JP2003268109A - Phosphorus-containing resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin with good color toner and having a high refractive index and low dispersibility in spite of being a thermoplastic resin. <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, 1-20C aliphatic hydrocarbon group, 1-20C aromatic hydrocarbon group, halogen atom and a nitro group; Y is selected from the group consisting of a single bond, oxygen atom, sulfur atom, alkylene group, alkylidene group, etc.), and a carbonate residue, and 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.). This resin is purified by using the steps of dissolving the resin in an organic solvent and adding the solution to another solvent held at a temperature higher than the boiling point of the organic solvent to isolate the resin. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an improved color tone,
It also relates to a thermoplastic resin having a high refractive index and a low dispersion.

[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, 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 a high refractive index but have problems such as high dispersibility and colorability, and thus cannot be applied to optical lens applications.

We have a phosphonic acid residue in the backbone,
Moreover, the inventors have focused on resins having thermoplasticity, have found a resin having high refraction and low dispersion, and have found that there is a possibility of meeting the demand for the optical resin. However, the resin having a phosphonic acid residue obtained by a known method is likely to be colored during the manufacturing process, and the reason has not been clear. As a result, the features of high refractive index and low dispersion cannot be fully utilized, and their use is limited.

[0006]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a colorless and transparent thermoplastic resin having high refractive index and low dispersion, which is a polymer having a phosphonic acid residue, and a method for producing the same. To do.

[0007]

To solve the above problems, the present invention has the following constitution. That is, (A) 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) are included, and a phosphonic acid residue and a carbonate residue are included. The mole fraction of satisfies the formula (3), and
A resin having a yellowness index (hereinafter referred to as ΔYI) of 5 or less when formed into a molded product having a thickness of mm, a general formula (1)

[0008]

[Chemical 5]

General formula (2)

[0010]

[Chemical 6]

[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, 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) [where (a) represents the phosphonic acid residue and (b) represents the number of moles of the carbonate residue.] ] (B) The resin according to (A), wherein the resin has a number average molecular weight of 20,000 or more. (C) The resin contains a phosphonite residue, and the content ratio of the phosphonite residue is not more than an equimolar amount with respect to the phosphonic acid residue. (A) or (B) A resin of (D), which is a method for producing a resin, including the step of contacting the resin dissolved in an organic solvent with another solvent to isolate the resin,
The other solvent is a solvent having a boiling point of the organic solvent or higher, and the resin is a phosphonic acid residue represented by the following general formula (1) and a phosphonic acid residue represented by the following general formula (2).
A method for producing a resin, which comprises a hydric phenol residue and a carbonate residue and in which the molar fraction of the phosphonic acid residue and the carbonate residue satisfies the formula (3), the general formula (1)

[0012]

[Chemical 7]

General formula (2)

[0014]

[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)
R's are each 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, 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) [where (a) represents the phosphonic acid residue and (b) represents the number of moles of the carbonate residue.] ] (E) The other solvent is water, the method for producing a resin according to (D), (F) The pH of the other solvent after being brought into contact with the other solvent swings to the same or acidic region, And (D) comprising a step of preparing a resin solution before contact so that the resin solution is finally neutral or acidic.
A method for producing the described resin.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a method for producing a resin having a phosphonic acid residue, which solves the above problem, that is, the coloring problem.

The present invention is characterized in that a solvent in which a resin described below is dissolved is brought into contact with another solvent having a boiling point of the solvent or higher.

The organic solvent in which the resin used in the present invention is dissolved is not particularly limited as long as it can dissolve the resin described below. Such solvents include, for example, halogen-based solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, chloroform, 1,1,1-trichloroethane, trichloroethylene, carbon tetrachloride, oxetane, tetrahydrofuran and tetrahydro. Examples include cyclic ether solvents such as Pian. Dichloromethane, chloroform and tetrahydrofuran are preferred, and dichloromethane is more preferred.

These solvents may be used alone, may be mixed at an arbitrary ratio, or may be water-containing.

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)

[0021]

[Chemical 9]

General formula (2)

[0023]

[Chemical 10]

Specific examples of the substituent R substituting the phosphorus atom of the phosphonic acid residue represented by the above general formula (1) include 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 examples of such phosphonite residues, the above-mentioned phosphonic acid residues can be mentioned as well as the corresponding phosphinic acid residues. By introducing this phosphinic acid residue, it is possible to impart oxidation resistance to the resin. Considering the stability of properties such as optical properties, the content thereof is preferably 50 mol% or less of the phosphonic acid residue, more preferably 25% or less, and further preferably 10% or less. The lower limit is preferably 1 mol%
That is all.

Specific examples of the divalent phenol residue represented by the general formula (2) as the basic structure divalent phenol are 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) 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-sec)
Butyl-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-tert-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 (3,3
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 (3,3
5-ditert-butyl-4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-3,5-dit)
ert-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 ter
t-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-methylpropane , 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-hydroxy) Phenyl) -2-
(2-Hydroxyphenyl) propane, bis (2-hydroxy-3-allylphenyl) methane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-
Methyl propane, 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-dit)
ert-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 (3,5-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 ter
t-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.

The carbonate residue of the present invention means a carbonic acid 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) [(a) represents the phosphonic acid residue, and (b) represents 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. Also, this ratio is 0.0
When it is less than 5, the properties as an optical material such as the refractive index are insufficient. The upper limit is preferably 0.90 or less, and more preferably 0.85. Further, the lower limit is preferably 0.30 or more, more preferably 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 specific method for obtaining 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 of reacting an acid halide and a divalent phenol in an organic solvent (A. Conix Ind. Eng. Chem.
51147, 1959, Japanese Examined 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, a divalent acid and a divalent acid.
-Polymerization method in which a divalent phenol is heated in the presence of diallyl carbonate (Japanese Examined Patent Publication No. 38-26299), a divalent acid halide dissolved in an organic solvent incompatible with water, and a divalent dissolved in an alkaline aqueous solution. Interfacial polymerization method (W.M. EAREKSON)
J. Poly. Sci. XL399 1959, Japanese Examined Patent Publication No. 40-1959), and the like. However, since 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, the solution polymerization method is particularly preferable. It is preferably adopted.

The solution polymerization method will be described with reference to an example. 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. The resin of the present invention can be obtained by adding a precursor molecule of, for example, triphosgene or the like 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, a monofunctional substance may 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.

In the method for producing a resin of the present invention, the resin obtained by the above-mentioned polymerization method or the like is made into a solution state dissolved in an organic solvent, and then the resin solution is brought into contact with another solvent to volatilize the solvent. While isolating the resin.

In order to obtain a resin solution, there may be mentioned a method in which the resin once isolated is dissolved in a solvent, polymerization is carried out in a solution state, and the solution is used. From the viewpoint of suppressing the deterioration of the resin and improving the color tone, it is preferable to carry out solution polymerization and use the solution as it is. It should be noted that there is no problem in adding another solvent after forming a solution or using a mixed solvent. Further, the other solvent is preferably a poor solvent for the resin of the present invention, and when it is not a poor solvent, the amount of recovered resin is small. The solvent is not particularly limited as long as it satisfies such conditions, and can be appropriately selected depending on the type of solvent in which the resin is dissolved.
Examples thereof include water, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, propyl alcohol, butyl alcohol, and ethylene glycol, and water is particularly preferable because impurities such as ammonium salts are easily dissolved. The temperature of the other solvent is preferably 20 ° C. or higher with respect to the boiling point of the solvent of the resin solution.

In the present invention, examples of the method of bringing the resin dissolved in the organic solvent into contact with the other solvent include a method of bringing the resin dissolved in the organic solvent into contact with the other solvent in a container equipped with a stirrer. However, the present invention is not limited to this. As an example, there is a method in which a resin dissolved in an organic solvent is mixed stepwise or all at once in a container containing another solvent which is kept at a boiling point of the solvent of the resin solution or higher. Regarding the container, it is desirable that the cooling device and the container for receiving the solvent are connected to each other so that the solvent vapor in which the resin is dissolved can be recovered.

Further, it is preferable that the resin solution is treated with an acidic aqueous solution or the like before being brought into contact with the other solvent so that the pH after the treatment is neutral or acidic. By making the resin neutral or acidic, decomposition and modification of the resin are suppressed, and even if it is affected by other components, it is unlikely to be affected, and the resin has a high molecular weight and good mechanical properties such as impact resistance. And the color tone can be improved.

In this way, the resin is brought into a resin solution state,
The solvent of the resin solution is volatilized by bringing this resin solution into contact with another solvent, which is a poor solvent for the resin preferably kept at a boiling point higher than the solvent of the resin solution, and impurities such as ammonium salts in the resin solution are volatilized. While being transferred to another solvent layer, the resin is precipitated / precipitated in the other solvent and recovered. By using the method of the present invention, the color tone, especially the yellowness, is dramatically improved and a resin suitable for optical use is obtained, but the reason why the color tone is improved is not always clear. Where considered, some impurities causing coloration contained in the resin migrate to the other solvent at the time of precipitation of the resin, and because the other solvent is the boiling point of the solvent of the resin solution or more, It is considered that the contact area with the solvent can be increased, and the resin can be efficiently removed even to the inside of the resin, which is an improvement.

The color tone of the resin of the present invention is dramatically improved by such a method. That is, the yellowness index (ΔYI) of the resin plate having a thickness of 3 mm is 5 or less. 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 Furthermore, since the resin of the present invention has a number average molecular weight of 20,000 or more, the mechanical strength of the molded product is also satisfactory. If the molecular weight is less than 20,000, mechanical strength such as toughness will be insufficient. The number average molecular weight was measured by gel permeation chromatography, and the molecular weight was calculated by using a calibration curve prepared in advance using polystyrene.

The resin of the present invention is used for lenses such as eyeglass lenses and contact lenses, housing applications for home electric appliances, recording media such as CD ROM and DVD ROM, film applications such as magnetic films and retardation films, and the like. It can be used for flame retardant applications.

[0046]

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

The yellowness was determined by the following measurement.

The resin sample was press-molded on a disk-shaped resin plate having a diameter of 30 mm and a thickness of 3 mm. The press molding was performed under the conditions of the glass transition temperature of the resin + 110 ° C., the press pressure of 2 t and the press time of 3 minutes.

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 the equation (5) was obtained. Then, YI ₂ is obtained. Further, X, Y, and Z are similarly obtained with the sample plate removed, the reference value YI ₁ is similarly obtained, and ΔYI is obtained by the equation (6).

YI = 100 × (1.28X−1.06Z) / Y (5) X, Y, Z: Tristimulus value of the sample under standard light C ΔYI = YI ₂ −YI ₁ (6) ΔYI: Yellowness YI ₁ : Reference value YI ₂ : Measured value of sample Glass transition temperature (Tg) was determined by the following measurement. A Seiko Denshi Kogyo DSC (SSC5200) system was used. Tg was observed when the temperature was raised to 250 ° C. at 10 ° C./min, held for 3 minutes, cooled to 0 ° C. at −50 ° C./min, held for 3 minutes, and then again raised to 10 ° C./min. The value calculated from the top of the peak. In addition, the measurement was performed using a sample dried under vacuum at 80 ° C. for 8 hours.

The number average molecular weight was based on the following measurements.

It was measured by 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.

[Preparation of Resin Solution 1] Methylbenzylidenebisphenol A (2 mol) and triethylamine (4 mol) were mixed in dichloromethane (5 L) under a nitrogen atmosphere, and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (2 mol) in dichloromethane (6 L) was added dropwise to this solution over 35 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 90 minutes. Then, the reaction solution was poured into 50 L of hexane for reprecipitation, and the polymer was collected by filtration, and then (1) ethanol 25 L (2)
Water / ethanol = 1/1 mixed solution 25 L (3) Water 25 L was washed with the resin produced in this order, and the crude resin powder was obtained in a yield of 9
Obtained at 0%.

Resin solution 1 was obtained by dissolving crude resin powder (100 g) in dichloromethane (1 L).

[Preparation of Resin Solution 2] Resin crude powder (100 g) obtained by the above-mentioned preparation method was dissolved in chloroform (1 L) to obtain Resin Solution 2.

[Preparation of Resin Solution 3] Under a nitrogen atmosphere, methylbenzylidene bisphenol A (2 mol) and triethylamine (4 mol) were mixed in dichloromethane (5 L), and the mixture was stirred under ice cooling. A solution of phenylphosphonic acid dichloride (2 mol) in dichloromethane (6 L) was added dropwise to this solution over 35 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 90 minutes. 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, the dichloromethane layer was washed twice with water (10 L) to obtain the target resin solution 3.

Example 1 Hot water (23 L) at 70 ° C. was placed in a stainless steel container having an inner volume of 35 L and equipped with a distillation solvent recovery facility at the lid. The resin solution 1 was added into the container over 20 minutes while distilling the solvent. After the addition was completed, a resin block was collected from the container.

The resin mass was crushed and then dried to obtain a target resin powder (number average molecular weight: 45,000, Tg: 141 ° C.).

The resin powder thus obtained was molded into a disk-shaped plate at 250 ° C., and the yellowness (ΔYI) was measured.
It was 1.5.

Example 2 Hot water (32 L) at 95 ° C. was placed in a stainless steel container having an internal volume of 35 L and equipped with a distillation solvent recovery facility at the lid. The resin solution 2 was added into the container over 20 minutes while distilling the solvent. After the addition was completed, a resin block was collected from the container.

The resin mass was crushed and then dried to obtain the target resin powder (number average molecular weight: 45,000, Tg: 141 ° C.).

Molding was carried out in the same manner as in Example 1 and the yellowness was measured and found to be 1.9.

Example 3 Hot water (23 L) at 70 ° C. was placed in a stainless steel container having an internal volume of 35 L and equipped with a distillation solvent recovery facility on the lid. The resin solution 3 was added into the container over 20 minutes while distilling the solvent. The pH of the aqueous layer after the addition was 7 was 7. After the addition was completed, a resin block was collected from the container.

The resin mass was crushed and then dried to obtain the target resin powder (number average molecular weight: 82000, Tg: 141 ° C.).

Molding was carried out in the same manner as in Example 1 and the yellowness was measured and found to be 1.8.

Comparative Example 1 The resin coarse powder obtained in [Resin Solution Preparation 1] was molded in the same manner as in Example 1 and the yellowness was measured.
It was 10.5.

From the above results, it is clear that a resin having an excellent color tone can be obtained according to the present invention.

Further, the resin molded product obtained in Example 1 was sanded with sandpaper so that the two surfaces perpendicular to each other were mirror-finished, 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.

[0073]

The present invention has a high refractive index and a low dispersion,
Further, it is possible to obtain a resin having thermoplasticity and excellent in moldability, color tone, heat resistance and flame retardancy. This resin is suitably used for optical applications, and can be used particularly in various fields such as optical films and lenses.

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

Claims (6)

[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. And the yellow fraction (hereinafter Δ) when a molded product having a thickness of 3 mm satisfies the formula (3).
YI) is 5 or less. 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, 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. ,
It is selected from the group consisting of aromatic phosphine oxide groups, alkylsilane groups, dialkylsilane groups, and fluorene groups. 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. The resin according to claim 1, which has a number average molecular weight of 20,000 or more. 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 an equimolar amount to the phosphonic acid residue. resin. 4. A method for producing a resin, which comprises a step of contacting a resin dissolved in an organic solvent with another solvent to isolate the resin, wherein the other solvent has a boiling point of the organic solvent or higher. And the resin contains a phosphonic acid residue represented by the following general formula (1), a divalent phenol residue and a carbonate residue represented by the following general formula (2), and a phosphonic acid residue And a resin in which the molar fraction of carbonate residues satisfies the formula (3). 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 an aromatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydrocarbon group and a nitro group, and p and q are p
+ Q = an integer from 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. ,
It is selected from the group consisting of aromatic phosphine oxide groups, alkylsilane groups, dialkylsilane groups, and fluorene groups. 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.] ] 5. The method for producing a resin according to claim 4, wherein the other solvent is water. 6. Prior to contacting with the other solvent,
The method for producing a resin according to claim 4, comprising a step of washing the resin solution by adding an acidic aqueous solution to the resin solution until the pH of the separated aqueous layer becomes neutral or acidic.