JPH0834853A - Optical material - Google Patents

Abstract

PURPOSE:To provide an optical material which has refractive index high enough to be used as a plastic optical lens or a phase contrast film and is excellent in heat resistance and transparency. CONSTITUTION:An optical material is provided which is an arom. polyethersulfone comprising 10-40mol% repeating units represented by formula I and 60-90mol% repeating units represented by formula II and has a reduced viscosity (at 30 deg.C) in dimethylformamide at a concn. of 1 g/dl) of 0.35-0.7dl/g.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an optical material comprising an aromatic polyether sulfone copolymer or an aromatic polyether sulfide copolymer having a refractive index of 1.70 or more.

[0002]

2. Description of the Related Art Plastic optical materials are lighter in weight than inorganic glass, less likely to break, and more easily processed, so that they have been rapidly prevailing in recent years as optical elements such as spectacle lenses and camera lenses.

Materials widely used as the above-mentioned plastic optical materials are, for example, those obtained by radical polymerization of diethylene glycol bisallyl carbonate. These have excellent properties such as light weight, excellent impact resistance, easy dyeing, and good workability such as cutting and polishing, but have a refractive index (n _D ) of that of inorganic glass. Since it is as low as 1.50 as compared with 0.52, for example, in order to obtain optical properties equivalent to those of a glass lens, the center thickness of the lens,
It is necessary to increase the edge thickness, the curvature, etc., so that there is an unavoidable drawback that the overall thickness is inevitable.

Japanese Unexamined Patent Publication (Kokai) No. 61-28513 discloses that a special polymer of fumaric acid diester has a high refractive index and is suitable for the above purpose, but the refractive index is about 1.53 at maximum. However, it was not always sufficient as a substitute for the inorganic glass.

Japanese Unexamined Patent Publication (Kokai) No. 2-18501 discloses a technique using polycarbonate having a high refractive index of 1.60, but has a low heat resistance of 150 ° C. Originally, it had a defect that it was deformed by the heat of the light source. Furthermore, polycarbonate has a low chemical resistance such as a ketone resistance chemical, and there is a problem that when forming an antireflection film, a hard coat film, etc. on a lens surface, the organic solvent usable as a paint is limited. It was

A higher refractive index of 1.70 or more is required for use as an optical multilayer film such as a selective reflection film and a selective transmission film, but the highest commercially available plastic optical material is manufactured by ICI. Polyethersulfone 1.
The number of plastic optical materials having a high refractive index is 64, and even if the refractive index exceeds 1.70, there are problems such as transparency, coloring of the material, and brittle fracture. There was no one available. Therefore,
The optical multilayer film currently used is made by vapor deposition of inorganic glass, but since it is difficult to vaporize a large area and the cost is high, it has not been widely used although it has potential market requirements. In this state, there is an increasing demand for a plastic optical material having a high refractive index capable of forming a coating film by a simple coating method.

On the other hand, the retardation film, which is one of the liquid crystal display members, tends to be selected with a material having a high refractive index with the use of a high-speed response liquid crystal. The range is up to 1.75, and therefore, a material having a high refractive index has been desired even for a retardation film material.

Further, the aromatic sulfur-containing polymer is useful as an engineering plastic excellent in heat resistance and chemical resistance, and due to the high molecular refraction of sulfur and aromatic rings, the polymer also has a high refractive index. Is believed to have. However, a sulfide-based polymer represented by PPS (polyphenylene sulfide) has a serious problem when used for optical applications because it is strongly colored and has poor transparency.

[0009]

In view of the above, the present invention is to provide an optical material having a high refractive index which can be used as a plastic optical lens and a retardation film, and which is excellent in heat resistance and transparency. To aim.

[0010]

DISCLOSURE OF THE INVENTION The gist of the present invention is to provide an optical material with repeating units 10 to 40 represented by the following formula (I).
Repeating unit 60 represented by mol% and the following formula (II)
.About.90 mol% and a reduced viscosity of 0.35 to 0.7 d
l / g (30 ° C., in dimethylformamide, concentration 1 g /
It is composed of an aromatic polyether sulfone copolymer which is dl).

[0011]

Embedded image

The repeating unit represented by the above formula (I) is
It is 10 to 40 mol%. When the repeating unit represented by the above formula (I) is less than 10 mol%, the refractive index is lowered and 4
If it exceeds 0 mol%, the crystallinity will develop and the transparency will be impaired, so the content is limited to the above range.

The monomer forming the repeating unit represented by the above formula (I) is not particularly limited, and examples thereof include:
2 ', 2 "-dihydroxy-m-quaterphenyl, 4,4'-dihydroxy-3,3'-diphenylbiphenyl, 4-hydroxy-4'-fluoro-3,3'
-Diphenylbiphenyl, 4,4'-difluoro-3,
3'-diphenylbiphenyl, 4-hydroxy-4'-
Chloro-3,3'-diphenylbiphenyl, 4-hydroxy-4'-bromo-3,3'-diphenylbiphenyl, 4,4'-dibromo-3,3'-diphenylbiphenyl, 4,4'-dichloro-3 , 3'-diphenylbiphenyl and the like. Preferred is 4,4'-dihydroxy-3,3'-diphenylbiphenyl.

The monomer forming the repeating unit represented by the above formula (II) is not particularly limited, and examples thereof include:
4,4'-dichlorodiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone and the like can be mentioned.

In the polyether sulfone copolymer of the present invention, in addition to the above-mentioned monomer, a monomer or the like copolymerizable with the above-mentioned monomer can be copolymerized. As the above-mentioned copolymerizable monomer, the following (1) group monomer, (2) group monomer and the like are used.

Monomers of group (1) 4,4'-dihydroxydiphenyl sulfone, 4,4 '
-Difluorodiphenyl sulfone, 4,4'-dichlorodiphenyl sulfone, 4,4'-dibromodiphenyl sulfone, 4-hydroxy-4'-fluorodiphenyl sulfone, 4-hydroxy-4'-chlorodiphenyl sulfone, 4-hydroxy-4 ′ -Bromodiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide,
4,4'-difluorodiphenyl sulfoxide, 4,
4'-dichlorodiphenyl sulfoxide, 4,4'-dibromodiphenyl sulfoxide, 4-hydroxy-4 '
-Fluorodiphenyl sulfoxide,

4-hydroxy-4'-chlorodiphenyl sulfoxide, 4-hydroxy-4'-bromodiphenyl sulfoxide, 4,4'-dihydroxydiphenyl ketone, 4,4'-difluorodiphenyl ketone, 4,
4'-dibromodiphenyl ketone, 4-hydroxy-
4'-fluorodiphenyl ketone, 4-hydroxy-
4'-chlorodiphenyl ketone, 4-hydroxy-4 '
-Bromo diphenyl ketone, 4,4'-difluorodiphenyl ether, 4,4'-dichlorodiphenyl ether, 4,4'-dibromodiphenyl ether, 4-hydroxy-4'-fluorodiphenyl ether, 4-hydroxy-4'-chlorodiphenyl ether, 4 -Hydroxy-4'-bromodiphenyl ether, 4,4'-methylenebisphenol,

4,4'-ethylidene bisphenol,
4,4'-methylenebis (2-methylphenol),
4,4'-methylenebis (2,6-dimethylphenol), 4,4'-isopropylidenebisphenol,
4,4'-isopropylidene bis (2-methylphenol), 4,4 '-(1,3-dimethylbutylidene) bisphenol, 4,4'-isopropylidene bis (2,2)
6'-dimethylphenol), 4,4 '-(1-phenylethylidene) bisphenol, 4,4'-isopropylidenebis (2-phenylphenol), 4-chloro-
4 '-(p-hydroxyphenyl) diphenylketone.

Group (2) Monomer 4,4'-dihydroxybiphenyl 4-hydroxy-4'-fluorobiphenyl, 4-hydroxy-4'-chlorobiphenyl, 4-hydroxy-
4′-bromobiphenyl, 4,4′-difluorobiphenyl, 4,4′-dichlorobiphenyl, 4,4′-dibromobiphenyl 4,4 ″ -dihydroxy-1,1 ′:
2 ', 1 "-terphenyl, 4,4"-dihydroxy-1,1': 3 ', 1 "-terphenyl, 4,
4 ″ -dichloro-1,1 ′: 2 ′, 1 ″ -terphenyl, 4,4 ″ -dichloro-1,1 ′: 3 ′, 1 ″
-Terphenyl, 4,4 "-dichloro-1,1 ':
4 ′, 1 ″ -terphenyl, 4-hydroxy-4 ″
-Chloro-1,1 ': 2', 1 "-terphenyl, 4
-Hydroxy-4 "-chloro-1,1 ': 3',
1 ″ -terphenyl, 4-hydroxy-4 ″ -chloro-1,1 ′: 4 ′, 1 ″ -terphenyl, 4,
4 ″ ″-dichloro-1,1 ′: 4 ′, 1 ″:
4 ″, 1 ″ ″-quaterphenyl,

4-hydroxy-4 ″ ″-chloro-1,
1 ′: 4 ′, 1 ″: 4 ″, 1 ″ ″-quaterphenyl, 4,4 ″ ″-dihydroxy-1,1 ′:
2 ′, 1 ″ ″: 2 ″, 1 ″ ″-quaterphenyl, 4,4 ″ ″-dichloro-1,1 ′: 2 ′,
1 ″: 2 ″, 1 ″ ″-quaterphenyl, 4-
Hydroxy-4 ″ ″-chloro-1,1 ′: 2 ′,
1 ″: 2 ″, 1 ″ ″-quaterphenyl, 4,
4 ″ ″-dihydroxy-1,1 ′: 3 ′, 1 ″:
3 ″, 1 ″ ″-quaterphenyl, 4,4 ″ ″
-Dichloro-1,1 ': 3', 1 ": 3",
1 ″ ″-quaterphenyl, 4-hydroxy-
4 ″ ″-chloro-1,1 ′: 3 ′, 1 ″ ″ 3 ″,
1 ″ ″-quaterphenyl, 4,4′-dimercaptodiphenyl sulfide, 4,4′-dichlorodiphenyl sulfide. The (1) group monomer or the (2) group monomer may be used alone or in combination of two or more kinds.

In the present invention, in addition to the (1) group monomer and the (2) group monomer, a dihydroxy compound monomer, a dihalogen compound monomer or the like copolymerizable with the polyether sulfone copolymer may be used.

The above-mentioned dihydroxy compound monomer and dihalogen compound monomer are not particularly limited.
p-cresol, 4,4'-dihydroxydiphenyl,
4,4 ″ -dihydroxy-p-terphenyl, 4,
4 ″ ′-dihydroxy-p-quaterphenyl,
2,2-bis- (4-hydroxyphenyl) -propane, bis- (4-hydroxyphenyl) -methane, 4,
4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 1,4-bis- (4-dihydroxydiphenyl) -ether, 1,4-bis- (4-dihydroxybenzoyl) -Benzene, 4-hydroxy-
4 '-(p-hydroxyphenyl) diphenyl sulfone, 4-chloro-4'-(p-hydroxyphenyl) diphenyl sulfone, 4,4'-dichlorodiphenyl ketone and the like can be mentioned.

The above dihydroxy compound monomer and dihalogen compound monomer account for 30 mol% of the resulting copolymer.
The following is preferred. When it exceeds 30 mol%, the refractive index is lowered.

The reduced viscosity of the above-mentioned aromatic polyether sulfone copolymer is 0.35 to 0.7 dl / g (concentration 1.0 g / dl in dimethylformamide at 30 ° C.).
When the reduced viscosity is less than 0.35 dl / g, the molded body causes brittle fracture, and when it exceeds 0.7 dl / g, the moldability is lowered and residual birefringence is exhibited, so that the range is limited.

The method for producing the aromatic polyether sulfone copolymer is not particularly limited, and for example, a nucleophilic substitution polycondensation method in which heat polymerization is performed in a polar solvent in the presence of an alkali metal salt can be used.

The alkali metal salt is not particularly limited, and for example, sodium carbonate, potassium carbonate, rubidium carbonate, potassium oxalate, potassium bicarbonate and the like are preferable, and potassium carbonate and sodium carbonate are particularly preferable.

The polar solvent is not particularly limited, and examples thereof include sulfolane, diphenyl sulfone, dimethyl sulfoxide, dimethyl sulfone, and other sulfone-based solvents; dimethylacetamide, dimethylimidazoline, N-methyl-2-pyrrolidone, N-cyclohexyl-2. -Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylimidazoline and other amide-based solvents; N-ethylcaprolactam, N-n-propylcaprolactam and other caprolactam-based solvents, and the like. These may be used alone or in combination of two or more. Further, in order to remove water, for example, a solvent that is azeotropic with water, such as toluene or chlorobenzene, may be used.

In the above heat polymerization, the polymerization temperature is usually in the range of 100 to 400 ° C, preferably 150 to 280 ° C.
Is preferred.

The method for carrying out the above heat polymerization is not particularly limited and, for example, a monomer forming the repeating unit represented by the above formula (I) and a repeating unit represented by the above formula (II) are formed. A method of collectively charging monomers into a polymerization tank, a monomer forming the repeating unit represented by the above formula (I), and a part of the monomer forming the repeating unit represented by the above formula (III) are polymerized. Examples thereof include a method of controlling the molecular structure which is introduced in the latter stage. In order to accelerate the heat polymerization, reflux dehydration may be performed using a solvent that is azeotropic with the water before the heat polymerization.

The method of collecting and purifying the aromatic polyether sulfone copolymer is not particularly limited. For example, after completion of the heat polymerization, the reaction is carried out using a good solvent for the aromatic polyether sulfone copolymer. After diluting the mixture, a reprecipitation method of adding a poor solvent for the aromatic polyether sulfone copolymer to precipitate the aromatic polyether sulfone copolymer, and washing with a suitable washing liquid,
A known method such as an extraction method in which impurities are partially removed from the aromatic polyether sulfone copolymer by using an extraction solvent, and the mixture is washed with an appropriate washing liquid and then collected is exemplified.

The optical material of the present invention 2 comprises 5 to 45 mol% of repeating units represented by the above formula (I) and the following formula (II)
I) consisting of 95 to 55 mol% of the repeating unit and having a reduced viscosity of 0.30 to 0.75 dl / g (30 ° C.,
(Concentration 0.5 g / dl in N-methyl-2-pyrrolidone)
Which is an aromatic polyether sulfide copolymer.

[0032]

[Chemical 4]

The repeating unit represented by the above formula (I) is
It is 5 to 45 mol%. When the repeating unit represented by the above formula (I) is less than 5 mol%, the heat resistance is lowered and 4
If it exceeds 5 mol%, crystallization will occur and the transparency will be impaired, so the content is limited to the above range.

The reduced viscosity of the aromatic polyether sulfide copolymer is 0.30 to 0.75 dl / g (in N-methyl-2-pyrrolidone, 30 ° C., 0.5 g / dl). When the reduced viscosity is less than 0.30 dl / g,
If brittle fracture occurs during molding and exceeds 0.75 dl / g, stress strain during molding remains in the molded body to cause birefringence and the like, so the range is limited to the above range.

The monomer forming the repeating unit represented by the above formula (III) is not particularly limited, and for example,
Bis- (4-hydroxyphenyl) sulfide, 4-hydroxy-4'-fluorodiphenylsulfide, 4-
Hydroxy-4'-chlorodiphenyl sulfide, 4-
Hydroxy-4'-bromodiphenyl sulfide, 4,
4'-dichlorodiphenyl sulfide, 4,4'-difluorophenyl sulfide and the like can be mentioned. Preferably, bis- (4-hydroxyphenyl) sulfide, 4
-Hydroxy-4'-chlorodiphenyl sulfide,
4,4'-dichlorodiphenyl sulfide and the like can be mentioned.

In the present invention 2, in addition to the above-mentioned monomers, the above-mentioned (1) group monomer and the above-mentioned (2) group monomer which are copolymerizable with the above-mentioned monomer may be used. The total addition amount of the above-mentioned (1) group monomers is preferably 50 mol% or less based on the total amount of the monomers. When it exceeds 50 mol%, the refractive index is 1.7.
It falls below 0. The total addition amount of the above-mentioned (2) group monomer is such that the total amount with the monomer forming the repeating unit represented by the above formula (I) is 45 mol% with respect to the total amount of the monomers.
The following range is preferable. If it exceeds 45 mol%, the crystallinity increases and the transparency decreases.

A monomer forming a repeating unit represented by the above formula (I), a monomer forming a repeating unit represented by the above formula (III), the above-mentioned (1) group monomer, and the above (2) group monomer The number of halogens contained in
It is preferably 0.95 to 1.05 times the number of hydroxyl groups. If it deviates from this range, the polymerization reaction is hindered and the reduced viscosity of the aromatic polyether sulfide copolymer is 0.3 dl /
It is less than g.

As the alkali metal salt, an alkali metal hydroxide may be used. The alkali metal hydroxide is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, rubidium hydroxide and the like.

The polymerization temperature in the above heat polymerization is 120 to 3
50 ° C is preferred. If the temperature is lower than 120 ° C., the reaction does not proceed and the reduced viscosity becomes less than 0.30 dl / g.
If it exceeds 0 ° C, the polymer is colored due to a side reaction. The temperature is preferably 150 to 320 ° C.

[0040]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1 A reaction vessel equipped with a stirrer, a gas introduction tube, a thermometer, and a condenser having a receiver at the tip thereof was added with 68.0 parts by weight of 2 ', 2 "-dihydroxy-m-quarterphenyl, 4,4. ′-
143.5 parts by weight of dichlorodiphenyl sulfone, 4,
75.0 parts by weight of 4'-dihydroxydiphenyl sulfone, 15.2 parts by weight of anhydrous potassium carbonate, N-methyl-2
-Pyrrolidone (500 parts by weight) and toluene (200 parts by weight) were charged, and the atmosphere was replaced with nitrogen. Next, under a nitrogen atmosphere, stirring and temperature increase were started, and toluene was distilled off at 170 ° C. to remove water in the system. Further raise the temperature 23
The polymerization reaction was carried out at 0 ° C for 2 hours. The obtained polymerization solution was cooled and poured into a mixed solvent of acetone and methanol to precipitate only the polymer. Potassium chloride is removed by further washing with water, and then dried in a vacuum dryer at 120 ° C for 24 hours.
After drying for an hour, a white polymer powder was obtained.

The reduced viscosity of this polymer powder was 1.0 g in dimethylformamide using an Ubbelohde viscometer.
It was measured at a concentration of / dl at 30 ° C. Next, this polymer powder was dissolved in dimethylformamide, a film was prepared by a casting method, and heat resistance, refractive index and transparency were measured as follows, and the results are shown in Table 1.

The heat resistance was judged by the glass transition temperature. The glass transition temperature is measured by Seiko Electronics DSC
Was conducted by a penetration method under the conditions of a temperature rising rate of 20 ° C./min. Refractive index is Abbe refractometer (Atago Co.,
4T type) was measured using diiodomethane as a contact liquid. Transparency is ○, 80 when the total light transmittance is 80% or more by molding the polymer powder into a 0.5 mm plate by press molding.
% Was judged to be opaque.

In Table 1, A represents 2 ', 2 "-dihydroxy-m-quaterphenyl, B represents 4,4'-dichlorodiphenyl sulfone, and C represents 4,4'-dihydroxydiphenyl sulfone. [1] represents the mole fraction of formula (I), and [2] represents the mole fraction of formula (II).

Examples 2 and 3, Comparative Examples 1 and 2 2 ', 2 "-dihydroxy-m-quaterphenyl, 4,4'-dichlorodiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone.
A polymer powder was obtained in the same manner as in Example 1 except that the amount of 4′-dihydroxydiphenyl sulfone was changed to the amount shown in Table 1.
A film was prepared and measured, and the results are shown in Table 1.

Comparative Example 3 Polyether sulfone (manufactured by ICI, VICTREX
PES) was used instead of the above polymer powder, and evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 4 100 parts by weight of diethylene glycol bisallyl carbonate and 3 parts by weight of diisopropyl peroxydicarbonate were added, poured into a mold of 50 × 50 × 105 mm, and kept in an oven at 40 ° C. for 24 hours under a nitrogen atmosphere. . Then, it was kept at 80 ° C. for 4 hours and further at 120 ° C. for 2 hours to complete the curing. Evaluation was performed by the same method as in Example 1, and the results are shown in Table 1.

Example 4 81.20 parts by weight of 4,4'-dividroxy-3,3'-diphenylbiphenyl were added to a reactor equipped with a stirrer, a gas introduction tube, a thermometer and a condenser equipped with a Dernsterk tube. 40 mol%, hereinafter, the mole fraction of the monomer in all the monomers), 13.4 parts by weight of 4,4'-dihydroxydiphenyl sulfide (10 mol%), 76.56 parts by weight of 4,4'-dichlorodiphenyl sulfide (50 mol%) and anhydrous potassium carbonate (45.6 parts by weight) were charged and the atmosphere was replaced with nitrogen. Next, under a nitrogen atmosphere, 500 parts by weight of N-methyl-2-pyrrolidone (hereinafter referred to as "NMP") and 200 parts by weight of toluene were charged, and the temperature increase was started while stirring. When the temperature reached 180 ° C., the temperature elevation was stopped, and in that state, toluene and water were azeotropically distilled for reflux dehydration. Next, the temperature was raised to 190 ° C., and the polymerization reaction was performed as it was for 5 hours. After the reaction is completed, the reaction solution is cooled to room temperature and NMP is added.
Was poured into 2000 parts by weight, then the solution was poured into a large amount of a mixed solvent of methanol-acetone, and the mixture was precipitated while stirring with a homogenizer. Then, the solvent and potassium chloride were removed by sequentially washing with methanol and water.

The reduced viscosity of the obtained polymer was 0.
40 dl / g (30 ° C., 0.5 g / dl in NMP). The polymer was then pelletized with a single screw extruder. Furthermore, 0.5 × under the condition of 300 ° C. on the injection molding machine.
A flat plate of 50 × 105 mm was prepared. Using the same test piece, tests of reduced viscosity, transparency and refractive index (n) were performed. The reduced viscosity was measured in NMP at 30 ° C. at a concentration of 0.5 g / dl. When it is 0.3 dl / g or more, molding can be performed without causing brittle fracture. Transparency is a total light transmittance of 75
% Or more was ◯, and less than 75% was opaque.
The refractive index was measured at a wavelength of 632.8 nm using a DVA-36L type automatic ellipsometer manufactured by Mizojiri Optical Co., Ltd. The results are shown in Table 3.

Example 5 40.60 parts by weight (20 mol%) of 4,4'-dihydroxy-3,3'-diphenylbiphenyl as a monomer,
4,4'-dihydroxydiphenyl sulfide 39.2
Example 4 except that 9 parts by weight (30 mol%), 4,4′-dichlorodiphenyl sulfide 76.56 parts by weight (50 mol%), and anhydrous potassium carbonate 45.6 parts by weight were used.
Polymerization, washing, molding and evaluation were carried out in the same manner as in. The results are shown in Table 3.

Example 6 20.30 parts by weight (10 mol%) of 4,4'-dihydroxy-3,3'-diphenylbiphenyl as a monomer,
4,4'-dihydroxydiphenyl sulfide 52.3
Example 4 except that 8 parts by weight (40 mol%), 4,4′-dichlorodiphenyl sulfide 76.56 parts by weight (50 mol%), and anhydrous potassium carbonate 45.6 parts by weight were used.
Polymerization, washing, molding and evaluation were carried out in the same manner as in. The results are shown in Table 3.

Example 7 As monomers, 4,4'-dihydroxydiphenyl sulfone 15.02 parts by weight (10 mol%), 4,4'-dichlorodiphenyl sulfone 15.02 parts by weight (10 mol%), 4,4 '-Dihydroxy-3,3'-diphenylbiphenyl 40.60 parts by weight (20 mol%), 4,4 '
Examples except that 26.18 parts by weight of dihydroxydiphenyl sulfide (20 mol%), 61.25 parts by weight of 4,4′-dichlorodiphenyl sulfide (40 mol%) and 45.6 parts by weight of anhydrous potassium carbonate were used. Polymerization, washing, molding and evaluation were carried out in the same manner as in 4. The results are shown in Table 3.

Example 8 As monomer, 4,4'-isopropylidene bisphenol (bisphenol A) 13.70 parts by weight (10 mol%), 4,4'-dichlorodiphenyl sulfone 15.0
2 parts by weight (10 mol%), 4,4'-dihydroxy-
40.60 parts by weight of 3,3'-diphenylbiphenyl (2
0 mol%), 4,4′-dihydroxydiphenyl sulfide 26.18 parts by weight (20 mol%), 4,4′-dichlorodiphenyl sulfide 61.25 parts by weight (40 mol%), anhydrous potassium carbonate 45.6 parts by weight Polymerization, washing, molding and evaluation were carried out in the same manner as in Example 4 except that parts were used. The results are shown in Table 3.

Example 9 41.38 parts by weight (20 mol%) of 4-chloro-4 '-(p-hydroxyphenyl) diphenylsulfone as a monomer, 4,4'-dihydroxy-3,3'-diphenylbiphenyl 40. 60 parts by weight (20 mol%), 4,
Other than using 26.18 parts by weight of 4'-dihydroxydiphenyl sulfide (20 mol%), 61.25 parts by weight of 4,4'-dichlorodiphenyl sulfide (40 mol%), and 45.6 parts by weight of anhydrous potassium carbonate. Polymerization, washing, molding and evaluation were carried out in the same manner as in Example 4. The results are shown in Table 3.
It was shown to.

Example 10 4,4'-dihydroxybiphenyl 2 as a monomer
2.24 parts by weight (20 mol%), 4,4'-dihydroxy-3,3'-diphenylbiphenyl 40.60 parts by weight (10 mol%), 4,4'-dihydroxydiphenyl sulfide 13.09 parts by weight ( 10 mol%), 4,4'-
Dichlorodiphenyl sulfide 76.56 parts by weight (50
Mol%) and 45.6 parts by weight of anhydrous potassium carbonate were used, and polymerization, washing, molding and evaluation were carried out in the same manner as in Example 4. The results are shown in Table 3.

Example 11 4,4 ″ ″-dihydroxy-1, as a monomer
1 ': 4', 1 '': 4 '', 1 '''-quaterphenyl 40.60 parts by weight (20 mol%), 4,4'-dihydroxy-3,3'-diphenylbiphenyl 40.6
0 parts by weight (10 mol%), 4,4′-dihydroxydiphenyl sulfide 13.09 parts by weight (10 mol%),
Polymerization and washing were carried out in the same manner as in Example 4, except that 76.56 parts by weight of 4,4′-dichlorodiphenyl sulfide (50 mol%) and 45.6 parts by weight of anhydrous potassium carbonate were used.
Molding and evaluation were performed. The results are shown in Table 3.

Example 12 4,4 ″ ″-dihydroxy-1, as a monomer,
1 ': 3', 1 '': 3 '', 1 '''-quarterphenyl 40.60 parts by weight (20 mol%), 4,4'-dihydroxy-3,3'-diphenylbiphenyl 40.6
0 parts by weight (10 mol%), 4,4′-dihydroxydiphenyl sulfide 13.09 parts by weight (10 mol%),
Polymerization and washing were carried out in the same manner as in Example 4, except that 76.56 parts by weight of 4,4′-dichlorodiphenyl sulfide (50 mol%) and 45.6 parts by weight of anhydrous potassium carbonate were used.
Molding and evaluation were performed. The results are shown in Table 3.

Example 13 4,4 ″ -dihydroxy-1,1 ′ as a monomer:
4 ', 1''-quaterphenyl 31.48 parts by weight (20 mol%), 4,4'-dihydroxy-3,3'-
40.60 parts by weight of diphenylbiphenyl (10 mol%), 4,4'-dihydroxydiphenyl sulfide 1
3.09 parts by weight (10 mol%), 4,4′-dichlorodiphenyl sulfide 76.56 parts by weight (50 mol%),
Polymerization, washing, molding and evaluation were carried out in the same manner as in Example 4 except that 45.6 parts by weight of anhydrous potassium carbonate was used.
The results are shown in Table 3.

Comparative Example 5 A polycarbonate resin panlite manufactured by Teijin Chemicals Ltd. was molded in the same manner as in Example 4 and its physical properties were measured. The results are shown in Table 3. Comparative Examples 6 and 7 4,4'-dihydroxy-3,3'-diphenylbiphenyl, 4,4'-dihydroxydiphenyl sulfide,
Polymerization and evaluation were carried out in the same manner as in Example 4 except that 4,4'-dichlorodiphenyl sulfide was used in the mole fraction shown in Table 2. The results are shown in Table 3.

In Table 2, D is 4,4'-dihydroxy-
3,3'-diphenylbiphenyl, E is 4,
4'-dihydroxydiphenyl sulfone ((1) group monomer), F represents 4,4'-isopropylidene bisphenol ((1) group monomer), G represents 4,
4'-dichlorodiphenyl sulfone ((1) group monomer), H is 4-chloro-4 '-(p-hydroxyphenyl) diphenyl sulfone ((1) group monomer)
I represents 4,4′-dihydroxybiphenyl ((2) group monomer), and J represents 4,4 ″ -dihydroxy-1,1 ′: 4 ′, 1 ″: 4 ″. ，
1 ″ ″-quaterphenyl (monomer (2) group), K is 4,4 ″ ″-dihydroxy-1,1 ′:
3 ′, 1 ″: 3 ″, 1 ″ ″-quaterphenyl ((2) group monomer), L is 4,4 ″ -dihydroxy-1,1 ′: 4 ′, 1 ″ -Terphenyl ((2) group monomer), M represents bis- (4-hydroxyphenyl) sulfide, and N represents 4,4'-.
Represents dichlorodiphenyl sulfide. [3] represents the mole fraction of the formula (I), [4] represents the mole fraction of the formula (III), [5] represents the mole fraction of the ether structure derived from the monomer of the (1) group monomer. Represents the rate, [6] is (2)
Group Monomer Represents the mole fraction of the ether structure derived from the monomer and the mole fraction of formula (I).

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

Since the optical material of the present invention uses the aromatic polyether sulfone copolymer having the above-mentioned constitution, it has a high refractive index of 1.70 or more, little coloring, transparency and heat resistance. Etc., and can be suitably used for various optical materials such as optical lenses, retardation compensating plates, and optical multilayer films.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiro Koremoto 32, Wadai, Tsukuba, Ibaraki Prefecture Sekisui Chemical Co., Ltd. In-house (72) Inventor Tomohiro Fukai 1259 Izumi, Mizuguchi-cho, Koga-gun, Shiga Prefecture Sekisui Chemical Co., Ltd. Note 1-11-3 Minami Kasugaoka, Ibaraki City, Osaka Prefecture

Claims (2)

[Claims] 1. A repeating unit 1 represented by the following formula (I):
0 to 40 mol% and 60 to 90 mol% of a repeating unit represented by the following formula (II), and a reduced viscosity of 0.35 to
An optical material comprising an aromatic polyether sulfone copolymer having a concentration of 0.7 dl / g (30 ° C., concentration: 1 g / dl in dimethylformamide). Embedded image 2. A repeating unit 5 represented by the following formula (I):
To 45 mol% and 95 to 55 mol% of repeating units represented by the following formula (III), and a reduced viscosity of 0.30 to
An optical material comprising an aromatic polyether sulfide copolymer having a concentration of 0.75 dl / g (30 ° C., N-methyl-2-pyrrolidone, concentration: 0.5 g / dl). Embedded image