JP2001106761A - Resin composition, optical element and optical aspherical lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a resin composition having excellent transparency, low optical anisotropy, heat resistance, high refractive index and low double refractive index and an optical aspherical lens having excellent optical characteristics by using the composition. SOLUTION: This resin composition comprises a polycondensate or polyaddition polymer containing at least one sulfur atom in a repeating unit obtained from a fluorene compound of formula (I), for example a compound of formula (II) and at least one kind of compound selected from a polyisothiocyanate compound, a polyisocyanate compound, a polyacyl chloride compound, a polydithioacyl compound, a polysulfonyl chloride compound, a phosgene compound and a thiophosene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition and an optical element, and more particularly to an aspheric lens.

[0002]

2. Description of the Related Art Plastics are widely used in optical products because of their light weight, difficulty in breaking, and safety. For example, various cameras such as glasses, cameras, film-integrated cameras (films with lenses), video cameras, CDs, CDs
-ROM, CD-R, CD-RW, CD-Video,
Conventionally, high-performance optical lenses used for various devices such as optical pickup devices such as MO and DVD, and OA devices such as copying machines and printers include polymethyl methacrylate (PMMA), polycarbonate (PC), and cyclopolyolefin. It is known that a plastic lens or the like injection-molded using such a thermoplastic resin is used for a part or all of the optical product. Further, it is also used in a wide range of fields, such as a base of the above-mentioned discs, a light guide plate of a liquid crystal display, a prism and the like. These resins are ideally required to have good moldability, low optical anisotropy (birefringence) and high refractive index, but it is difficult to satisfy all of these properties. Came. In general, it is known that the refractive index of these properties can be increased by introducing an aromatic ring into the material (for example, a polycarbonate resin), but as a result, the resin (polymer) molecules are oriented. In injection molding, there is a conflicting relationship that optical anisotropy (birefringence) increases and the optical product is unsuitable.

As a material having a small optical anisotropy and a high refractive index in order to solve the above problem, Japanese Patent Application Laid-Open No.
No. 01 (fluorene polyester), 8-10924
No. 9 (fluorene polyester), 9-302077
No. (fluorene polyester), No. 8-160222 (fluorene polycarbonate), No. 5-215902
No. (fluorene acrylic crosslinked polymer), 6-2872
As described in, for example, JP-A No. 30 (a crosslinked polymer of a fluorene allyl compound), there are proposals of a resin containing a fluorene skeleton, and an application of an optical lens using the resin. However, it is insufficient to obtain a sufficiently high refractive index resin, only a crosslinked polymer can be formed, or the use is limited.

On the other hand, as a means for increasing the refractive index, a method of introducing a large number of halogen atoms into a material, a method of introducing sulfur atoms into a material, and the like are known. An example of an optical product using a polymer material having a sulfur atom is disclosed in
No. 6525 (polyisocyanate / polythiol crosslinked polymer), No. 5-208950 (polyisothiocyanate, crosslinkable polymer of polyisocyanate and polymercapto compound), and No. 8-208795 (polyisocyanate, polyisocyanate) A cross-linked polymer of thioisocyanate and a polymercapto compound) or No. 10-319201 (cross-linked polymer of polyisocyanate isocyanate and polyol or polythiol) as a high refractive index optical material Although there is a description, in the case of a crosslinkable polymer, injection molding cannot be performed, and its use is limited.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high refractive index having excellent optical performance such as high refractive index, excellent transparency, small optical anisotropy, heat resistance and the like. Another object of the present invention is to provide a resin composition having a low birefringence and an optical element using the resin composition having a high refractive index and a low birefringence, in particular, an optical aspherical lens. Is to do.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have developed a resin composition having a high refractive index, excellent melt moldability, low optical anisotropy, transparency and heat resistance. As a result of diligent research on optical lenses using the product, a polymer having a structure in which the ratio of aromatics is high and the molecular orientation is difficult to be formed during molding by polymerizing a fluorene compound having a large steric hindrance was found. Since the polymer has a sulfur atom in the molecule, it is possible to obtain a polymer having a higher refractive index and a lower birefringence and an improved heat resistance, thereby achieving the object of the present invention. .

The present invention has the following configuration.

(1) A fluorene compound represented by the following general formula (I) and a polyisothiocyanate compound, a polyisocyanate compound, a polyacyl chloride compound, a polydithioacyl compound, a polysulfonyl chloride compound,
A resin composition containing a polycondensation or polyaddition polymer having at least one sulfur atom in a repeating unit with at least one compound selected from a phosgene compound and a thiophosgene compound.

[0009]

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Wherein X and Y are -O-, -S-, -NH-
Or -NR'-, X and Y may be the same or different, R 'is an alkyl group, R is a divalent linking group, m is 0 or 1, and X is a bond at any position of the benzene ring. Have been. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 each} represent a hydrogen atom, a halogen atom, a sulfur atom-containing group,
Represents any of an alkyl group, an aryl group, a nitro group, a cyano group, and a carboxyl group, each of which may be the same group or different groups; and R ¹ , R ² , R ³ , R ⁴ , R
⁵ , R ⁶ , R ⁷ and R ⁸ represent any of a hydrogen atom, a halogen atom, a sulfur atom-containing group, an alkyl group, an aryl group, a nitro group, a cyano group, and a carboxyl group, even if each is the same group. It may be another group.

(2) The resin composition according to (1), wherein the polycondensation or polyaddition polymer is a linear polymer.

(3) The resin composition according to (1) or (2), wherein X is bonded to each of the 4 'positions of two benzene rings.

(4) The resin composition according to any one of (1) to (3), wherein R is an alkylene group having 2 to 4 carbon atoms.

(5) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
Any of R ₇ and R ₈ is a halogen atom, an alkylthio group,
The resin composition according to any one of (1) to (4), which is at least one group selected from an arylthio group and an oxycarbonyloxyalkylthio group.

(6) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
The resin composition according to (5), wherein any one of R ₇ and R ₈ is bonded to the 3′-position or 5′-position of two benzene rings.

(7) Fluorene compounds having a condensed ring represented by the following formula (II) and polyisothiocyanate compounds, polyisocyanate compounds, polyacyl chloride compounds, polyacyl ester compounds, polythioacyl compounds, polysulfonyl chlorides A resin composition mainly containing a polycondensation or polyaddition polymer with at least one reactive compound selected from a compound, a phosgene compound and a thiophosgene compound.

[0017]

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In the formula, L and M each represent a condensed ring;
And Y are -O-, -S-, -NH- or -NR'-,
X and Y may be the same or different, R 'is an alkyl group, R is a divalent linking group, m is 0 or 1, and X is bonded to any position of the condensed ring. Also, (R _a ) _n is R
₁ , R ₂ , R ₃ , R ₄ , R ₅ ,... R _n represent a plurality of substituents bonded to the substituted positions of the condensed ring, and when the number of benzene rings constituting the condensed ring is c, n Is 2 (c + 2),
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,..., R _n represent any one of a hydrogen atom, a halogen atom, a sulfur atom-containing group, an alkyl group, an aryl group, a nitro group, a cyano group, and a carboxyl group. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom, a halogen atom, a sulfur atom-containing group, an alkyl group,
Represents an aryl group, a nitro group, a cyano group, or a carboxyl group, each of which may be the same or different.

(8) The resin composition according to (7), wherein the polycondensation or polyaddition polymer is a linear polymer.

(9) The resin composition according to (7) or (8), wherein R is an alkylene group having 2 to 4 carbon atoms.

(10) Any one of (R _a ) _n is at least one group selected from a halogen atom, an alkylthio group, an arylthio group and an oxycarbonyloxyalkylthio group (7) to (9). The resin composition according to any one of the above.

(11) Any one of (1) to (10)
An optical element formed by injection-molding the resin composition according to the above item.

(12) Any one of (1) to (10)
An optical aspherical lens formed by injection-molding the resin composition described in the above section.

Hereinafter, the present invention will be described in detail.

Here, the numbering of carbon substituent positions of the fluorene compound will be described. In the fluorene ring, as shown below, the methylene connecting the two benzene rings is at the 9-position, and any of the substituent positions of the two benzene rings of the fluorene compound bonded to the 9-position of the fluorene ring of the general formula (I) is Represented as 1 ', 2', 3 ', 4', 5 'and 6' positions. When the condensed ring bonded to the 9-position of the fluorene ring of the general formula (II) is a naphthalene ring, 1 ′,
2 ', 3', 4 ', 5', 6 ', 7' and 8 'positions;
When the fused ring is an anthracene ring, 1 ′, 2 ′,
3 ', 4', 5 ', 6', 7 ', 8', 9 'and 10'
Rank.

[0026]

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The polycondensation or polyaddition polymer having a fluorene compound represented by the above general formula (I) of the present invention has at least one sulfur atom in the repeating unit of the polymer, and has a repeating unit having the sulfur atom. It is preferable to have 10 mol% or more of units. The presence of a fluorene ring and a sulfur atom further develops heat resistance, a high refractive index, and low birefringence.

The resin composition of the present invention contains the above-mentioned polycondensation or polyaddition polymer, and preferably contains the polycondensation or polyaddition polymer in an amount of 50% by weight or more.

The polycondensation or polyaddition polymer of the present invention may be a linear polymer or a crosslinked polymer, but a linear polymer having moldability is preferred.

The polycondensation or polyaddition polymer of the present invention comprises a fluorene compound represented by the above general formula (I) and a polyisothiocyanate compound, a polyisocyanate compound, a polyacyl chloride compound, a polythioacyl compound, a phosgene compound, It is a polymer with at least one reactive compound selected from thiophosgene compounds. These reactive compounds may be used in combination of two or more.

In the general formula (I), the fluorene ring 9
In the two benzene rings bonded to the position, a terminal -XH (when m is 0) or -YH
(Where m is 1), which is a hydroxyl group, a mercapto group or an amino group or an imino group, and has at least one bond (two or more per one fluorene compound) on each of two benzene rings. are doing. X may be bonded to any position of the benzene ring, but is preferably bonded to the 4'-position. When m is 1, X (-O directly bonded to the benzene ring as shown in the above general formula (I)
-, -S-, -NH- or -NR'-) through -Y
R linked to H is not particularly limited as a substituent, but may be any divalent linking group such as an alkylene group, an arylene group, or an aralkylene group. To 8 alkylene groups are preferable, and alkylene having 2 to 4 carbon atoms is particularly preferable. This alkylene may be linear or branched.

In the general formula (I), the fluorene ring 9
R ₁ bonded to the two benzene rings bonded to the
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are not particularly limited as substituents, but include a hydrogen atom, a halogen atom, a sulfur atom-containing group, an alkyl group, an aryl group, and a nitro group. , A cyano group or a carboxyl group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a bromine atom or an iodine atom is preferable. Examples of the sulfur atom-containing group include an alkylthio group (methylthio group, ethylthio group, butylthio group, etc.), an arylthio group (phenylthio group, naphthylthio group, etc.), a heterocyclic thio group (oxazolethio group, thiazolethio group, etc.), an alkylsulfinyl group (Methylsulfinyl group, ethylsulfinyl group, etc.), arylsulfinyl group (phenylsulfinyl group, substituted phenylsulfinyl group, naphthylsulfinyl group, etc.) heterocyclic sulfinyl group (oxazolesulfinyl group, thiazolesulfinyl group, etc.), alkylsulfonyl group (methylsulfonyl) Group, ethylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, substituted phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfonamide group (methylsulfonamide group, Phenylsulfonamide group, substituted phenylsulfonamide group, naphthylenesulfonamide group, etc., heterocyclic sulfonamide group (oxazolesulfonamide group, thiazolesulfonamide group, etc.), oxy Carbonyloxyalkylthio group (oxycarbonyloxyethylthio group, oxycarbonyloxybutyl group, etc.), alkylaminosulfonyl group (methylaminosulfonyl group, propylaminosulfonyl group, etc.), arylaminosulfonyl group (phenylaminosulfonyl group, substituted phenylamino Sulfonyl group,
Naphthylaminosulfonyl group, etc.). The aralkyl group and the substituted alkyl group may be a straight-chain or branched alkyl group. Of these, an alkylthio group, an arylthio group and an oxycarbonyloxyalkylthio group are preferred. Examples of the alkylaminocarbonyl group (for example, ethylaminocarbonyl group), oxycarbonylalkyl group (for example, oxycarbonylmethyl group), and arylaminocarbonyl group include substituted and unsubstituted phenyl groups and aminocarbonyl groups of naphthyl group. Can be mentioned. In the present invention, among the above substituents, a halogen atom, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, It preferably has at least one group selected from an alkylsulfonamide group, an arylsulfonamide group, a heterocyclic sulfonamide group, an oxycarbonyloxyalkylthio group, an alkylaminosulfonyl group, and an arylaminosulfonyl group. It is particularly preferable to have at least one group selected from an atom, an alkylthio group, an arylthio group and an oxycarbonyloxyalkylthio group. R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be the same or different groups, and each may be the 2′-position or 3′-position of the benzene ring. Position, 4 'position, 5' position or 6 '
As long as it is attached to any of the
It is more preferable that the compound is bonded at the position (or 5 'position), and the refractive index can be further increased by introducing these. Also, R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituents of a fluorene ring, and the types of the substituents are R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
Same as R ₆ , R ₇ and R ₈ , but the type may be the same or different. Further, in the present invention, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ other than the above-mentioned halogen atom or sulfur atom-containing group, and R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are not particularly limited as substituents, but include a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a nitro group and a cyano group as described above. Etc. are bonded, and these may be the same or different.

In the general formula (II) of the present invention, L and M each have a condensed ring bonded to the 9-position of the fluorene ring, and the condensed ring includes a naphthalene ring, an anthracene ring, and a benzoanthracene ring. And a phenanthrene ring, a fluorene ring, a pyrene ring and the like, and a naphthalene ring and an anthracene ring are preferred.

The substituent of the fluorene compound having a condensed ring according to the present invention may have a terminal -XH (when m is 0) or -YH (when m is 1) as a reactive group. One mercapto group, an amino group, or an imino group is added to each condensed ring (two per fluorene compound).
X) may be bonded to each other, and X may be bonded to any position of the condensed ring. (R _a ) _n represents a substituent bonded to the bonding position of the condensed ring other than X, and n is 2 (c + 2), where c is the number of benzene rings constituting the condensed ring;
(R _{a) n} is _{R1, R2, R3, R 4} , R 5, ··· R
_{n represents} a hydrogen atom, a halogen atom, a sulfur atom-containing group, an alkyl group, an aryl group, a nitro group, a cyano group, or a carboxyl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷
And R ⁸ represent a hydrogen atom, a halogen atom, a sulfur atom-containing group, an alkyl group, an aryl group, a nitro group, a cyano group, or a carboxyl group, each of which may be the same or different. The substituents other than X are the same as those described in detail in formula (I).

The synthesis examples of the fluorene compound useful in the present invention are shown below.

[Synthesis of fluorene compound] [Synthesis of 9,9-bis {3'-bromo-4 '-(2 "-hydroxyethoxy) phenyl} fluorene] 9,9-
Bis {4 '-(2 "-hydroxyethoxy) phenyl}
Fluorene (BPEF, manufactured by Osaka Gas Chemical Co., Ltd.) 4
39 g was dissolved in 5000 ml of chloroform, and this solution was cooled on ice to obtain a solution at about 5 ° C. To this, 360 g of N-bromosuccinimide was added little by little (so that the temperature of the reaction solution did not exceed 15 ° C.), and after adding the whole amount, the mixture was stirred at room temperature for 3 hours. The reaction solution was transferred to a separating funnel, washed three times with 1000 ml of water, and the obtained organic layer was dried over anhydrous magnesium sulfate. The solution was concentrated to dryness, and the obtained solid was recrystallized from ethanol to give 9.9 of white crystals.
511 g of -bis {3'-bromo-4 '-(2 "-hydroxyethoxy) phenyl} was obtained in a yield of 86%, and the structure was determined by ¹ H NMR spectrum, IR spectrum and FD-mass spectrum. Identified.

[9,9-bis {3'-bromo-4'-
(2 ″ -Hydroxyethylthio) phenyl） fluorene synthesis] 300 g of 9,9-bis (3′-bromo-4′-mercaptophenyl) fluorene was dissolved in 1500 ml of dimethylsulfoxide (hereinafter abbreviated as DMSO), and 38 ml of triethylamine was dissolved. Was added, and the solution was heated to reflux.80 g of ethylene oxide was added to DMSO100
The solution dissolved in ml was added dropwise over 30 minutes,
Heat at 00 ° C. for 6 hours. The reaction solution was transferred to a separating funnel, washed three times with 2000 ml of water, and the obtained organic layer was dried over anhydrous magnesium sulfate. After the inorganic salt was filtered, the solution was concentrated to dryness and recrystallized from a mixed solution of toluene and tetrahydrofuran to give 9,9-bis {3'-bromo-4 '-(2 "-hydroxyethylthio) as a white solid. ) 264 g of phenyl difluorene was obtained with a yield of 72
%Met. The structure is ¹ H NMR spectrum, IR
Spectrum and FD-mass spectrum.

[9,9-bis {3'-phenylthio-
Synthesis of 4 ′-(2 ″ -hydroxyethoxy) phenyl} fluorene] Benzenethiol 1 in 300 ml of DMSO
The solution in which 19.0 g was dissolved was cooled in a water bath, and into this solution was added sodium ethoxide in 200 ml of DMSO.
A solution in which 0 g was dissolved was dropped in 30 powders. Next, 300 g of 9,9-bis {3′-bromo-4 ′-(2 ″ -hydroxyethoxy) phenyl} fluorene was added to DM
In 30 minutes, the solution was added dropwise to a solution dissolved in 1500 ml of SO.
Heat at 00 ° C. for 5 hours. The reaction solution was transferred to a separating funnel, and after three lines with 2000 ml of water, the obtained organic layer was dried over anhydrous magnesium sulfate. After filtration of the inorganic salt, the solution was concentrated, and the solution was concentrated and recrystallized with a mixture of toluene and tetrahydrofuran to give 9,9-bis {3′-phenylthio-4 ′-(2 ″ -hydroxyethoxy) phenyl} as a white solid. 241.1 g of fluorene was obtained with a yield of 82%, and the structure was identified by ¹ H NMR spectrum, IR spectrum, and FD-mass spectrum.

[9,9-bis [2 '-{6'-(2 "-
Synthesis of mercaptoethoxy) naphthalene}] fluorene] 300 g of 9,9-bis {2 ′-(6′-hydroxynaphthalene)} fluorene was dissolved in 1500 ml of DMSO, 47 ml of triethylamine was added, and the solution was heated to reflux. Here, a solution in which 96.8 g of ethylene sulfide was dissolved in 100 ml of DMSO was added dropwise over 30 minutes.
After adding the whole amount, the mixture was heated at 100 ° C. for 6 hours. The reaction solution was transferred to a separating funnel, washed three times with 2000 ml of water, and the obtained organic layer was dried over anhydrous magnesium sulfate. After the inorganic salts were filtered, the solution was concentrated to dryness and recrystallized from toluene-tetrahydrofuran to give 9,9 as a white solid.
325.0 g of 9-bis {2 '-(6'-hydroxynaphthalene)} fluorene was obtained, and the yield was 85%. The structure is ¹ HNMR spectrum, IR spectrum, F
It was identified by D-mass spectrum.

Examples of the fluorene compound used in the present invention are shown below, but are not limited thereto.

Examples of the fluorene compounds represented by the general formulas (I) and (II) include 9,9-bis (4'-hydroxyphenyl) fluorene and 9,9-bis (4'-hydroxy-3'-). Methylphenyl) -fluorene, 9,9
-Bis (4'-hydroxy-3'-ethylphenyl)-
Fluorene, 9,9-bis (4'-hydroxy-3'-
Propylphenyl) -fluorene, 9,9-bis (4-
Hydroxy-3'-methyl-5'-ethylphenyl) fluorene, 9,9-bis (4'-hydroxy-3 ',
5'-dimethylphenyl) fluorene, 9,9-bis (4'-hydroxy-3 ', 5'-diethylphenyl)
Fluorene, 9,9-bis (3'-hydroxyphenyl) fluorene, 9,9-bis (3-hydroxy-4 '
-Methylphenyl) fluorene, 9,9-bis (3-hydroxy-4'-ethylphenyl) fluorene, 9,9
-Bis (3'-hydroxy-4'-propylphenyl)
Fluorene, 9,9-bis (3-hydroxy-4'-methyl-5'-ethylphenyl) fluorene, 9,9-bis (3'-hydroxy-4 ', 5'-dimethylphenyl) fluorene, 9,9 -Bis (3-hydroxy-
4 ', 5'-diethylphenyl) fluorene, 9-
(4'-hydroxyphenyl) -9- (4'-hydroxymethoxyphenyl) fluorene, 9- (4'-hydroxyphenyl) -9- (4'-hydroxyethoxyphenyl) fluorene, 9- (4'-hydroxyphenyl )
-9- (4'-hydroxyprotoxyphenyl) fluorene, 9- {4 '-(2 "-hydroxyethoxy) phenyl} -9- {4'-(3" -hydroxyprotoxy)
Phenyl {fluorene, 9,9-bis} 4 '-(2 "-
(Hydroxyethoxy) phenyl} fluorene, 9,9-
Bis {4 ′-(2 ″ -hydroxyethoxy) -3′-methylphenyl} fluorene, 9,9-bis {4′-
(2 "-hydroxyethoxy) -3 ', 5'-dimethylphenyl fluorene, 9,9-bis {4'-(2"-
(Hydroxyethoxy) -3′-ethylphenyl} fluorene, 9,9-bis {4 ′-(2 ″ -hydroxyethoxy) -3 ′, 5′-diethylphenyl} fluorene,
9,9-bis {4 '-(2 "-hydroxyethoxy)-
3'-propylphenyl {fluorene, 9,9-bis {4 '-(2 "-hydroxyethoxy) -3', 5'-
Dipropylphenyl fluorene, 9,9-bis 4 '
-(2 "-hydroxyethoxy) -3'-isopropylphenyl {fluorene, 9,9-bis {4 '-(2"-
(Hydroxyethoxy) -3 ', 5'-diisopropylphenyl {fluorene, 9,9-bis {4'-(2 "-hydroxyethoxy) -3 '-(n) butyl-phenyl}
Fluorene, 9,9-bis {4 '-(2 "-hydroxyethoxy) -3', 5'-di- (n) butylphenyl}
Fluorene, 9,9-bis {4 '-(2 "-hydroxyethoxy) -3'-isobutylphenyl} fluorene,
9,9-bis {4 '-(2 "-hydroxyethoxy)-
3 ', 5'-diisobutylphenyldifluorene, 9,
9-bis {4 '-(2 "-hydroxyethoxy) -3'
-(1 "-methylpropyl) phenyl @ fluorene,
9,9-bis {4 '-(2 "-hydroxyethoxy)-
3 ', 5'-bis (1 "-methylpropyl) phenyl
Fluorene, 9,9-bis {4 '-(2 "-hydroxyethoxy) -3'-phenyl-phenyl} fluorene,
9,9-bis {4 '-(2 "-hydroxyethoxy)-
3 ', 5'-diphenyl-phenyldifluorene, 9,
9-bis {4 '-(2 "-hydroxyethoxy) -3'
-Benzylphenyl {fluorene, 9,9-bis} 4 '
-(2 "-hydroxyethoxy) -3 ', 5'-dibenzylphenyl {fluorene, 9,9-bis {4'-
(3 "-hydroxypropoxy) -3'-phenyl} fluorene, 9,9-bis {4 '-(4" -hydroxybutoxy) -3'-phenyl} fluorene and

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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Examples are, but not limited to, these.

In the synthesis of the fluorene oxyethoxy compound used in the present invention, when ethylene oxide is added to phenolic -OH, one impurity is added to one -OH as an impurity remaining in the synthesis or purification process. In addition to the addition of ethylene oxide, the addition of two or more ethylene oxides is produced, but the addition of one ethylene oxide is 85 mol% or more, preferably 95 mol% or more. The same applies to the case where ethylene sulfide is added to phenolic -OH and ethylene oxide or ethylene sulfide is added to thiophenolic -SH.

The polythiocyanate compound used in the present invention includes 1,2-ethylenedithiocyanate,
3-propylene dithiocyanate, 1,4-butylene dithiocyanate, 1,5-pentyl dithiocyanate,
1,6-hexyldithiocyanate, 1,7-heptyldithiocyanate, 1,8-octyldithiocyanate, p-phenylenedithiocyanate, m-phenylenedithiocyanate, 2,4-toluyldithiocyanate, m-xylylene-2,5-dithiocyanate, 1,
4-naphthylene dithiocyanate, 2-6-naphthylene dithiocyanate, p-dimethylphenylene dithiocyanate, cyclohexylene dithiocyanate, p-phenylene diisopropylidene dithiocyanate, 4,4 '
-Dithiocyanato benzophenone, diphenyl ether-4,4'-dithiocyanate, diphenylamine-
4,4'-dithiocyanate, diphenyl sulfide-
4,4'-dithiocyanate, 2,4,6-triisothiocyanate-1,3,5-triazine, thiobis (3
-Isothiocyanatopropane), thiobis (2-isothiocyanatoethane), 1-isothiocyanato-4
-{(2-isothiocyanato) sulfonyl} benzene, thiobis (4-isothiocyanatobenzene) and the like,
Examples of the polyisocyanate compound include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butylene diisocyanate, 1,5-pentyl diisocyanate, and 1,6-hexyl diisocyanate. Nate, 1,7-heptyl diisocyanate, 1,8-octyl diisocyanate, p-phenylene diisocyanate, 1,4-naphthylene diisocyanate, 2,6-
Naphthylene diisocyanate, p-dimethylphenylene diisocyanate, cyclohexylene diisocyanate, p-phenylene diisopropylidene diisocyanate, 4,4'-diisocyanato benzophenone, diphenyl ether-4,4'-diisocyanate, Diphenylamine-4,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 2,4,6
-Triisocyanate-1,3,5-triazine, thiobis (3-isocyanatopropane), thiobis (2-
Isocyanatoethane), 1-isocyanato-4-
Examples of polyacyl chloride compounds such as {(2-isocyanato) sulfonyl} benzene and thiobis (4-isocyanatobenzene) include succinic dichloride, glutaric dichloride, adipic dichloride, pimelic dichloride, suberic dichloride, and azelaic acid. Dichloride, sebacic dichloride, terephthalic dichloride,
Examples of dithioacyl compounds such as phthalic acid dichloride and naphthalenedicarboxylic acid include ethylenedithioic acid dichloride, butylenethioic acid dichloride, trimesic acid trichloride, and pyromellitic acid tetrachloride. Examples of the phosgene compound include phosgene, ethylene bischloroformate, p-phenylenediisopropylidenebischloroformate, and the like, and examples of thiophosgene include thiophosgene, ethylene bischlorothioester, and the like. It is not limited. The said compound can use a commercial item.

The process for producing the linear polycondensation or polyaddition polymer of the general formulas (I) and (II) useful in the present invention is carried out by a conventional diisocyanate compound, dithioisocyanate compound, acid chloride compound, phosgene And the like, a solution reaction or an interfacial reaction, a two-phase reaction in the presence of a phase transfer catalyst, or the like. As the surfactant, any of quaternary ammonium salts, phosphonium salts, crown ethers and the like may be used or used in combination.

A method for producing a polymer by performing a polycondensation or polyaddition reaction using the fluorene compound and the reactive compound will be described below with some examples.

[Production of polymer by polycondensation or polyaddition reaction] [Production of P-1 by polythiourethane polyaddition reaction]
65.3 g of 9,9-bis {3'-bromo-4 '-(2 "-hydroxyethoxy) phenyl} fluorene and p-
19.2 g of phenylenediisothiocyanate in 500 m
of ethyl acetate, and 3.0 g of p-toluenesulfonic acid was further added as a catalyst, and the mixture was refluxed under heating for 5 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate, transferred to a separating funnel, and washed with water 3
After washing three times with 00 ml, the obtained organic layer was dried over anhydrous magnesium sulfate. This solution was concentrated to dryness to obtain 62.0 g of colorless polythiourethane P-1. The yield was 98%.

[P- by polythiourethane polyaddition reaction
Production of 2,9] -bis {3'-bromo-4 '-(2 "
-Mercaptoethylthio) phenyl @ fluorene in 7
2.7 g and p-phenylenediisothiocyanate in 1
9.2 g was dissolved in 500 ml of ethyl acetate, and 3.0 g of p-toluenesulfonic acid was further added as a catalyst, and the mixture was heated under reflux for 5 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate, transferred to a separating funnel and washed three times with 300 ml of water, and the obtained organic layer was dried over anhydrous magnesium sulfate. The solution was concentrated to dryness, and 8 parts of colorless polythiourethane P-2 was added.
3.6 g were obtained. The yield was 91%.

[P- by polythioester polycondensation reaction
Preparation of 3] 595 ml of dehydrated pyridine was added to 4000 ml of dehydrated tetrahydrofuran, and the solution was cooled in an ice bath. 1000 ml of dehydrated tetrahydrofuran into this solution
Then, 300 g of terephthalic acid chloride dissolved in the above was added dropwise.
To this solution, 978 g of 9,9-bis {3'-bromo-4 '-(2 "-hydroxyethylthio) phenyl} fluorene dissolved in 1000 ml of dehydrated tetrahydrofuran was added, and the mixture was heated under reflux for 8 hours. The hydrochloride was collected by filtration, tetrahydrofuran was removed under reduced pressure, the obtained residue was dissolved in chloroform, and reprecipitated by slowly dropping it into methanol, and the obtained solid was collected by filtration, dried and dried to obtain 949 g. Polythioester P-3 was obtained.
The yield was 81%.

[Production of P-4 by polythiocarbonate polycondensation reaction] 9,9-bis {3'-phenylthio-
500 g of 4 '-(2 "-hydroxyethylthio) phenyl fluorene and 152 g of sodium hydroxide and 17 g of benzyltriethylammonium chloride dissolved in 2000 ml of water are added to 1500 ml of methylene chloride, and 500 ml of methylene chloride is added to this solution.
A solution in which 268 g of bischloroformate was dissolved was added dropwise. After the reaction solution was stirred at room temperature for 2 hours, the separated organic layer was washed with 2,000 ml of 10% hydrochloric acid, and then 2,000 ml of water.
Washed twice with ml. The methylene chloride solution was poured into methanol, and the precipitated polymer was filtered, washed with methanol, and dried at 60 ° C. under reduced pressure to obtain 580 g of polythiocarbonate P-4. The yield was 88%.

[Production of P-5 by polydithiocarbonate polycondensation reaction] 9,9-bis {3'-methylthio-
500 g of 4 '-(2 "-mercaptoethoxy) phenyl fluorene, 137 g of sodium hydroxide and 17 g of benzyltriethylammonium chloride dissolved in 2000 ml of water are added to 1500 ml of methylene chloride, and 113 g of phosgene is added to 500 ml of methylene chloride. After the reaction solution was stirred at 20 ° C. for 2 hours, the separated organic layer was separated into 2000 ml of 10% hydrochloric acid.
, And then twice with 2000 ml of water. The methylene chloride solution was poured into methanol, and the precipitated polymer was filtered, washed with methanol, and dried at 60 ° C. under reduced pressure to obtain 521 g of polydithiocarbonate P-5. The yield was 85%.

[Production of P-6 by polytrithiocarbonate polycondensation reaction] 9,9-bis {3'-bromo-4 '
500 g of-(2 "-mercaptoethoxy) phenyl difluorene and 64.7 g of tetrabutylammonium bromide dissolved in 3400 ml of 1 mol of sodium hydroxide were added to 2800 ml of methylene chloride, and 97 g of thiophosgene dissolved in 500 ml of methylene chloride were added dropwise. .
After the reaction solution was stirred at 20 ° C. for 3 hours, the separated organic layer was poured into methanol, and the precipitated polymer was filtered, washed with methanol, dried at 40 ° C. under reduced pressure, and dried over polytrithiocarbonate P-6. 416 g was obtained. Yield 8
5%.

[Production of P-7 by polythioisocyanate polyaddition reaction] 3,6-dimethylthio-9,9-
A solution prepared by dissolving 66.5 g of tetramethylene diisocyanate in 440 ml of anhydrous anisole while cooling with ice and stirring with a solution of 300 g of {4 '-(2 "-mercaptoethylthio) phenyl} fluorene and 130 ml of anhydrous anisole. Is added from the dropping funnel over 30 minutes After the addition is completed, the mixture is heated on an oil bath at 60 to 70 ° C. for 30 minutes, and the remaining 5% diisocyanate solution is added, and the temperature of the oil bath is increased. The mixture was allowed to react for 3.5 hours while stirring at 150 ° C. The contents were poured into a vessel with a wide rim, filtered, and thoroughly washed with alcohol. After drying under reduced pressure, colorless polythioisocyanate P
326 g of -7 were obtained. The yield was 88%.

[Production of P-8 by polythiocarbonate polycondensation reaction] 322 g of 9,9-bis {3'-methyl-4'-hydroxyphenyl} fluorene and 354 g of bisphenol A bischloroformate were added to P-4. The organic layer separated by polycondensation in the same manner as in
, And then twice with 2000 ml of water. The methylene chloride solution was poured into methanol, and the precipitated polymer was filtered, washed with methanol, and dried at 60 ° C. under reduced pressure to obtain 530 g of polythiocarbonate P-8.
The yield was 88%.

[P- by polythioester polycondensation reaction
Production of 9] 9,9-bis {4'-hydroxyphenyl}
294 g of fluorene and thioterephthalic dichloride 23
5 g was reacted and purified in the same manner as for P-3 to obtain 355 g of polythioester P-9. The yield was 48%.

Since P-10 to P-18 can be produced in the same manner, the polycondensation or polyaddition reaction method is omitted. Here, n represents a polymer, and n ₁ and n ₂ represent weight ratios.

For the production (polycondensation or polyaddition) method, reference can be made to “Experimental Method for Polymer Synthesis” (1996), published by Kagaku Dojin, co-authored by Takayuki Otsu and Masayoshi Kinoshita.

Examples of the polycondensation or polyaddition linear polymer from the fluorene compound and the reactive compound of the present invention are shown below.
Although described as 1 to 18, it is not limited to these.

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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The resin composition of the present invention may contain other resins, antioxidants, and slipping agents according to the purpose of molding the above-mentioned polycondensation or polyaddition polymer of the present invention, as long as the effects of the present invention are not impaired. , A heat-resistant agent, an ultraviolet absorber, a pigment, an antistatic agent, and the like.

Other resins which can be mixed and used in the present invention may have any refractive index, but preferably have a high refractive index or low birefringence as much as possible, and include polyesters and polycarbonates having an aromatic ring. , Polyurethane, polythiourethane, polyether sulfone, polyphenylene ether, polynorbornene resin, polyphenylene sulfide, polyester of a hydroxyl group-containing fluorene compound and dicarboxylic acid, and copolycondensation carbonate of a hydroxyl group-containing fluorene compound with phosgene and bisphenol A, etc. May be appropriately mixed. In this case, those having similar melting points and fluidity to the polycondensation or polyaddition polymer of the present invention are preferable.

It is preferable to add an antioxidant in order to prevent oxidation, thermal deterioration and thermal decomposition in melting and molding the resin composition of the present invention. As the antioxidant, any antioxidant that can impart heat resistance can be used without limitation. An example is shown below.

AON-1: Irganox 1010 (Ciba-Geigy) AON-2: Etanox (Ethyl Corporation) AON-3: Tinuvin 770 (Ciba-Geigy) AON-4: Irgafos (Ciba-Geigy) AON-5: DLTDP: (American Cyanamide) AON-6: Naugard XLI (Uniroyal)
Chemicals) AON-7: Irganox MD 1024 (Ciba
Geigy)

[0082]

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[0083]

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A polycondensation or polyaddition polymer is prepared by mixing the above-mentioned additive, for example, an antioxidant with the above-mentioned polycondensation or polyaddition polymer of the present invention. Depending on the molding temperature, the composition may be molded with 100% polycondensation or polyaddition polymer, but it may be preferable to add an antioxidant. When an antioxidant is contained, the amount of the antioxidant is 0.01 to 10% by weight, preferably 0.1 to 5%, based on the weight of the polycondensation or polyaddition polymer.
More preferably, it is 0.5 to 3%.

The method for preparing the resin composition of the present invention can be used without any limitation as long as it can be uniformly mixed. For example, a simple solid (powder) mixer may be used. In order to form the polycondensation or polyaddition polymer of the present invention in a stable state later, it is preferable to avoid unnecessary heating, sufficiently dry the mixture, and introduce the mixture into a mixer. Examples of the mixer include a ribbon type, a helical type, a paddle type, a screw type and the like. During drying or mixing, it is preferable to remove air as much as possible and to always fill the space with an inert gas such as nitrogen gas. Further, the composition of the present invention may be supplied to a molding machine in the form of a powder, but it is preferable that the composition of the present invention is once solidified into pellets. Further, a dryer capable of reducing the pressure to a vacuum or reduced pressure is more preferable. Pelletization may be performed by melting the composition into pellets or by solidifying the composition like tablets. In any case, it is important that the composition of the present invention is not changed (does not cause deterioration, discoloration, oxidation, decomposition, etc.).

The optical elements to which the resin composition of the present invention is suitable include, for example, microscopes, spectacles, telescopes, cameras, V
Optical lenses such as TRs, backlight optical systems such as light guide plates and prism sheets, illumination optical systems such as projectors, optical disk substrates and pickup lenses such as CDs and DVDs, especially VTRs, or digital still cameras (DSCs), lens shutters Cameras, integrated cameras (film with lens), various cameras such as video cameras, CDs, CD-ROMs, CD-Rs, CD-RWs,
CD-Video, magneto-optical disk, DVD, DVD-
RAM, DVD-ROM, DVD-RW, DVD + R
High-performance optical lenses used in various devices such as optical pickup devices such as W and super audio, OA devices such as copiers and printers, and optical elements such as disk bases, prisms, and light guide plates, particularly, aspherical surfaces Performance suitable for the lens can be provided. These molded products are prepared by a method such as injection molding in which a resin is melted and injected into a mold, or, in the case of a thermosetting resin, a reactive compound, a reactive compound, a cross-linkable compound, etc. In a liquid state. The preferred method of the present invention is the former injection molding.

The optical lens using the resin composition of the present invention can be formed by a conventionally known molding method, for example, injection molding, injection compression molding, compression molding, vacuum molding, transfer molding, or the like.
It can be obtained by a method such as a blow molding method, an extrusion molding method, a pressure molding method, and a casting molding method. The injection compression molding method is preferable from the viewpoint of mass productivity. In the molding by the injection compression molding machine, a plastic lens with small optical distortion is obtained by appropriately selecting molding conditions such as resin temperature, mold temperature, and holding pressure (holding pressure). Can be easily obtained. The molding conditions, especially the molding temperature, vary depending on the resin composition, the degree of polymerization, and the like, and cannot be specified unconditionally. However, the resin temperature is about 150 ° C. higher than the glass transition temperature of each resin used.
The temperature is 350C, preferably 240-300C. The mold temperature is a glass transition temperature or a temperature 20 ° C lower than the glass transition temperature, preferably a temperature lower by 2 to 10 ° C, and specifically 100 to 250 ° C, preferably 120 to 230 ° C.

The precision of the molded plastic lens is represented by dimensional precision and surface characteristics. If these precisions are poor, optical distortion increases. However, since the resin composition of the present invention is non-crystalline, the transparency is low. It has excellent melt viscoelastic properties, so that it has excellent moldability, has little residual stress distortion and molecular orientation during molding, and has very little optical anisotropy.

In the injection molding, when the optical element shape is symmetrical with respect to the gate, which is a path for filling the molding cavity with the resin, the resin flow, the injection pressure and the holding pressure when the resin is filled through the gate. Since the stress and the like inside the resin due to these also occur symmetrically with respect to the gate, birefringence also occurs substantially symmetrically with respect to the gate when the optical element is viewed from the optical axis. This generally means that birefringence appears as astigmatism to optical performance.

The phase angle of birefringence of the optical lens made of the resin composition of the present invention is from -40 to + 40 °, preferably from -30 to + 30 °. Because the resin composition of the present invention can be configured with a gentle curvature on the optical surface for a high refractive index,
If the edge thickness of the lens is increased accordingly, it is possible to make the gate size slightly larger. The high refractive index of the resin of the present invention is 1.60 or more, preferably 1.65 or more, and more preferably 1.70 or more. Thus, the resin composition of the present invention is characterized by having a high refractive index and a low birefringence. Incidentally, the astigmatism of the aspheric lens made by the resin composition of the present invention is 0 to 15 mλ, preferably 0 to 15 mλ.
〜１０10 mλ.

Further, the resin composition of the present invention has a large MFR and good fluidity, and the shearing force applied to the gate at the time of filling can be made smaller than that of the conventional resin. Moreover, since it is a resin composition having a small optical anisotropy, it is possible to create an optical element superior to the conventional resin by individually performing an optical design according to each refractive index as described above. I can do it.

When the resin composition of the present invention is applied to an optical element, a raw material charging step, a polymerization step, a step of forming a polymer into pellets, a step of injection molding, a step of forming into a sheet or a film, and the like are performed. Care must be taken to prevent dust from entering, and a cleanness of class 10000 or less for ordinary high-performance optical lenses and a class 1000 or less for more sophisticated information recording is preferable.

When the polycondensation or polyaddition polymer of the present invention is a crosslinked polymer, optical products, lenses for spectacles, prisms and the like can be produced by ordinary cast polymerization. Specifically, a fluorene compound and a reactive compound are mixed, the mixed solution is defoamed by an appropriate method as necessary, and injected into a mold, and usually from a low temperature of about 0 to 50 ° C to 100 to 180 ° C. Polymerization is performed while gradually raising the temperature to a high temperature of about ° C. At this time, a known release treatment may be applied to the mold in order to facilitate the release property after the polymerization.

The linear polycondensation or polyaddition polymer of the present invention has a high refractive index and low birefringence, and is excellent in injection moldability, birefringence, heat resistance and transparency. It is useful as an optical element, and is particularly suitable for an aspherical lens. In addition, the crosslinked polymer can be used for optical products such as eyeglasses, for example, by charging it into a mold before polymerization and heating to perform crosslink polymerization.

Various coating layers may be provided on the surface of the optical lens of the present invention for various purposes. An antireflection layer can be provided to increase light transmittance. Further, a hard coat layer may be provided to prevent scratches on the surface of the plastic lens. The antireflection film may be a single layer or a multilayer film obtained by laminating thin films having different refractive indices, and may be an inorganic or organic material as long as the reflectance is reduced. . However, in order to emphasize the surface hardness and prevention of interference fringes, it is most preferable to provide a single-layer or multilayer antireflection film made of an inorganic substance. Examples of usable inorganic substances include oxides and fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, hafnium oxide, and magnesium fluoride. So-called PVD such as ion plating, vacuum deposition and sputtering
It can also be applied by a method. Preferred examples of the hard coat layer include those obtained by applying and curing a coating composition containing the following (a) and (b) as main components. (A) One or more silane compounds having at least one reactive group. (B) Composite using two or more of metal oxide fine particles such as silicon oxide, antimony oxide, zirconium oxide, tungsten oxide, tantalum oxide, aluminum oxide, titanium oxide, cerium oxide, zirconia, silicon oxide, and iron oxide At least one selected from metal oxide fine particles and composite metal fine particles coated with fine tin oxide with composite metal fine particles of tin oxide and tungsten oxide.
(B) is an effective component for adjusting the refractive index of the hard coat layer and increasing the hardness. The thickness of the hard coat layer is usually preferably about 0.2 to 10 μm. More preferably, it is about 1-3 μm.

[0096]

EXAMPLES The embodiments of the present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 Table 1 shows the resins obtained by the polycondensation or polyaddition polymerization of the present invention and the following comparative resins C-1 to 4 (polycondensation or polyaddition was carried out in the same manner as the resin of the present invention). And 99 parts by weight of an antioxidant and 1 part by weight of an antioxidant were mixed at a set temperature of 140 ° C. and under a nitrogen gas pressure, using a Banbury mixer (manufactured by Moriyama Co., Ltd.).
(MS-0.5 type), mixed at a constant rotation for 3 hours, and then pelletized with a pelletizer and cooled to prepare a resin composition. The resin composition pellets were dried with a vacuum dryer for 3 hours before use, and then exposed to air using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SH50) under the following conditions (a certain condition). Condition, refractive index n is 1.61
In the example), injection molding was performed on a 2 mm DVD double-sided aspherical pickup objective lens mold as a molded product. The schematic diagram of the lens is shown below. FIG. 1 is a side view of a double-sided aspherical pickup objective lens for DVD. In the figure, 1 is a double-sided aspherical pickup objective lens for DVD,
Reference numeral 2 denotes a disk for DVD, 3 denotes a surface on the aspherical surface of the double-sided aspherical pickup objective lens for DVD, a first surface and surface number 1, and 4 denotes a surface on the back surface and a second surface and surface number 2. . Also, in the figure, reference numeral 5 denotes a surface on the lens side of the transparent substrate of the DVD disk, which is designated as surface number 3, and surface 6 on the back side of the transparent substrate of the DVD disk is designated as surface number 4. Further, in the figure, 7 represents an optical axis, and 8 represents incident light.

[0098]

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(Conditions) Resin temperature (° C.): 240 to 260 (glass transition temperature of each resin + 150) Injection position (mm): S0: 14.0, S1: 12.0,
S2: 10.0, S3: 7.0, S4: 2.0 Injection speed (mm / sec): V0: 16, V1: 14, V
2: 6, V3: 8, V4: 6 Filling time (sec): 2.0 Holding pressure (Pa): 0.735 Holding pressure time (sec): 25 Measurement switching position (mm): S6: 12.0, S7: 20.
0, S8: 24.0 S9: 28.0 Measurement back pressure (%): P6: 4, P7: 5, P8: 5, P
9: 0 Metering rotation (rpm): r6: 24, r7: 12, r8:
10, r9: 1 Mold temperature (° C.): 135 to 165 (glass transition temperature of each resin −3) Molding cycle (second): 80 (numerical value of aspherical lens) Paraxial data Focal length f = 3.36 ( mm) Disk side numerical aperture NA 0.60 Magnification m = 0 Light source wavelength λ = 650 (nm) (reading laser) Surface number r (mm) d (mm) n (refractive index) 1 2.245 2.20 1 0.71 (n changes) 2 -14.817 1.73 1.00 3 ０．６ 0.60 1.58 4 ∞ Aspherical surface first surface K = −0.96963 A ₄ = 0.55344 × 10 ^{− 2} A ₆ = 0.28877 × 10 ⁻³ A ₈ = 0.10743 × 10 ⁻⁴ A ₁₀ = −0.10915 × 10 ⁻⁵ Second surface K = −24.8230 A ₄ = 0.98535 × 10 ^{− _{2 A 6 = -0.24617 × 10 -3}} A 8 = 0.370 Here _{^{5 × 10 -4 A 10 = -0.25736}} × 10 -5, d is interplanar distance between each surface and the surface, the d of the surface number 1 the distance between the surface numbers 1 and the 2, i.e. DVD The distance at the thickest point of the aspherical pickup lens, d of surface number 2 is the distance between surface numbers 2 and 3, that is, the distance between the second surface and the front side of the disk, and the air is between them. d is surface number 3
And the thickness of the transparent substrate of the same disk. r is the radius of curvature of each surface, and n is the refractive index of each surface. K, A _i is DVD
Coefficient X of the following aspheric shape equation of the aspheric pickup lens
Where K is a conic coefficient and A _i is an i-th order aspherical surface.

[0100]

(Equation 1)

[Measurement Method and Evaluation Method] The refractive index nd, optical anisotropy (birefringence phase angle), and total light transmittance of the optical lenses in the examples were measured by the following methods.

<Refractive Index> The refractive index of a measuring piece having a thickness of 3 mm and a diameter of 30 mm was measured using an Abbe refractometer (trade name: 2T, manufactured by Atago Co., Ltd.).

<Total light transmittance> Thickness 3 mm, diameter 30 m
The light transmittance of a 400-850 nm region of the measuring piece of m was measured with a visible ultraviolet spectrophotometer (Hitachi self-recording spectrophotometer).

<Optical Anisotropy> Thickness 3 mm, diameter 30 mm
Was prepared, and the phase difference (nm) was measured with an automatic birefringence measuring instrument (manufactured by Konica). (Shows the fluidity of the molten resin during molding.) <Evaluation of Appearance> Hold the lens over the light
0 pieces were placed in a transparent resin container, and transparency and coloring were observed. Evaluation is expressed in words.

The results of the evaluation are shown in Table 1 below.

[0106]

[Table 1]

(Results) As shown in FIG. 1, the double-sided aspherical pickup objective lens for DVD has a large difference in thickness between the central portion and the peripheral portion, and the gate size at the time of injection molding should not be small for the size of the lens. Must have a shape that is easy to generate birefringence by molding, but the resin composition of the present invention has high fluidity and low optical anisotropy, and is extremely good in fluidity in a thermoplastic state, An aspherical surface with excellent optical properties of high refractive index and low birefringence, with the packing pressure well transmitted to the end of the cavity after filling the resin into the cavity of the mold, without birefringence due to molecular orientation. I got a lens. Refractive index is also around 1.70 or 1.70
As described above, the refractive index is very high, and the birefringence is as small as +36 or less. In contrast, the comparative resin has a low high refractive index,
Moreover, the fluidity was poor and the value of birefringence was very large, which proved to be unsuitable as an optical lens, particularly an aspherical lens.

[0108]

The resin of the present invention has a refractive index of 1.60 or more. Most of the resins have a high refractive index of about 1.70 or more and have a small optical anisotropy. (Having a small birefringence), which is suitable for molding aspherical lenses and has high industrial value.

[Brief description of the drawings]

FIG. 1 is a side view of a double-sided aspherical pickup objective lens for DVD.

[Explanation of symbols]

 1 Double-sided aspherical pickup objective lens for DVD 2 Disc for DVD 7 Optical axis 8 Incident light

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G02B 1/04 G02B 1/04 3/02 3/02 F term (reference) 4J001 DA01 DA02 DB01 DC05 DC08 DC15 DD01 DD03 DD04 DD07 DD16 DD18 DD20 EB04 EB06 EB07 EB08 EB09 EB35 EB37 EB46 EC74 EE26D EE35E EE43D EE74D FB03 FC03 GA13 GA16 HA01 HA02 HA04 HA05 JA01 JA20 JB18 JB41 JB42 4J029 AA01 AA09 AB01 BG01B01 CB01 BA16 BA19 BA20 BA23 BA43 BA44 BA45 BB14 BB36 BC08 BC09 BF19 BG25 4J034 CA04 CA15 CA24 CA32 CB03 CC12 CC13 CC26 CC54 CC61 CC62 CC69 CD01 CD04 CD08 CD09 CD11 CD13 CD14 HA01 HA07 HB02 HC03 HC12 HC17 HC22 HC35 HC46 HC68 HC70 Q

Claims (12)

[Claims] 1. A fluorene compound represented by the following general formula (I) and a polyisothiocyanate compound, a polyisocyanate compound, a polyacyl chloride compound, a polydithioacyl compound, a polysulfonyl chloride compound, a phosgene compound and a thiophosgene compound. A resin composition containing a polycondensation or polyaddition polymer having at least one sulfur atom in a repeating unit with at least one selected compound. Embedded image Wherein X and Y are -O-, -S-, -NH- or -N
In R'-, X and Y may be the same or different, and R '
Is an alkyl group, R is a divalent linking group, m is 0 or 1, X
Is attached to any position of the benzene ring. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 each} represent a hydrogen atom, a halogen atom, a sulfur atom-containing group, an alkyl group, an aryl group, a nitro group, a cyano group, Represents any of carboxyl groups, each of which may be the same group or different groups, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ and R ⁸ represent any one of a hydrogen atom, a halogen atom, a sulfur atom-containing group, an alkyl group, an aryl group, a nitro group, a cyano group, and a carboxyl group. You may. 2. The resin composition according to claim 1, wherein the polycondensation or polyaddition polymer is a linear polymer. 3. X is 4 'of each of two benzene rings.
The resin composition according to claim 1, wherein the resin composition is bonded to a position. 4. The resin composition according to claim 1, wherein R is an alkylene group having 2 to 4 carbon atoms. 5. At _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is selected from a halogen atom, an alkylthio group, an arylthio group and an oxycarbonyloxyalkylthio group. The resin composition according to any one of claims 1 to 4, wherein the resin composition is one group. 6. Any one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 is} the 3′-position or 5 ′ of two benzene rings.
The resin composition according to claim 5, wherein the resin composition is bonded to a position. 7. A fluorene compound having a condensed ring represented by the following general formula (II) and a polyisothiocyanate compound, a polyisocyanate compound, a polyacyl chloride compound, a polyacyl ester compound, a polythioacyl compound, and a polysulfonyl chloride compound. A resin composition mainly containing a polycondensation or polyaddition polymer with at least one reactive compound selected from phosgene compounds and thiophosgene compounds. Embedded image In the formula, L and M each represent a condensed ring, and X and Y represent -O
-, -S-, -NH- or -NR'-, wherein X and Y may be the same or different, R 'is an alkyl group, and R is 2
A valent linking group, m is 0 or 1, and X is bonded to any position of the condensed ring. (R _a ) _n is R ₁ , R ₂ , R
₃ , R ₄ , R ₅ ,... R _n represent a plurality of substituents bonded to the substituted position of the condensed ring, and n is 2 (c + 2), where c is the number of benzene rings constituting the condensed ring. Yes, R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ ,..., R _n are a hydrogen atom, a halogen atom,
Sulfur atom-containing group, an alkyl group, an aryl group, a nitro group, a cyano group, represents one of a carboxyl group, R ^1,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent any one of a hydrogen atom, a halogen atom, a sulfur atom-containing group, an alkyl group, an aryl group, a nitro group, a cyano group, and a carboxyl group And each may be the same group or different groups. 8. The resin composition according to claim 7, wherein the polycondensation or polyaddition polymer is a linear polymer. 9. The resin composition according to claim 7, wherein R is an alkylene group having 2 to 4 carbon atoms. 10. The method according to claim 7, wherein any one of (R _a ) _n is at least one group selected from a halogen atom, an alkylthio group, an arylthio group and an oxycarbonyloxyalkylthio group. Item 2. The resin composition according to item 1. 11. An optical element formed by injection molding the resin composition according to claim 1. Description: 12. An optical aspherical lens formed by injection molding the resin composition according to claim 1. Description: