JP2003268111A - Resin for lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin for a lens having a high refractive index and a high Abbe's number with improved color tone. <P>SOLUTION: This resin comprises a phosphonic residue expressed by the formula (1) (R is a 1-20C hydrocarbon group; X denotes oxygen, sulfur or selenium), a bivalent phenolic residue expressed by the formula (2) (R's are each independently selected from the group consisting of a hydrogen atom, a 1-20C aliphatic hydrocarbon group, a 1-20C aromatic hydrocarbon group, a halogen atom and a nitro group; 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, the mole fractions of the phosphonic residue and the carbonate residue satisfy the inequality (3): 1>(a)/[(a)+(b)]≥0.05 (wherein (a) and (b) denote mole numbers of the phosphonic residue and the carbonate residue, respectively.) and the content of sodium is less than 5 ppm. <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 resin for lenses having a high refractive index and a high dispersibility, which has improved coloring problems and heat resistance.

[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 CR39, acrylic, and urethane (Japanese Patent Laid-Open No. 06-016).
No. 729, etc.), 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, because of its low refractive index (1.58), it is applied only to protective eyeglasses as an eyeglass lens application. Aromatic thermoplastic resins other than polycarbonate have a high refractive index but have problems such as high dispersibility and colorability, and thus cannot be applied to optical lens applications.

Under these circumstances, a thermoplastic resin having a phosphonic acid residue in its main chain (US Pat. No. 6,288,210)
No.) is a resin having properties suitable for spectacle lens applications because of its high refraction and low dispersion. However, since the resin having a phosphonic acid residue has poor solubility / meltability, there is also a problem of clouding when a lens is molded. Further, there is a problem of coloring during manufacturing and a problem of poor heat resistance. As a result, the features of high refractive index and low dispersion cannot be fully utilized, and their use is limited.

[0006]

Therefore, in view of such background of the prior art, the present invention provides a resin for a lens in which the cause of coloring during manufacturing is identified and the coloring problem is solved. .

[0007]

To solve the above problems, the present invention has the following constitution. That is, (A) contains a phosphonic acid residue represented by the following general formula (1) and a divalent phenol residue and a carbonate residue represented by the following general formula (2), and contains a phosphonic acid residue and a carbonate residue. The mole fraction of satisfies Equation (3),
And a resin for lenses, characterized in that the content of sodium is less than 5 ppm, the general formula (1)

[0008]

[Chemical 7]

General formula (2)

[0010]

[Chemical 8]

[In the formula (1), R represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents oxygen, sulfur or selenium. Formula (2)
Each R'is independently selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydrocarbon group and a nitro group. p and q are integers of p + q = 0 to 8, Y is a single bond, oxygen atom, sulfur atom, alkylene group, alkylidene group, cycloalkylene group, cycloalkylidene group, halo-substituted alkylene group, halo-substituted alkylidene group, phenylalkylidene group. A carbonyl group, a sulfone group, an aliphatic phosphine oxide group, an aromatic phosphine oxide group, an alkylsilane group, a dialkylsilane group, a fluorene group, a branched chain-containing alkylidene group, and a branched chain-containing cycloalkylidene group. 1> (a) / [(a) + (b)] ≧ 0.05 (3) [where (a) represents the phosphonic acid residue and (b) represents the number of moles of the carbonate residue.] ] (B) A resin for a lens, wherein the general formula (2) described in the above (A) is represented by any one of the following general formulas (4) to (7). General formula (4)

[0012]

[Chemical 9]

General formula (5)

[0014]

[Chemical 10]

General formula (6)

[0016]

[Chemical 11]

General formula (7)

[0018]

[Chemical 12]

(C) The resin contains a phosphonite residue, and the content ratio of the phosphonite residue is not more than an equimolar amount to the phosphonic acid residue. The resin described in B).

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have detected that the cause of coloring of such a resin is not the original component of the resin and also sodium ion which is not actively used during the process, and removes it. It was clarified that the coloring property at the time of melt molding can be dramatically reduced by.

The resin used in the present invention is a resin containing a phosphonic acid residue represented by the following general formula (1) and a divalent phenol residue and a carbonate residue represented by the following general formula (2). General formula (1)

[0022]

[Chemical 13]

General formula (2)

[0024]

[Chemical 14]

Specific examples of the substituent R substituting the phosphorus atom of the phosphonic acid residue represented by the general formula (1) are phenyl, halo-substituted phenyl, methoxyphenyl, ethoxyphenyl, ethyl, isopropyl, cyclohexyl,
Examples thereof include vinyl, allyl, benzyl, aminoalkyl, hydroxyalkyl, halo-substituted alkyl and alkylsulfide groups.

Specific examples of such a phosphonic acid residue as its basic structure, phosphonic acid, include methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, isobutylphosphonic 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, 2-dichloroethylphosphonic acid, 2-bromoethylphosphonic acid, 1,2-dibromoethylphosphonic acid, 3-chloropropylphosphonic acid, 2,3-dichloropropylphosphonic acid 3-bromopropylphosphonic acid,
2,3-dibromopropylphosphonic 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, 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, Two
-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-chlorophenylphosphonic 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 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) butylphosphonic acid, 4- (3,4-dibromophenyl) butylphosphonic acid, 4- (3,5-dibromophenyl) butylphosphonic acid, 2-pyridylphosphonic acid Acid, 3-pyridylphosphonic acid, 4-pyridylphosphonic acid, 1-pyrrolidinomethylphosphonic acid, 1-pyrrolidinoethylphos Acid, 1-pyrrolidinopropyl phosphonic acid, 1-pyrrolidinopyridine butyl phosphonic acid, pyrrole-1-phosphonic acid, pyrrole-2-phosphonic acid, pyrrole-3-phosphonic acid, thiophene -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, allylphosphonic acid, etc. Further, thiophosphonic acid in which an oxygen atom bonded to these phosphorus atoms by a double bond is substituted with a sulfur atom is also included. These may be one kind or may contain plural kinds.

Further, the resin of the present invention may contain a phosphonite residue having a trivalent phosphorus functional group as another phosphorus-containing unit. As an example of such a phosphonite residue, the above-mentioned phosphonic acid residue can be similarly mentioned as the corresponding phosphinic acid residue. By introducing this phosphinic acid residue, it is possible to impart oxidation resistance to the resin. The content thereof is preferably 50 mol% or less of the phosphonic acid residue, more preferably 25 mol% or less, and further preferably 10 mol% or less in consideration of stability of properties such as optical properties. The lower limit is preferably 1 mol% or more.

Specific examples of the divalent phenol residue represented by the general formula (2) as the basic structure of the divalent phenol include 1,1-bis (4-hydroxyphenyl) methane and 1-bis (4-hydroxyphenyl) methane. , 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) -4-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 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-tert-butyl-5-methylphenyl) methane,
1,1-bis (4-hydroxyphenyl) diphenylmethane, terpene diphenol, 1,1-bis (3-te
rt-Butyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-methyl-4-hydroxy-5-)
tert-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-di ter
t-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′-tetratert-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 contained in one kind or in plural kinds.

Among these dihydric phenols, 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -4 are particularly preferable.
-Methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 2,
2-bis (4-hydroxyphenyl) -4-methylpentane is preferably adopted. By using such a dihydric phenol, it has excellent optical properties, that is, a high refractive index and a low dispersion, and it can be suitably used particularly in lens applications.

The carbonate residue of the present invention is a carbonate skeleton. The introduction can be performed by using a carbonic acid ester such as diphenyl carbonate or a carbonic acid derivative such as carbonic acid halide such as phosgene or triphosgene.

The resin used in the present invention is represented by the above general formula (1).
The mole fraction of the phosphonic acid residue represented by and the carbonate residue satisfies the formula (3).

1> (a) / [(a) + (b)] ≧ 0.05 (3) [where (a) is the phosphonic acid residue and (b) is the number of moles of the carbonate residue. . When this ratio is 1, the meltability and solubility of the resin are extremely deteriorated and the moldability is also deteriorated. If this ratio is less than 0.05, the characteristics such as the refractive index as an optical material are insufficient. It is preferably 0.90 or less and 0.30 or more, and more preferably 0.85 or less and 0.50 or more.

The resin used in the present invention is a resin in which other residues are copolymerized in addition to the residues represented by the above general formulas (1) and (2) as long as the object of the present invention is not impaired. Alternatively, it may be a blend of other resin components.

Next, a concrete method of the resin of the present invention will be described with reference to examples.

The resin of the present invention can be obtained by a melt polymerization method, a solution polymerization method, an interfacial polymerization method or the like. The monomer to be used can be appropriately selected depending on the polymerization method, but as the monomer constituting the phosphonic acid residue of the general formula (1), phosphonic acid chloride, phosphonic acid ester, phosphonic acid amide and the like phosphonic acid can be used. Examples include derivatives.

The resin polymerization method will be described in more detail below.

As the method for producing the resin of the present invention, a solution polymerization method (A. Conix Ind. Eng. Che, in which an acid halide and a divalent phenol are reacted in an organic solvent).
m. , 51, 147, 1959, Japanese Examined Patent Publication No. 37-559
No. 9), 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 (special JP-B-38-26299), an interfacial polymerization method (WM EAREKKS) in which a divalent acid halide dissolved in an organic solvent incompatible with water and a divalent phenol dissolved in an alkaline aqueous solution are mixed.
ON J. Poly. Sci. XL399, 1959
, Japanese Patent Publication No. 40-1959) and the like,
The solution polymerization method is particularly preferably used because the resin is easily colored by the melt polymerization method and it is difficult to synthesize a high molecular weight resin by the interfacial polycondensation method.

An example of the solution polymerization method will be described. A phosphonic acid derivative which is a precursor molecule of a phosphonic acid residue,
The resin of the present invention can be obtained by mixing and reacting a dihydric phenol in the presence of a base such as triethylamine, followed by addition of a precursor molecule of a carbonate residue such as triphosgene and 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 adjusting the molecular weight, a monofunctional substance can be added during the polymerization. Examples of the monofunctional substance used as the molecular weight regulator include monohydric phenols such as phenol, cresol and p-tert-butylphenol, monohydric acid chlorides such as benzoic acid chloride, methanesulfonyl chloride and phenylchloroformate. Is mentioned.

The amount of sodium contained in the resin of the present invention is 5 ppm or less. The sodium content is calculated by converting the sodium contained in the resin into the weight of metallic sodium. Sodium content is 5ppm
The problem of coloration during melt molding can be solved by setting the content to 1 ppm or less, more preferably below.

In the present invention, the method for measuring the sodium content uses the fluorescent X-ray analysis method.

Contamination of sodium is due to the use of sodium phenolate in the general melt transesterification reaction. Usually, the melting method cannot remove sodium because there is no washing step. When interfacial polycondensation is carried out, sodium salt of bisphenol is used as a monomer. Although there is a water washing step in the interfacial polycondensation, washing with water is difficult because the sodium salt is produced in an equimolar amount of the monomer, and the sodium salt remains in the resin. Therefore, the polymerization method using sodium phenolate is not preferable from the viewpoint of suppressing coloration.

On the other hand, it was found that sodium can be mixed in the solution polymerization without using sodium phenolate. This is because the bisphenols contain sodium. It is presumed that this is because sodium is eluted from the glass during the filtration and is mixed into the bisphenols, because the glass filters are used in the manufacturing process of the bisphenols. When such bisphenol is used as a raw material, sodium remains in the resin.
In solution polymerization, usually, the resin solution after completion of polymerization is subjected to treatment such as neutralization with hydrochloric acid and washing with water, but the contact time between the resin solution and hydrochloric acid is short, which is insufficient from the viewpoint of sodium removal. It was

It was found that sodium in the resin can be removed by heat treatment in dilute hydrochloric acid at 60 ° C. or higher.
The heating time is preferably 30 minutes or more and less than 24 hours, more preferably 1 hour or more and less than 12 hours. If the treatment time is less than 30 minutes, sodium removal is insufficient. On the other hand, if the time is 24 hours or more, there is a concern that the molecular weight will decrease. The concentration of hydrochloric acid used for the heat treatment is preferably 1N or less of dilute hydrochloric acid. When concentrated hydrochloric acid is used, there is still a concern that the molecular weight will decrease.

To the polymer of the present invention, various hindered phenol-based, hindered amine-based, thioether-based, and phosphorus-based antioxidants can be added within a range that does not impair 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
The presence or absence of the melting point may be confirmed by a known method such as differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement.

The resin of the present invention dramatically improves the color tone of the resin after melt molding by such a method. That is, the yellowness index (ΔYI) of a resin plate having a thickness of 3 mm is 5
It is the following. It is preferably 2.5 or less, more preferably 2.0 or less. This yellowness is defined by the following equation.

YI = 100 × (1.28X-1.06Z) / Y X, Y, Z: Tristimulus value ΔYI = YI ₂ −YI ₁ ΔYI of sample under standard light C: Yellowness YI ₁ : Reference value YI ₂ : Measured value of sample The resin of the present invention is used for, for example, lens applications such as eyeglass lenses and contact lenses, housing applications for home appliances, CD
It can be used for substrates for recording media such as ROM and DVD ROM, film applications such as magnetic films and retardation films, flame retardant applications and the like.

[0049]

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

The sodium content was based on the following measurements.
RIX-1000 manufactured by Rigaku Denki was used. The amount of sodium was measured from a calibration curve at a tube voltage of 50 kV and a tube current of 50 mA using a chrome tube. The polymer obtained by polymerization was press-molded into a disk-shaped molded product of 30 mmφ × 3 mm thickness, and the measurement was performed using a 30 mmφ folder.

The yellowness index (ΔYI) was based on the following measurement.

A resin sample is press-molded with a diameter of 30 m.
m, and molded into a disk-shaped resin plate having a thickness of 3 mm. Then, the tristimulus values (X, Y, Z) of this sample were determined by a transmission method using a digital color computer (SM-7-CH manufactured by Suga Test Instruments Co., Ltd.), and YI was calculated by the equation (6).
Ask for ₂ . Moreover, X, Y, Z are similarly obtained from the air,
Similarly, the reference value YI ₁ is calculated, and ΔYI is calculated by the equation (7).

YI = 100 × (1.28X−1.06Z) / Y (6) X, Y, Z: Tristimulus value of sample under standard light C ΔYI = YI ₂ −YI ₁ (7) ΔYI: Yellowness YI ₁ : Reference value (measured from air) YI ₂ : Measured value of sample The number average molecular weight was determined by the following measurement.

It was measured using gel permeation chromatography (GPC: SC-8020 manufactured by Tosoh Corporation). The measurement conditions are columns (shodex GP
CK-806L 2 direct connection), column temperature is 35
C., the flow was chloroform 1 ml / min, and the detector was UV. The sample injection amount was 50 μl of the 0.2 wt% solution. For the calculation of the molecular weight, a calibration curve prepared in advance using polystyrene was used. [Resin Polymerization 1] Dichloromethane (10
L-) was mixed with 1,1-bis (4-hydroxyphenyl) cyclohexane (4 mol · sodium content was 10 ppm) and triethylamine (8.8 mol), and the mixture was stirred under ice cooling. Phenylphosphonic acid dichloride in this solution
A solution of (3 mol) in dichloromethane (9 L) was added dropwise over 60 minutes, and after completion of the addition, the mixture was stirred at room temperature for 120 minutes. Then, a dichloromethane (583 mL) solution of triphosgene having a concentration of 0.571 mol / L was added dropwise over 30 minutes, and after the addition was completed, the mixture was stirred for 120 minutes.

Then, using an oil bath, the solution was stirred at a temperature of 30 ° C. for 120 minutes. Then, the mixture was stirred for 12 hours at room temperature.

1N Hydrochloric acid (10 L) was added to the reaction solution, and the mixture was stirred for 5 minutes. After allowing to stand, the upper aqueous layer was confirmed to be acidic and then removed. Further, similarly, treatment with 0.1N hydrochloric acid was performed twice to obtain a resin solution. The resin solution was added to the container over 20 minutes while distilling the solvent into a stainless steel container having an internal volume of 35 L and equipped with a distillation solvent recovery facility in a lid portion containing warm water (23 L) at 70 ° C. After the addition was completed, a resin block was collected from the container.

A resin lump was obtained by crushing the resin mass and then drying. The sodium content is 8.5 ppm. The number average molecular weight is 82,000.

Example 1 50 g of resin coarse powder and 500 ml of 0.1N hydrochloric acid were placed in a stainless steel container coated with tetrafluoroethylene resin, and heat-treated at 70 ° C. for 6 hours while stirring with a stirring blade made of tetrafluoroethylene resin. did.

After cooling, filtration was performed using a polyester filter cloth to obtain a resin powder 2. Sodium content is 0.3p
It was pm. The number average molecular weight was 82,000.

The resin powder 2 obtained was placed in a mold heated to 250 ° C., which is higher than the glass transition temperature of the resin, and press-molded. 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. Φ3 by dividing the mold
A disk-shaped resin plate having a thickness of 0 mm and a thickness of 3 mm was obtained.

When the degree of yellowness of the obtained resin plate was measured using a digital color computer,
It was 1.1. Further, the resin plate was treated at 60 ° C. for 2 weeks in a hot air oven (Tabay: PHH-200), and the yellowness was measured again.

Comparative Example 1 When the yellowness of the resin coarse powder was measured by the same method as in Example 1, the yellowness before the heat treatment was 1.8 and the yellowness after the heat treatment was 10.9.

From the above results, it is clear that the present invention can improve the color tone. It was also found that the heat resistance was also improved.

Further, two surfaces of the resin molded product obtained in Example 1 which were perpendicular to each other were sanded with sandpaper so that the two surfaces had a mirror finish, and then buffed.

The polished resin sample piece was evaluated with a refractometer (KPR-2 manufactured by Calnew Optical Co., Ltd.),
d-line (wavelength: 587.6 nm) refractive index (nd), formula (4)
The Abbe number (νd) obtained from the above was measured, and it was found that the resin had a high refractive index and a low dispersion with a refractive index of 1.629 and an Abbe number of 27.2.

The Abbe number is an index representing optical dispersibility and is defined by the following equation (7).

Abbe number (νd) = (nd-1) / (nf-nc) (7) nd: d line (wavelength 587.6 nm) Refractive index nf: f line (wavelength 656.3 nm) Refractive index nc: c Line (wavelength 486.1 nm) Refractive index A resin molded product for an eyeglass lens was molded using the resin obtained in Example 1. As a result, a very good molded product with good moldability and little distortion was obtained. .

Further, when a stretched film was produced using the resin obtained in Example 1, it was found that a retardation film having excellent transparency and color tone and good wavelength dispersion characteristics can be produced.

[0069]

According to the present invention, a thermoplastic resin having a high refractive index and a high Abbe number and an improved color tone can be provided, and a lens made of this resin can be used in various fields.

Claims (3)

[Claims] 1. A phosphonic acid residue represented by the following general formula (1) and a divalent phenol residue and a carbonate residue represented by the following general formula (2), and a phosphonic acid residue and a carbonate residue. The resin for lenses is characterized by satisfying the formula (3) and having a sodium content of less than 5 ppm. General formula (1) General formula (2) [In the formula (1), R represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents oxygen, sulfur or selenium. In formula (2), R'is each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms,
It is selected from the group consisting of aromatic hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, hydrocarbon groups and nitro groups. p and q are integers of p + q = 0 to 8, Y is a single bond, oxygen atom, sulfur atom, 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,
It is selected from the group consisting of an aromatic phosphine oxide group, an alkylsilane group, a dialkylsilane group, a fluorene group, a branched chain-containing alkylidene group, and a branched chain-containing cycloalkylidene group. 1> (a) / [(a) + (b)] ≧ 0.05 (3) [where (a) represents the phosphonic acid residue and (b) represents the number of moles of the carbonate residue.] ] 2. A resin for lenses, characterized in that the general formula (2) according to claim 1 is represented by any one of the following general formulas (4) to (7). General formula (4) General formula (5) General formula (6) General formula (7): [In formulas (4) to (7), R'is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydrocarbon group, It is selected from the group consisting of nitro groups. p and q are integers of p + q = 0 to 8. ] 3. The resin according to claim 1, wherein the resin contains a phosphonite residue, and the content ratio of the phosphonite residue is not more than equimolar to the phosphonic acid residue. resin.