JP2003268112A - Phosphorus-containing resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin having a low haze value, a high refractive index and a high Abb's number. <P>SOLUTION: The resin composition is composed of a recurring unit expressed by the formula (1) (R is a 1-20C hydrocarbon group; X denotes oxygen, sulfur or selenium), a recurring unit expressed by the formula (2) (R's are each selected from the specific substituent groups; p and q are each an integer satisfying p+q=0 to 8; Y is selected from the group consisting of a single bond, an oxygen atom, a sulfur atom and a specified substituent group) and a carbonate residue, and the mole fractions of the recurring unit of the formula (1) and the recurring unit of the formula (2) satisfy the inequality (3): 1≥(a)/[(a)+(b)]≥0.05 (wherein (a) denotes a mole number of the recurring unit of the formula (1) and (b) denotes the mole number of the carbonate residue). The number-average molecular weight of the resin composition is ≥300,000 and its molding with 3 mm thickness has 70% or more whole light transmittance and 30% or less haze. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorless and transparent thermoplastic resin having a low dispersion, a high refractive index and extremely high transparency.

[0002]

2. Description of the Related Art Optical lenses are used mainly as colorless transparent materials. Among them, spectacle lenses are being actively developed from the viewpoints of thinning, weight saving and fashionability. At present, 90% of the market is occupied by resin lenses due to advantages such as impact resistance and light weight.

Conventional spectacle lens resins are roughly classified into three types, CR39, acrylic, and urethane (Japanese Patent Laid-Open No. 06-0167).
No. 29), many resins have been developed and put to practical use aiming at low dispersion and high refraction. Since all of these resins are thermosetting, casting polymerization is used for molding into an optical lens, but this method has a problem that the polymerization time is long and the manufacturing cost is high, such as the subsequent annealing process.

On the other hand, polycarbonate is a typical thermoplastic optical resin. This is used for a disk substrate or the like by taking advantage of its colorless transparency and impact resistance. When this resin is applied to a lens, it has an advantage that it has good moldability because it is thermoplastic and that the lens manufacturing cost can be significantly reduced as compared with a thermosetting resin. However, due to its low refractive index (1.58), it is applied only to protective eyewear as a spectacle lens application. Aromatic thermoplastic resins other than polycarbonate have high refractive index, but have problems such as high dispersibility and colorability. Further, it is reported that an aromatic polyphosphonate thermoplastic resin (US Pat. No. 6,288,210), which has a phosphonic acid residue in the main chain and is a condensation polymer with bisphenols, etc., has high refractive index characteristics. However, there are problems such as lack of toughness. As an attempt to improve the toughness of the polyphosphonate resin, it has been reported that the polyphosphonate resin has a high molecular weight (Japanese Patent Laid-Open No. 61-285225).
The present inventors have confirmed that coloring occurs due to heating at a temperature of not lower than 0 ° C., and the resin obtained by this is not suitable for optical use. In addition, as a means for increasing the molecular weight, there is a report on a polymerization method of reacting in an aqueous solution containing an alkaline earth metal hydroxide in the presence of a phase transfer catalyst (JP-A-61-238826). The present inventors have confirmed that high molecular weight cannot be obtained by a similar method. When the polyphosphonate resin is made to have a high molecular weight (number average molecular weight: 30,000 or more), depending on the molecular structure of the bisphenol portion, the resin composition has poor solubility and meltability, so that the molded product becomes cloudy and remarkably transparent. There was a problem of being damaged.

[0005]

The present invention has a high refractive index,
It has low dispersion properties, is extremely transparent, and
An object is to provide a thermoplastic resin having high toughness.

[0006]

The present invention has the following constitution in order to solve the above problems.

A resin comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2) and a carbonate residue, wherein the repeating unit of the above formula (1) and the above formula (2) The molar fraction of the repeating unit is represented by the formula (3)
And a molded product having a thickness of 3 mm is satisfied, the total light transmittance is 70% or more, the haze is 30% or less, and the number average molecular weight is 300.
A resin characterized by being 00 or more.

[0008]

[Chemical 3]

[0009]

[Chemical 4]

[In the formula (1), R represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 20 carbon atoms, X represents oxygen, sulfur or selenium, and R or a phosphonic acid residue having different X are both present. May be included. R'in the formula (2) is independently selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a nitro group, p and q are integers of p + q = 0 to 8. Y is a single bond, an oxygen atom, a sulfur atom, an alkylene group,
Alkylidene group, cycloalkylene group, cycloalkylidene group, halo-substituted alkylene group, halo-substituted alkylidene group, phenylalkylidene group, carbonyl group, sulfone group, aliphatic phosphine oxide group, aromatic phosphine oxide group, alkylsilane group, dialkylsilane group , A fluorene group. 1 ≧ (a) / {(a) + (b)} ≧ 0.05 (3) [In the formula (3), (a) is the number of moles of the repeating unit of the formula (1), and (b) is Number of moles of carbonate residues. ]

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphonate resin used in the present invention has the following structure. That is, the following formula (1)
The resin is composed of a repeating unit represented by, a repeating unit represented by the following formula (2), and a carbonate residue.

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[In the formula (1), R represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 20 carbon atoms, X represents oxygen, sulfur or selenium, and R or a phosphonic acid residue having different X together. May be included. In formula (2), R'is independently selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group, and a nitro group, and p and q are p + q = An integer of 0 to 8, Y is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group, a halo-substituted alkylene group, a halo-substituted alkylidene group, a phenylalkylidene group, a carbonyl group, a sulfone group. , An aliphatic phosphine oxide group, an aromatic phosphine oxide group, an alkylsilane group, a dialkylsilane group, and a fluorene group. ] The substituent R on the phosphorus atom of the compound represented by the above formula (1)
Specific examples of phenyl, halo-substituted phenyl, methoxyphenyl, ethoxyphenyl, ethyl, isopropyl, cyclohexyl, vinyl, allyl, benzyl, aminoalkyl, hydroxyalkyl, halo-substituted alkyl,
An alkyl sulfide group etc. are mentioned. Specific examples of the phosphonic acid constituting the phosphonic acid residue represented by the formula (1) include methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid and isobutyl. Phosphonic acid,
t-butylphosphonic acid, n-pentylphosphonic acid, neopentylphosphonic acid, cyclohexylphosphonic acid, benzylphosphonic acid, chloromethylphosphonic acid, dichloromethylphosphonic acid, bromomethylphosphonic acid, dibromomethylphosphonic acid, 2-chloroethylphosphonic acid, 1, Two
-Dichloroethylphosphonic acid, 2-bromoethylphosphonic acid, 1,2-dibromoethylphosphonic acid, 3-chloropropylphosphonic acid, 2,3-dichloropropylphosphonic acid 3-bromopropylphosphonic acid, 2,3-dibromopropyl Phosphonic acid, 2-chloro-1-methylethylphosphonic acid, 1,2-dichloro-1-methylethylphosphonic acid, 2-bromo-1-methylethylphosphonic acid, 1,
2-dibromo-1-methylethylphosphonic acid, 4-chlorobutylphosphonic acid, 3,4-dichlorobutylphosphonic acid, 4-bromobutylphosphonic acid, 3,4-dibromobutylphosphonic acid, 3-chloro-1-methylpropylphosphonic acid Acid, 2,3-dichloro-1-methylpropylphosphonic acid, 3-bromo-1methylpropylphosphonic acid, 2,
3-dibromo-1-methylphosphonic acid, 1-chloromethylpropylphosphonic acid, 1-chloro-1-chloromethylpropylphosphonic acid, 1-bromomethylpropylphosphonic acid, 1-bromo-1-bromomethylpropylphosphonic acid, 5- Chloropentylphosphonic acid, 4,5-dichloropentylphosphonic acid, 5-bromopentylphosphonic acid,
4,5-dibromopentylphosphonic acid, 1-hydroxymethylphosphonic acid, 2-hydroxyethylphosphonic acid,
3-hydroxypropylphosphonic acid, 4-hydroxybutylphosphonic acid, 5-hydroxypentylphosphonic acid,
1-aminomethylphosphonic acid, 2-aminoethylphosphonic acid, 3-aminopropylphosphonic acid, 4-aminobutylphosphonic acid, 5-aminopentylphosphonic acid, methylthiomethylphosphonic acid, methylthioethylphosphonic acid,
Methylthiopropylphosphonic acid, methylthiobutylphosphonic acid, ethylthiomethylphosphonic acid, ethylthioethylphosphonic acid, ethylthiopropylphosphonic acid, propylthiomethylphosphonic acid, propylthioethylphosphonic acid, butylthiomethylphosphonic acid, phenylphosphonic acid, 4-chlorophenyl Phosphonic acid, 3,4-dichlorophenylphosphonic acid, 3,5-dichlorophenylphosphonic acid, 4-bromophenylphosphonic acid, 3,4-bromophenylphosphonic acid, 3,5-bromophenylphosphonic acid, 4-methoxyphenylphosphonic acid 3,4-dimethoxyphenylphosphonic acid, 1-naphthylphosphonic acid, 2
-Naphthylphosphonic acid, benzylphosphonic acid, 4-bromophenylmethylphosphonic acid, 3,4-dibromophenylmethylphosphonic acid, 3,5-dibromophenylmethylphosphonic acid, 2-phenylethylphosphonic acid, 2- (4
-Bromophenyl) ethylphosphonic acid, 2- (3,4-dibromophenyl) ethylphosphonic acid, 2- (3,5-dibromophenyl) ethylphosphonic acid, 3-phenylpropylphosphonic acid, 3- (4-bromophenyl) ) Propylphosphonic acid, 3- (3,4-dibromophenyl) propylphosphonic acid, 3- (3,5-dibromophenyl) propylphosphonic acid, 4-phenylbutylphosphonic acid, 4- (4-bromophenyl) butylphosphone Acid, 4- (3,4-dibromophenyl) butylphosphonic acid, 4- (3,5-dibromophenyl) butylphosphonic acid, 2-pyridylphosphonic acid, 3-pyridylphosphonic acid, 4-pyridylphosphonic acid, 1- Pyrrolidinomethylphosphonic acid, 1-pyrrolidinoethylphosphonic acid, 1-pyrrolidinopropylphosphonic acid, 1-pyrrolidinobutylphosphonic acid Acid, pyrrole-1
Phosphonic acid, pyrrole-2-phosphonic acid, pyrrole-3
-Phosphonic acid, thiophen-2-phosphonic acid, thiophen-3-phosphonic acid, dithian-2-phosphonic acid, trithian-2-phosphonic acid, furan-2-phosphonic acid, furan-3-phosphonic acid, vinylphosphonic acid, Examples thereof include allylphosphonic acid and the like, and thiophosphonic acid in which the oxygen atom bonded to these phosphorus atoms by a double bond is substituted with a sulfur atom is also included. These are just one
It may include a plurality of types.

Regarding these phosphonic acid residues,
It can be preferably partially substituted with the corresponding phosphonite residue which is a trivalent phosphorus functional group. This makes it possible to impart the oxidation resistance of the resin. The substitution ratio is 50 when considering the characteristic stability such as optical characteristics.
% Or less, more preferably 25% or less, still more preferably 10% or less.

Next, the dihydric phenol constituting the dihydric phenol residue represented by the formula (2) will be specifically exemplified.
1,1-bis (4-hydroxyphenyl) methane, 1,
1-bis (4-hydroxyphenyl) ethane, 1,1-
Bis (4-methyl-2-hydroxyphenyl) methane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1 , 1-bis (4-hydroxyphenyl) cycloheptane, 1,1-bis (4
-Hydroxyphenyl) cyclooctane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -2- Ethylhexane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane,
1,1-bis (3-methyl-4-hydroxyphenyl)
Methane, 4,4'-biphenol, 2,2-bis (4-
Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane,
2,2-bis (4-hydroxyphenyl) octane,
1,1-bis (3-methyl-4-hydroxyphenyl)
Cyclohexane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-
Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-secbutyl-4-)
Hydroxyphenyl) propane, bisphenolfluorene, 1,1-bis (2-methyl-4-hydroxy-5)
-Tert-butylphenyl) -2-methylpropane,
4,4 '-[1,4-phenylene-bis (2-propylidene)]-bis (2-methylphenol), 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 4,4'- Dihydroxyphenyl ether,
1,1-bis (2-hydroxyphenyl) methane, 2,
4'-methylenebisphenol, 1,1-bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-5-methylphenyl) ) Ethane, 1,
1-bis (4-hydroxyphenyl) -3-methyl-butane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1 , 1-bis (3-methyl-
4-hydroxyphenyl) cyclopentane, 3,3-bis (4-hydroxyphenyl) pentane, 3,3-bis (3-methyl-4-hydroxyphenyl) pentane,
3,3-bis (3,5-dimethyl-4-hydroxyphenyl) pentane, 2,2-bis (2-hydroxy-3,
5-dimethylphenyl) propane, 2,2-bis (4-
Hydroxyphenyl) nonane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (2-hydroxy-3-t
ert-butyl-5-methylphenyl) methane, 1,1
-Bis (4-hydroxyphenyl) diphenylmethane,
Terpene diphenol, 1,1-bis (3-tert-
Butyl-4-hydroxyphenyl) cyclohexane,
1,1-bis (2-methyl-4-hydroxy-5-te
rt-Butylphenyl) -2-methylpropane, 2,2
-Bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3,5-ditert-butyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-disecbutyl- 4-hydroxyphenyl)
Methane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-
Hydroxy-3,5-ditert-butylphenyl) ethane, 1,1-bis (3-nonyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-ditert-butyl-4-hydroxyphenyl) ) Propane, 1,1-bis (2-hydroxy-3,5-ditert-butyl-6)
-Methylphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane,
4,4-bis (4-hydroxyphenyl) pentanoic acid,
Bis (4-hydroxyphenyl) acetic acid butyl ester,
1,1-bis (3-fluoro-4-hydroxyphenyl) methane, 1,1-bis (2-hydroxy-5-fluorophenyl) methane, 2,2-bis (4-hydroxyphenyl) -1,1, 1,3,3,3-hexafluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 1,1-bis (3-fluoro-
4-hydroxyphenyl) -1-phenylmethane, 1,
1-bis (3-fluoro-4-hydroxyphenyl)-
1- (p-fluorophenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- (p-fluorophenyl) methane, 2,2-bis (3-chloro-4-hydroxy-5-methylphenyl) ) Propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 1,1-bis (3,5-dibromo) -4-
Hydroxyphenyl) methane, 2,2-bis (3,5-
Dibromo-4-hydroxyphenyl) propane, 2,2
-Bis (3-nitro-4-hydroxyphenyl) propane, 3,3'-dimethyl-4,4'-biphenol, 3,
3 ', 5,5'-tetramethyl-4,4'-biphenol, 3,3', 5,5'-tetra-tert-butyl-4,
4'-biphenol, bis (4-hydroxyphenyl)
Ketone, 3,3'-difluoro-4,4'-biphenol, 3,3 ', 5,5'-tetrafluoro-4,4'-biphenol, bis (4-hydroxyphenyl) dimethylsilane, bis (4- Hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone,
Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) thioether, bis (3-methyl-4-hydroxyphenyl) Ether, bis (3-methyl-4-hydroxyphenyl) thioether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) thioether, 1,1-bis (2,3,5-Trimethyl-4-hydroxyphenyl) -1-phenylmethane, 2,2-bis (4-hydroxyphenyl) dodecane, 2,2-bis (3-methyl-)
4-hydroxyphenyl) dodecane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) dodecane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1 , 1-Bis (3,5-ditert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -2
-Methyl propane, 1,1-bis (2-hydroxy-
3,5-ditert-butylphenyl) ethane, 2,2
-Bis (4-hydroxyphenyl) propanoic acid methyl ester, 2,2-bis (4-hydroxyphenyl) propanoic acid ethyl ester, isatin bisphenol, isatin biscresol, 2,2 ', 3,3', 5 5'-hexamethyl-4,4'-biphenol, bis (2-hydroxyphenyl) methane, 2,4'-methylenebisphenol, 1,2-bis (4-hydroxyphenyl) ethane, 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane, bis (2-hydroxy-3)
-Allylphenyl) methane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-5-tert-butylphenyl) ethane, bis ( 2-hydroxy-5-phenylphenyl) methane, 1,1-bis (2-methyl-)
4-hydroxy-5-tert-butylphenyl) butane, bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methane, 2,2-bis (4-hydroxyphenyl) pentadecane, 2,2-bis (3 -Methyl-4-hydroxyphenyl) pentadecane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) pentadecane, 1,2-bis (3,5-ditert-butyl-4-hydroxyphenyl) ethane , Bis (2-hydroxy-3,5-ditert-butylphenyl) methane,
2,2-bis (3-styryl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1- (p-nitrophenyl) ethane, bis (3,3
5-difluoro-4-hydroxyphenyl) methane, bis (3,5-difluoro-4-hydroxyphenyl)-
1-phenylmethane, bis (3,5-difluoro-4-
Hydroxyphenyl) diphenylmethane, bis (3-fluoro-4-hydroxyphenyl) diphenylmethane,
2,2-bis (3-chloro-4-hydroxyphenyl)
Propane, 3,3 ', 5,5'-tetra-tert-butyl-2,2'-biphenol, 2,2'-diallyl-4,
4'-biphenol, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3
5,5-tetramethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,4-trimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl-5 -Ethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,
3,5-trimethyl-cyclopentane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -3,
3,5-Trimethyl-cyclohexane, 1,1-bis (3,5-diphenyl-4-hydroxyphenyl)-
3,3,5-Trimethyl-cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,3
5-trimethyl-cyclohexane, 1,1-bis (3-
Phenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 9,9- Bis (4-hydroxyphenyl) fluorene, 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 1,1-
Bis (3,5-dibromo-4-hydroxyphenyl)-
Examples include 3,3,5-trimethyl-cyclohexane, α, α-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene and the like, and these may be one kind or a plurality of kinds may be contained. These dihydric phenols can be used depending on the performance of the obtained polymer.

Furthermore, a dihydroxybenzene unit can be contained within a range that does not impair the effects of the present invention,
Examples of dihydroxybenzenes that give these dihydroxybenzene residues include resorcinol, hydroquinone, and 1,2-dihydroxybenzene.
These may be contained in one kind or in plural kinds.

Further, the polymer of the present invention does not necessarily have to be linear, and a polyhydric phenol can be copolymerized depending on the performance of the obtained polymer. Specific examples of such polyphenols include tris (4-hydroxyphenyl) methane, 4,4 ′-[1- [4- [1
-(4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,3,4
4'-tetrahydroxybenzophenone, 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, tris (3-methyl-4-hydroxyphenyl) methane, 4- [bis (3-methyl-4-hydroxy) Phenyl) methyl] -2-methoxyphenol, 4-
[Bis (3,5-dimethyl-4-hydroxyphenyl)
Methyl] -2-methoxyphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3-methyl-4-hydroxyphenyl) ethane,
1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, tris (3-methyl-4-hydroxyphenyl) methane, tris (3,5-dimethyl-4)
-Hydroxyphenyl) methane, 2,6-bis [(2-
Hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2-dihydroxybenzene, 2- [bis (2-methyl- 4-hydroxy-5
-Cyclohexylphenyl) methyl] -phenol, 4
-[Bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl] -1,2-dihydroxybenzene, 4-methylphenyl-1,2,3-trihydroxybenzene, 4-[(4-hydroxyphenyl ) Methyl] -1,2,3-trihydroxybenzene, 4- [1
-(4-hydroxyphenyl) -1-methyl-ethyl]
-1,3-dihydroxybenzene, 4-[(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,
3-trihydroxybenzene, 1,4-bis [1-bis (3,4-dihydroxyphenyl) -1-methyl-ethyl] benzene, 1,4-bis [1-bis (2,3,4-)
Trihydroxyphenyl) -1-methyl-ethyl] benzene, 2,4-bis [(4-hydroxyphenyl) methyl] -1,3-dihydroxybenzene, 2- [bis (3
-Methyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (3-methyl-4-hydroxyphenyl) methyl] phenol, 2- [bis (2-methyl-4)
-Hydroxyphenyl) methyl] phenol, 4- [bis (3-methyl-4-hydroxyphenyl) methyl]-
1,2-dihydroxybenzene, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol,
2- [bis (2,3-dimethyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] phenol, 3
-[Bis (3,5-dimethyl-4-hydroxyphenyl) methyl] phenol, 2- [bis (2-hydroxy-3,6-dimethylphenyl) methyl] phenol, 4
-[Bis (2-hydroxy-3,6-dimethylphenyl) methyl] phenol, 4- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] -2-methoxyphenol, 3,6- [bis ( 3,5-dimethyl-4-
Hydroxyphenyl) methyl] -1,2-dihydroxybenzene, 4,6- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-trihydroxybenzene, 2- [bis (2 , 3,6-Trimethyl-
4-hydroxyphenyl) methyl] phenol, 2-
[Bis (2,3,5-trimethyl-4-hydroxyphenyl) methyl] phenol, 3- [bis (2,3,5-
Trimethyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (2,3,5-trimethyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (2,3,5-trimethyl-4-hydroxyphenyl) )
Methyl] -1,2-dihydroxybenzene, 3- [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl] phenol, 4- [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) Methyl] phenol, 4- [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl] -2-methoxyphenol, 2,4,6- [tris (4-hydroxyphenylmethyl) -1,3- Dihydroxybenzene, 1,1,2,2-tetra (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetra (3
5-dimethyl-4-hydroxyphenyl) ethane, 1,
4-[[bis (4-hydroxyphenyl) methyl]] benzene, 1,4-di [bis (3-methyl-4-hydroxyphenyl) methyl] benzene, 1,4-di [bis (3,5-dimethyl) -4-hydroxyphenyl) methyl] benzene, 4- [1,1-bis (4-hydroxyphenyl) ethyl] aniline, (2,4-dihydroxyphenyl) (4-hydroxyphenyl) ketone, 2- [bis (4 -Hydroxyphenyl) methyl] phenol,
1,3,3-tri (4-hydroxyphenyl) butane and the like are listed, and these may be used alone or in combination of two or more.

The carbonate residue is a structural unit obtained from a carbonic acid ester, a carbonic acid halide or the like as a raw material, and examples thereof include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate and m-.
Cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate,
Examples thereof include carbonic acid esters such as dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and dicyclohexyl carbonate, and carbonic acid halides such as phosgene and triphosgene.

In the polymer of the present invention, the ratio of the repeating unit represented by the formula (1) to the carbonate residue is 1 ≧ (a) / {(a) + (b)} ≧ 0.05. (3) [where (a) is the number of moles of the repeating unit of the formula (1), and (b) is the number of moles of the carbonate residue. ].
When this value is less than 0.05, high refractive index and high Abbe number characteristics are not exhibited, and it is insufficient for use in lenses. The lower limit is preferably 0.20 or more, more preferably 0.50 or more. Further, since the toughness is improved and the impact resistance is improved, the upper limit is preferably 0.8 or less, more preferably 0.7.
It is the following.

Further, in the present invention, in consideration of mechanical properties, optical properties can be maintained even if the polymer is a high molecular weight substance. The number average molecular weight of the resin composition according to the present invention is 300.
00 to 1,000,000 is preferably used, and more preferably 30,000 to 500,000. In addition, for application to optical applications, those having a low melt viscosity are preferably used in order to suppress orientation, birefringence, etc. Therefore, for such applications, a number average molecular weight of 10,000 to 200,000 is preferably used.

Next, the method for producing the polymer of the present invention will be described with reference to examples.

The method for producing the polymer of the present invention includes, for example, a solution polymerization method (A. Conix Ind. En.) In which an acid halide and a divalent phenol are reacted in an organic solvent.
g. chem. 51, 147, 1959, Japanese Patent Publication No. 37
-5599), a melt polymerization method of heating an acid halide and a divalent phenol in the presence of a catalyst such as magnesium chloride, and a melt polymerization method of heating a divalent acid and a divalent phenol in the presence of diallyl carbonate ( Japanese Patent Publication 38-262
99), an interfacial polymerization method of mixing a divalent acid halide dissolved in an organic solvent incompatible with water and a divalent phenol dissolved in an alkaline aqueous solution (WM EAR).
ECKSON J. Poly. Sci. XL399,1
959, Japanese Patent Publication No. 40-1959), and the like, but the solution polymerization method is particularly preferably adopted. Explaining one example of the solution polymerization method, a phosphonic acid derivative which is a precursor molecule of a phosphonic acid residue and a dihydric phenol are mixed and reacted in the presence of a base such as triethylamine, and then a precursor molecule of a carbonate residue, For example, the resin of the present invention can be obtained by adding triphosgene and conducting condensation polymerization. As the phosphonic acid derivative or carbonate derivative, halides, acid anhydrides, esters and the like thereof are used, but are not particularly limited.

As a method for controlling the molecular weight of the polymer of the present invention, a monofunctional substance can be added during the polymerization. Examples of the monofunctional substance used as the molecular weight regulator here include phenol, cresol, and p-ter.
Examples include monohydric phenols such as t-butylphenol, monohydric acid chlorides such as benzoic acid chloride, methanesulfonyl chloride, and phenylchloroformate.
The resin of the present invention is extremely excellent in transparency, but the cause of the high haze value of the polyphosphonate resin is attributed to the production method of the resin and the essential properties of the resin. In the former case, there is a case where fine foreign substances are mixed in the resin.Specifically, the foreign substances mixed in the salts and monomers produced by the reaction, the foreign substances mixed in during the polymerization. As a result of the investigation, it was found that the cause was foreign matter mixed in during the post-treatment. on the other hand,
The present inventors have vigorously studied the latter, and in the case of polyphosphonates, depending on the molecular structure of the bisphenol residue or the like, the resin tends to precipitate as the molecular weight increases, and the resin is dissolved. It was confirmed that the opacity and the meltability were deteriorated and that white turbidity occurred due to such a cause.
This tendency was particularly remarkable in bisphenols having a rigid skeleton. Therefore, as a result of intensive studies to solve these problems, the present inventors have found that removal of precipitates and salts is washing in a resin solution state, filtration, and that carbonate groups are used as an improvement in essential properties of the resin. It was found that the copolymerization improves the solubility and the meltability.

As a specific means for improving the transparency, for example, during the polymerization of the present invention, an ammonium salt consisting of triethylamine is produced as a by-product in the polymerization solution, and therefore this ammonium salt is mixed into the polymer solution. Haze value deteriorates. Specifically, it has been confirmed that if the ammonium salt can be desalted to a resin weight ratio of 100 ppm or less, the transmittance is improved and the haze value is also improved. Further, solution filtration and solution washing can be used as extremely effective means for removing ammonium salts.

The weight ratio of ammonium hydrochloride can be measured by
It can be calculated from the peak (3.14 ppm) derived from the methylene group of the ethyl group of triethylamine hydrochloride in ¹ HNMR.

Solution cleaning is also effective for removing ammonia salts, and soluble components other than ammonia salts can also be removed. The washing liquid is not particularly limited, but water is preferably used because of low cost, good desalting efficiency, incompatibility with the polymerization solution, and the like, and pure water is most preferably used. The washing method is not particularly limited, but a method of mixing the washing liquid and the polymerization solution and stirring is preferably used. By carrying out such stirring, the ammonium salt contained in the reaction solution is dissolved in the washing solution, so that the ammonium salt in the polymerization solution is removed. The concentration of the polymerization solution at the time of washing is not particularly limited, but it is preferably used because the washing efficiency can be improved by diluting the concentration of the polymerization solution. After stirring, the polymerization solution and the washing solution may be phase-separated and the washing solution may be discharged. The number of times of washing is not particularly limited, but washing twice or more is preferable because it allows more desalting.

Further, removal of foreign matter by solution filtration can also be used as a measure for improving the transmittance and reducing the haze value. In the case of optical use, since it is necessary to remove foreign matter within a range visible to humans, solution filtration of 0.5 μm or less is preferably used. The filtration method is not particularly limited and includes pressure filtration, reduced pressure filtration and atmospheric filtration, but pressure filtration is preferably used in terms of shortening the filtration time.
The material of the filtration filter is not particularly limited,
Sintered metal, wire mesh, filter paper, woven cloth, non-woven cloth, glass filter, membrane filter and the like can be used. For these solution filtrations, it is possible to use some filters in combination, and it is also possible to combine with a filter of 0.5 μm or more. By the manufacturing method including the above-described filtration step, the fine foreign matter mixed in the resin and the ammonium salt described above can be removed to obtain a resin having a high transmittance and a low haze value.

The resin polymerization solution of the present invention is preferably used to obtain a resin solid content by a known wet coagulation method,
A water-soluble substance is preferably used as the poor solvent of the wet coagulation method from the viewpoint of good desalination efficiency. Specifically, ethanol,
Alcohols such as methanol are preferably used. Further, these poor solvents may be used alone or in a mixed solution. Even when the above-mentioned treatment is performed, a small amount of ammonium salt may remain inside the resin, and it is difficult to desalt this by washing. Therefore, a method of desalting the resin composition by vacuum heat treatment is also effective. It is preferable that the degree of vacuum is 10 mmHg or less and the atmosphere is such that the salt is easily sublimated, and if it is 1 mmHg or less, it is most preferable because the resin is less likely to be colored when heated. The heating temperature is not particularly limited, but it is preferably used that is higher than the sublimation temperature of the salt,
More preferably, it is heated to a temperature not lower than the sublimation temperature of the salt and not lower than the glass transition temperature of the resin. By this treatment, the ammonium salt remaining inside the resin can be removed by causing the resin to flow even slightly at the glass transition temperature. The heat treatment time is not particularly limited,
The range of 0.5 to 5 hours is preferably used. Further, if the heating temperature is too high or the heating time is too long, problems such as coloring of the resin and decomposition of the resin occur.

The above-mentioned methods can be used alone or in combination preferably.

By the production method of the present invention as described above, a highly transparent resin can be obtained.

The total light transmittance of the resin of the present invention is 70% or more,
Further, the haze needs to be 30% or less, preferably 80% or more of total light transmittance, and 15% or less of haze, most preferably 85% or more and 3% or less of haze. By satisfying such characteristics, it can be suitably used for lens applications and optical film applications.

The total light transmittance and the haze value (cloudiness value) are in accordance with Japanese Industrial Standard JIS K7105. The haze value is a value represented by the following formula (4).

Haze value (%) = diffuse transmittance / total light transmittance × 100 (4) Further, the resin of the present invention has an optically low dispersibility, that is, of the dispersion of light of an optical substance. The Abbe number is preferably 30 or more as an index indicating the degree. This Abbe number is calculated by the equation (5).

[0035]   Abbe number (νd) = (nd-1) / (nf-nc) (5) nd: d line (wavelength 587.6 nm) Refractive index nf: f line (wavelength 486.1 nm) Refractive index nc: c line (wavelength 656.3 nm) Refractive index The larger this value is, the lower the dispersion is.

To the polymer of the present invention, various antioxidants of hindered phenol type, hindered amine type, thioether type, and phosphorus type can be added within the range not impairing the properties thereof.

The polymer of the present invention has a high solubility in organic solvents, and examples of such solvents include methylene chloride, chloroform, 1,1,2,2-tetrachloroethane, 1, 2-dichloroethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, γ-butyrolactone, benzyl alcohol, isophorone, chlorobenzene, dichlorobenzene, hexafluoroisopropanol and the like can be mentioned. Further, the polymers of the present invention are amorphous and whether amorphous
Whether or not the glass transition point or the melting point is present may be confirmed by a known method such as differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement.

The resin of the present invention is preferably used in optical fields such as lens applications and optical film applications, but as other applications, liquid crystal display panel, plasma display panel, plastic substrate application such as organic electric field display, and CD. -It can be used as a core material of an optical fiber or the like by taking advantage of high refractive index characteristics in optical recording applications such as -ROM, DVD-ROM, MO and the like, and in the field of optical communication.

[0039]

EXAMPLES Specific embodiments of the present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 Methylbenzylidene bisphenol A (80 mmol) and triethylamine (168 mmol) were mixed in methylene chloride (50 ml) under a nitrogen atmosphere and stirred under ice cooling. Phenylphosphonic acid dichloride (60
A solution of mmol) in methylene chloride (10 ml) was added dropwise over 15 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene having a concentration of 0.571 mol / l in methylene chloride (11.68 ml) was added dropwise over 10 minutes,
After completion of dropping, the mixture was stirred for 60 minutes.

For post-treatment, 300 m of pure water was added to the reaction solution.
The washing process of adding 1 and stirring the mixed solution was performed three times. Subsequently, after phase-separated resin reaction solution is separated, foreign matter is removed by solution filtration with a 0.5 μm filter, then put into 2000 ml of ethanol for reprecipitation, and the polymer is collected by filtration. (1) Ethanol 1000 ml (2) Water / ethanol =
The 1/1 polymer mixture was washed with 1000 ml (3) of water 1000 ml in this order, vacuum dried at 80 ° C for 15 hours, and then vacuum dried at 150 ° C for 4 hours to obtain the desired resin powder. Obtained at 90%. The obtained resin powder was molded and evaluated by the method shown below. That is, in the case of press molding, the molding temperature was set to 250 ° C. and the mold was heated above the glass transition temperature point of the resin. The obtained resin powder was put into a mold heated to 250 ° C. The mold used was one capable of forming a disk-shaped plate having a diameter of 30 mm. The mold was closed, and after applying pressure of 2 t, the mold was cooled. A disk-shaped resin plate having a diameter of 30 mm and a thickness of 3 mm was obtained by dividing the mold. The obtained resin molded sample was sanded and buffed. Two surfaces that were perpendicular to each other were polished and then mirror-finished.

The polished resin sample was evaluated with a refractometer (KPR-2 manufactured by Calnew Optical Co., Ltd.), and d
The line (wavelength: 587.6 nm) refractive index (nd) and the Abbe's number (νd) obtained from the equation (4) were measured.

Abbe number (νd) = (nd-1) / (nf-nc): Formula (4) nd: d line (wavelength 587.6 nm) Refractive index nf: f line (wavelength 486.1 nm) Refractive index nc : C-line (wavelength 656.3 nm) Refractive index The obtained resin molded sample was measured for total light transmittance and haze with a digital haze computer (Huga-2DP manufactured by Suga Test Instruments Co., Ltd.). Further, the molecular weight was measured by measuring a 0.1 wt% chloroform solution of the resin with GPC (gel permeation chromatography) [GPC8020 manufactured by Tosoh Corporation] to obtain the number average molecular weight (Mn). The measured values are standard polystyrene equivalent values.

Example 2 Methylbenzylidene bisphenol A (80 mmol) and triethylamine (168 mmol) were mixed in methylene chloride (50 ml) under a nitrogen atmosphere and stirred under ice cooling. Add phenylthiophosphonic acid dichloride to this solution.
A solution of (60 mmol) in methylene chloride (10 ml) was added dropwise over 15 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene in methylene chloride (11.68 ml) having a concentration of 0.571 mol / l was added dropwise over 10 minutes, and the mixture was stirred for 60 minutes after completion of the addition.

Thereafter, washing, solution filtration and reprecipitation treatment (yield 90%) were carried out in the same manner as in Example 1, and then the mold temperature during press molding was changed to 250 ° C. It was molded by the method and evaluated.

Example 3 Bisphenol A (80 mmol) and triethylamine (168) in methylene chloride (50 ml) under a nitrogen atmosphere.
Mmol) was mixed and stirred under ice cooling. A solution of phenylphosphonic acid dichloride (60 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. After that, the density is 0.571mo
1 / l triphosgene methylene chloride (11.68 m
l) The solution was added dropwise over 10 minutes, and after the completion of the addition, the solution was stirred for 60 minutes.

Thereafter, washing, solution filtration, solution filtration and reprecipitation treatment (yield 89%) were carried out in the same manner as in Example 1, and subsequently the mold temperature during press molding was changed to 220 ° C. Molded and evaluated in the same manner as in.

Example 4 Bisphenol A (80 mmol), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (methylene chloride (50 ml) under nitrogen atmosphere) 0.15 g), and triethylamine (1
68 mmol) were mixed and stirred under ice cooling. A solution of phenylthiophosphonic acid dichloride (60 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 60 minutes. After that, the density is 0.5
71 mol / l triphosgene methylene chloride (1
1.68 ml) solution was added dropwise over 10 minutes and after completion of the addition 6
Stir for 0 minutes.

Thereafter, washing, solution filtration and reprecipitation treatment (yield 91%) were carried out in the same manner as in Example 1, and then the mold temperature during press molding was changed to 220 ° C. It was molded by the method and evaluated.

Example 5 Bisphenol A (72 mmol), α, α-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (8 mmo) in methylene chloride (50 ml) under a nitrogen atmosphere.
l), pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] (0.
15 g) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (60 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene in methylene chloride (11.68 ml) having a concentration of 0.571 mol / l was added dropwise over 10 minutes, and the mixture was stirred for 60 minutes after completion of the addition.

Thereafter, washing, solution filtration and reprecipitation treatment (yield 88%) were carried out in the same manner as in Example 1, and then the mold temperature during press molding was changed to 220 ° C. It was molded by the method and evaluated.

Example 6 Bisphenol A (72 mmol), α, α-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (8 mmo) in methylene chloride (50 ml) under a nitrogen atmosphere.
l), pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] (0.
15 g) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. To this solution was added phenylthiophosphonic acid dichloride (60mmol) in methylene chloride (10m).
l) Add the solution dropwise over 15 minutes, then at room temperature 60
Stir for minutes. Then, 1 solution of triphosgene in methylene chloride (11.68 ml) with a concentration of 0.571 mol / l was added.
The solution was added dropwise over 0 minutes and stirred for 60 minutes after the completion of the addition.

Thereafter, washing, solution filtration and reprecipitation treatment (yield 90%) were carried out in the same manner as in Example 1, and then the mold temperature during press molding was changed to 220 ° C. It was molded by the method and evaluated.

Example 7 1,1 Bis (4-hydroxyphenyl) cyclohexane (80 mm) in methylene chloride (50 ml) under nitrogen atmosphere
Ol) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (60 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene in methylene chloride (11.68 ml) having a concentration of 0.571 mol / l was added dropwise over 10 minutes, and the mixture was stirred for 60 minutes after completion of the addition. Thereafter, the same treatment as in Example 1 (yield 90%) was followed, except that the mold temperature during press molding was changed to 240 ° C.
Molded and evaluated in the same manner as in.

Thereafter, washing, solution filtration and reprecipitation treatment (yield 92%) were carried out in the same manner as in Example 1, and then the mold temperature during press molding was changed to 250 ° C. It was molded by the method and evaluated.

Example 8 1,1 Bis (4-hydroxyphenyl) cyclohexane (80 mm) in methylene chloride (50 ml) under nitrogen atmosphere
Ol) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. To this solution was added phenyl thiophosphonic acid dichloride (60 mmol) in methylene chloride (10 mL).
The solution was added dropwise over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene at a concentration of 0.571 mol / l in methylene chloride (11.68 ml) was added 10 times.
The solution was added dropwise over minutes, and after the completion of the addition, the mixture was stirred for 60 minutes. Thereafter, washing, solution filtration and reprecipitation treatment (yield 91%) were carried out in the same manner as in Example 1, and subsequently the mold temperature during press molding was 250.
Molding and evaluation were carried out in the same manner as in Example 1 except that the temperature was changed to ° C.

Example 9 1,1 bis (4-hydroxyphenyl) cyclododecane (80 mm) in methylene chloride (50 ml) under nitrogen atmosphere
Ol) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (60 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene in methylene chloride (11.68 ml) having a concentration of 0.571 mol / l was added dropwise over 10 minutes, and the mixture was stirred for 60 minutes after completion of the addition. Then, washing, solution filtration, and reprecipitation treatment (yield 87
%), Followed by molding and evaluation in the same manner as in Example 1 except that the mold temperature during press molding was changed to 255 ° C.

Example 10 1,1 Bis (4-hydroxyphenyl) cyclododecane (80 mm) in methylene chloride (50 ml) under nitrogen atmosphere
Ol) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. To this solution was added phenyl thiophosphonic acid dichloride (60 mmol) in methylene chloride (10 mL).
The solution was added dropwise over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene at a concentration of 0.571 mol / l in methylene chloride (11.68 ml) was added 10 times.
The solution was added dropwise over minutes, and after the completion of the addition, the mixture was stirred for 60 minutes. Thereafter, washing, solution filtration, and reprecipitation treatment (yield 88%) were carried out in the same manner as in Example 1, and subsequently the mold temperature during press molding was set to 255
Molding and evaluation were carried out in the same manner as in Example 1 except that the temperature was changed to ° C.

Example 11 1,1 bis (4-hydroxyphenyl) cyclooctane (80 mm) in methylene chloride (50 ml) under nitrogen atmosphere
Ol) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (60 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene in methylene chloride (11.68 ml) having a concentration of 0.571 mol / l was added dropwise over 10 minutes, and the mixture was stirred for 60 minutes after completion of the addition. Thereafter, washing, solution filtration, and reprecipitation treatment (yield 89
%), Followed by molding and evaluation in the same manner as in Example 1 except that the mold temperature during press molding was changed to 240 ° C.

Example 12 1,1 bis (4-hydroxyphenyl) cyclohexane (80 mm) in methylene chloride (50 ml) under nitrogen atmosphere
Ol) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (40 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene in methylene chloride (23.35 ml) having a concentration of 0.571 mol / l was added dropwise over 10 minutes, and after the completion of the addition, the mixture was stirred for 60 minutes. Thereafter, washing, solution filtration and reprecipitation treatment (yield 92
%), Followed by molding and evaluation in the same manner as in Example 1 except that the mold temperature during press molding was changed to 230 ° C.

Example 13 1,1 bis (4-hydroxyphenyl) cyclohexane (80 mm) in methylene chloride (50 ml) under nitrogen atmosphere
Ol) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (4 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Then, a solution of triphosgene in methylene chloride (44.37 ml) having a concentration of 0.571 mol / l was added dropwise over 10 minutes, and the mixture was stirred for 60 minutes after completion of the addition. Thereafter, washing, solution filtration and reprecipitation treatment (yield 90%) are carried out in the same manner as in Example 1.
Then, the molding was performed and evaluated in the same manner as in Example 1 except that the mold temperature during press molding was changed to 240 ° C.

Comparative Example 1 Methylbenzylidene bisphenol A (80 mmol) and triethylamine (168 mmol) were mixed in methylene chloride (50 ml) under a nitrogen atmosphere and stirred under ice cooling. Add phenylphosphonic acid dichloride (80
A solution of mmol) in methylene chloride (10 ml) was added dropwise over 15 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 60 minutes. Then, the reaction solution was poured into 500 ml of hexane to reprecipitate,
After collecting the polymer by filtration, (1) 250 ml of ethanol (2)
Water / ethanol = 1/1 mixed solution 250 ml (3) water 25
The polymer produced in the order of 0 ml was washed and dried to obtain a polyphosphonate resin powder with a yield of 90%. The obtained resin powder was molded and evaluated by the method shown below. That is, in the case of press molding, the obtained resin powder was put into a mold heated to 250 ° C., which is higher than the glass transition temperature of the resin. The mold used was one capable of forming a disk-shaped plate having a diameter of 30 mm. The mold was closed, and after applying pressure of 2 t, the mold was cooled. A disk-shaped resin plate having a diameter of 30 mm and a thickness of 3 mm was obtained by dividing the mold. The obtained resin molded sample was sanded and buffed. Two surfaces that were perpendicular to each other were polished and then mirror-finished.

The polished resin sample was evaluated with a refractometer (KPR-2 manufactured by Calnew Optical Co., Ltd.), and d
The line (wavelength: 587.6 nm) refractive index (nd) and Abbe number (νd) were measured.

A resin haze sample obtained was used for a digital haze computer (manufactured by Suga Test Instruments Co., Ltd .: HGM-2D).
In P), the total light transmittance and haze were measured. For the measurement of molecular weight, a 0.1 wt% chloroform solution of resin is used.
The number average molecular weight (Mn) was determined by measuring with GPC (gel permeation chromatography) [GPC8020 manufactured by Tosoh Corporation]. The measured values are standard polystyrene equivalent values.

Comparative Example 2 Bisphenol A (80 mmol) and triethylamine (168) in methylene chloride (50 ml) under a nitrogen atmosphere.
Mmol) was mixed and stirred under ice cooling. A solution of phenylphosphonic acid dichloride (80 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 60 minutes. Then, reprecipitation treatment (yield 92%) was carried out in the same manner as in Comparative Example 1, and subsequently, molding was carried out and evaluated in the same manner as in Comparative Example 1 except that the mold temperature at the time of press molding was changed to 250 ° C.

Comparative Example 3 1,1 bis (4-hydroxyphenyl) cyclohexane (80 mmo in methylene chloride (50 ml) under a nitrogen atmosphere.
l) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (80 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 60 minutes. Then, the reprecipitation treatment (yield 90
%), Followed by molding and evaluation in the same manner as in Comparative Example 1 except that the mold temperature during press molding was changed to 230 ° C.

Comparative Example 4 1,1 bis (4-hydroxyphenyl) cyclohexane (80 mmo in methylene chloride (50 ml) under a nitrogen atmosphere.
l) and triethylamine (168 mmol) were mixed, and the mixture was stirred under ice cooling. To this solution was added phenylthiophosphonic acid dichloride (80 mmol) in methylene chloride (10 mL).
The solution was added dropwise over 15 minutes, and after completion of the addition, the mixture was stirred at room temperature for 60 minutes. Then, reprecipitation treatment (yield 90%) was carried out in the same manner as in Comparative Example 1, and subsequently the mold temperature during press molding was set to 230.
Molding and evaluation were carried out in the same manner as in Comparative Example 1 except that the temperature was changed to ° C.

Comparative Example 5 Under a nitrogen atmosphere, 1,1 bis (4-hydroxyphenyl) dodecane (80 mmol) and triethylamine (168 mmol) were mixed in methylene chloride (50 ml), and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (80 mmol) in methylene chloride (10 ml) was added dropwise to this solution over 15 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 60 minutes.
Then, reprecipitation treatment (yield 92%) was performed in the same manner as in Comparative Example 1,
Subsequently, the molding was performed and evaluated in the same manner as in Comparative Example 1 except that the mold temperature during press molding was changed to 255 ° C.

The evaluation results of the resins prepared by the methods of Examples 1 to 13 and Comparative Examples 1 to 5 were evaluated. The weight ratio of ammonium salt to be contained in the resin of Comparative Example 1-5 to Example 1-13, the respective resins to prepare a chloroform 3 wt% of the solution, ¹
Calculated from 1 HNMR. Table 1 shows the above evaluation results.

[0070]

[Table 1]

From the comparative example, the conventional polyphosphonate resin has a high refractive index and a low dispersion, but has a low total light transmittance and a high haze value, and therefore is insufficient for use in an optical material such as a lens or a film. . On the other hand, the resin of the present invention
^{From the 1} HNMR measurement results, the peak derived from the methylene group of the ethyl group of triethylamine hydrochloride (3.14 ppm)
However, it could not be detected in the resins of all the examples. That is, since all the ammonium salts have been removed, the total light transmittance is high and the haze value is low, so that it has useful optical characteristics.

[0072]

INDUSTRIAL APPLICABILITY The present invention can provide a thermoplastic resin having a low haze value, a high refractive index and a high Abbe number, and lenses and films made of this resin can be used in various fields.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J030 CA01 CB33 CB34 CB35 CC25                       CD11 CE02 CE11 CF09 CG06

Claims (6)

[Claims] 1. A repeating unit represented by the following formula (1):
A resin comprising a repeating unit represented by the following formula (2) and a carbonate residue, wherein the mole fraction of the repeating unit of the formula (1) and the repeating unit of the formula (2) satisfies the formula (3). A resin having a total light transmittance of 70% or more and a haze of 30% or less and a number average molecular weight of 30,000 or more when formed into a molded product having a thickness of 3 mm. [Chemical 1] [Chemical 2] [In the formula (1), R represents an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, X represents oxygen, sulfur, or selenium, and may include phosphonic acid residues having different R or X. . In formula (2), R'is independently a hydrogen atom,
It is selected from the group consisting of a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a nitro group, and p and q are integers of p + q = 0 to 8. Y is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group, a halo-substituted alkylene group, a halo-substituted alkylidene group, a phenylalkylidene group, a carbonyl group, a sulfone group, an aliphatic phosphine oxide group. , An aromatic phosphine oxide group, an alkylsilane group, a dialkylsilane group, and a fluorene group. 1 ≧ (a) / {(a) + (b)} ≧ 0.05 (3) [In the formula (3), (a) is the number of moles of the repeating unit of the formula (1), and (b) is Number of moles of carbonate residues. ] 2. A resin in which 50 mol% or less of the phosphonic acid residue, which is the repeating unit represented by the formula (1), is replaced with a corresponding phosphonite residue, and (a) in the formula (3) is replaced by The formula (3) is satisfied as the sum of the phosphonic acid residue and the phosphonite residue.
The listed resin. 3. The content of ammonium salt is 100 by weight.
It is below ppm, The resin of Claim 1 or 2 characterized by the above-mentioned. 4. The method for producing a resin according to claim 1, further comprising a solution filtration step of 0.5 μm or less. 5. The method for producing a resin according to claim 1, further comprising a solution washing step. 6. The method for producing a resin according to claim 1, further comprising a vacuum heating step.