normal pressure or reduced pressure using the above-mentioned raw materials and catalyst to remove by-products. The reaction is generally carried out in a multi-step process of two or more steps.

Specifically, the first-stage reaction is carried out at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours under normal pressure or reduced pressure. Next, the reaction temperature was raised while increasing the degree of pressure reduction of the reaction system to carry out the reaction between the diol component and the carbonic acid diester, and finally polycondensation was carried out at a temperature of 200 to 350 ° C. for 0.05 to 2 hours under a reduced pressure of 1 mmHg or less. Make a reaction. Such a reaction may be carried out continuously or in a batch manner. The reactor used to carry out the above reaction is equipped with paddle blades, lattice blades, glasses blades, etc., even if it is a vertical type equipped with anchor type stirring blades, max blend stirring blades, helical ribbon type stirring blades, etc. It may be a horizontal type or an extruder type equipped with a screw, and it is preferably carried out by using a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer.

In the method for producing a compound having a repeating unit represented by the general formula (I), the catalyst is removed or inactivated after the completion of the polymerization reaction in order to maintain thermal stability and hydrolysis stability. In general, a method of deactivating the catalyst by adding a known acidic substance is preferably carried out. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluene sulfonic acid, and aromatic sulfonic acids such as butyl p-toluene sulfonic acid and hexyl p-toluene sulfonic acid. Esters, phosphoric acids such as sulphonic acid, sulphonic acid, phosphonic acid, triphenyl sulphonate, monophenyl sulphonate, diphenyl sulphonate, diethyl sulphonate, din-propyl sulphonate, sulphate Subphosphate esters such as din-butyl, din-hexyl sulfonate, dioctyl sulfonate, monooctyl sulfonate, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphorus Phosphonates such as dioctyl acid and monooctyl phosphate, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid, phosphonic acid esters such as diethylphenylphosphonate, triphenylphosphine, bis (diphenylphosphino) ) Phosphins such as ethane, boric acids such as boric acid and phenylboric acid, aromatic sulfonates such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid, organic halogens such as chloride stearate, benzoyl chloride and chloride p-toluenesulfonic acid. Compounds, alkyl sulfates such as dimethyl sulfate, organic halides such as benzyl chloride, and the like are preferably used. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol, based on the amount of catalyst. If it is less than 0.01 times the molar amount of the catalyst amount, the deactivating effect becomes insufficient, which is not preferable. On the other hand, if the amount is more than 50 times the molar amount of the catalyst, the heat resistance of the compound is lowered and the molded product is easily colored, which is not preferable.

After the catalyst is deactivated, a step of volatilizing and removing the low boiling point compound in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350 ° C. may be provided. A horizontal device having a stirring blade having excellent surface renewal ability such as a blade, or a thin film evaporator is preferably used.

The molded product of the present invention may contain a compound having a repeating unit represented by the above general formula (I), and is not particularly limited, but has high moldability, high transparency, and high refractive index. Since it can form a thin film, it can be preferably used for optical materials, especially optical lenses.

Since it is desired that the molded product contains as little foreign matter as possible, filtration of the molten raw material and filtration of the catalyst solution are preferably carried out when producing the compound. The mesh of the filter used for filtration is preferably 5 μm or less, more preferably 1 μm or less. Further, filtration of the obtained compound with a polymer filter is preferably performed. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Further, the step of collecting the pellets of the above compound must naturally be in a low dust environment, and is preferably class 1000 or less, and more preferably class 100 or less.

The molded product of the present invention can be obtained by injection molding a compound having a repeating unit represented by the above general formula (I) into a desired shape by an injection molding machine or an injection compression molding machine. The molding conditions for injection molding are not particularly limited, but the molding temperature is preferably 180 to 280 ° C. The injection pressure is preferably 50 to 1700 kg / cm ² .

In order to avoid foreign matter from being mixed into the molded product as much as possible, the molding environment must naturally be a low dust environment, preferably class 1000 or less, and more preferably class 100 or less.

The molded product (optical lens) of the present invention thus obtained has a refractive index of 1.60 to 1.65, preferably 1.62 to 1.64, as measured by the method of JIS-K-7142.

A coat layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical lens, if necessary. The antireflection layer may be a single layer or a multi-layer structure, and may be an organic substance or an inorganic substance, but is preferably an inorganic substance. Specific examples thereof include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide and magnesium fluoride. Of these, more preferred are silicon oxide and zirconium oxide, and even more preferred are combinations of silicon oxide and zirconium oxide.
The antireflection layer is not particularly limited in terms of the combination of single layer / multilayer, their components, the combination of thickness, and the like, but is preferably a two-layer structure or a three-layer structure, and particularly preferably a three-layer structure. Further, the entire antireflection layer is preferably formed to have a thickness of 0.00017 to 3.3% of the thickness of the optical lens, specifically 0.05 to 3 μm, particularly preferably 1 to 2 μm. ..

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

<Example 1>
The above compound No. A1; 1514 g (4.0 mol), diphenyl carbonate; 878.2 g (4.1 mol), and sodium bicarbonate; 2.1 mg (2.5 x ^10-5 mol) in 5 liters with stirrer and distiller It was placed in a reactor and heated to 215 ° C. over 1 hour under a nitrogen atmosphere of 760 Torr and stirred.

Then, the degree of reduced pressure was adjusted to 150 Torr over 15 minutes, and the transesterification reaction was carried out by holding the mixture under the conditions of 215 ° C. and 150 Torr for 20 minutes. Further, the temperature was raised to 240 ° C. at a rate of 37.5 ° C./hr, and the temperature was maintained at 240 ° C., 150 Torr for 10 minutes. Then, it was adjusted to 120 Torr over 10 minutes and kept at 240 ° C. and 120 Torr for 70 minutes. Then, it was adjusted to 100 Torr over 10 minutes and kept at 240 ° C. and 100 Torr for 10 minutes. Further, the temperature was reduced to 1 Torr or less over 40 minutes, and the polymerization reaction was carried out under the conditions of 240 ° C. and 1 Torr or less for 10 minutes with stirring. After completion of the reaction, nitrogen was blown into the reactor to bring it to normal pressure, and compound No. I got 1.

<Comparative example 1>
Compound No. of Example 1 The same operation as in Example 1 was carried out except that A1 was changed to bisphenol A, and the comparative compound No. I got 1.

<Comparative example 2>
Compound No. of Example 1 The same procedure as in Example 1 was carried out except that A1 was changed to 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. I got 2.

<Comparative example 3>
Compound No. of Example 1 The same operation as in Example 1 was carried out except that A1 was changed to 1,4-butanediol. I got 3.

<Example 2, Comparative Examples 4 to 6>
The obtained compound No. 1 and Comparative Compound No. The following physical properties of 1 to 3 were measured by the methods shown below. The obtained measurement results are shown in Table 1.

<Polystyrene equivalent weight average molecular weight (Mw)>
Using GPC (manufactured by Hitachi, model number: ELITE LaChrom L-2000, column: KF-805, -804, -803 connection), using chloroform as the developing solvent, using standard polystyrene with a known molecular weight (molecular weight distribution = 1). A calibration curve was created. Based on this calibration curve, it was calculated from the retention time of GPC.

<Glass transition temperature (Tg)>
Measurement was performed using a differential thermal scanning calorimeter (DSC: manufactured by Hitachi, model number: DSC7000X), and the temperature at the intersection of the baseline of the obtained DSC curve and the tangent at the inflection point was defined as Tg.

<Refractive index>
The obtained compound was press-molded into a rectangular parallelepiped having a thickness of 3 mm × 8 mm × 8 mm, and measured by the method of JIS-K-7142 with a refractive index meter manufactured by ATAGO Co., Ltd.

<Melting viscosity>
Using a thin tube flow rheometer manufactured by Toyo Seiki Seisakusho Co., Ltd., the following operation was performed to measure the melt viscosity.
After heating the obtained compound to 300 ° C. to completely melt it, the injection rate was set to 0.01 to 150 mm / s, and the ratio (L / D) of the length (L) to the diameter (D) was 40. Measurements were made using six types of capillaries for measuring melt viscosity: / 2, 20/1, 10 / 0.5, 15/1, 10/1, and 5/1.
In the above evaluation, those having a melt viscosity of less than 800 Pa · s were rated as 〇, those having a melt viscosity of 800 Pa · s or more and less than 1000 Pa · s were rated as Δ, and those having a melt viscosity of 1000 Pa · s or more were rated as x.

As shown in Table 1, the compound of the present invention is useful because it can provide a high-quality optical material. Specifically, it is possible to provide an optical material having high heat resistance (high Tg), low film thickness (high refractive index), and excellent moldability (low melt viscosity).

Claims (7)

A compound having a repeating unit represented by the following general formula (I).

(In the formula, M represents a substituent selected from the group represented by the following formula (a) or (b).
The hydrogen atom in the group represented by M may be replaced with a halogen atom.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, respectively.
X ¹ represents a single bond or -R ⁹ O-
X ² represents a single bond or a -OR ⁹ - represents,
R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms.
One or more of the methylene groups among the groups represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 have oxygen atoms next to each other.} In some cases, it may be replaced with -O- under no conditions.
^{R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X ¹ , X ^2, and M, which are present in a plurality in the structure of the compound, are the same, respectively. In some cases, it may be different. )

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R. ²⁶ independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group containing a heterocycle and having 2 to 20 carbon atoms, or a halogen atom.
^{At least one of R 15} , R ¹⁶ , R ¹⁷ and R ¹⁸ of (a) is an aryl group or at least one of R ²³ , R ²⁴ , R ²⁵ and R ²⁶ of (b) is an aryl group.
Represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ^26. One or more of the methylene groups in the group may be replaced with -O- or -S- under the condition that the oxygen atom or the sulfur atom is not adjacent to each other.
R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁹ and R ²⁰ , R ²⁰ and R ²¹ and R ²¹ and R ²² may combine to form a ring.
* In the formulas means that the groups represented by these formulas are bonded to adjacent groups at the * part. ) In the above general formula (I), ^{at least one of R 15} , R ¹⁶ , R ¹⁷ and R ¹⁸ of (a) is a phenyl group or at least one of R ²³ , R ²⁴ , R ²⁵ and R ²⁶ of (b). The compound according to claim 1, wherein one is a phenyl group. In the above general formula (I), R of (a) ¹⁵ Is an aryl group or R of (b) ²³ And R ²⁵ The compound according to claim 1, wherein at least one of them is an aryl group. The compound according to claim 2 or 3 , wherein in the general formula (I), R ^{15 of} (a) is a phenyl group or ^{at least one of R 23} and R ²⁵ of (b) is a phenyl group. The compound according to any one of claims 1 to 4 , wherein in the general formula (I), M is (a). A molded product containing the compound according to any one of claims 1 to 5. An optical material comprising the molded product according to claim 6.