JP2734532B2 - High refractive index optical lens - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical high refractive index lens made of co-polycarbonate resin, such as a microscope, a camera, a telescope, an optical device such as a copying machine, and glasses. By using this lens as the lens, not only the lens system can be made compact and lightweight, but also there is an advantage that aberrations such as spherical surfaces can be reduced.

[Conventional method and its problems]

Generally, as a method of improving the refractive index of plastic,
There is known a method of introducing a phenyl group, halogen, sulfur or the like into a molecular structure. In the case of polycarbonate resin, a phenyl group on the side chain or aromatic ring of dihydric phenol,
By using a compound into which halogen is introduced, the refractive index increases, but the fluidity deteriorates, the moldability becomes poor, and it becomes difficult to mold a target lens.

Further, when a compound in which sulfur is introduced into the main chain of dihydric phenol is used, this homopolycarbonate resin has poor solubility in a solvent, and is difficult to produce by a solution method.

[Problems to be solved by the invention]

As described above, a polycarbonate resin which improves the refractive index of a conventional polycarbonate resin, has excellent fluidity, and can easily form a lens has not been found.

[Means for solving the problem]

The present inventors synthesized a copolymerized polycarbonate resin using at least one dihydric phenol having a phenyl group in the side chain and one or more dihydric phenols having a sulfur in the main chain and optionally having a halogen in an aromatic ring. By doing so, it was found that a co-polycarbonate resin having a high refractive index and excellent moldability was obtained, and based on this, the present invention was completed.

That is, the present invention relates to a co-product produced using a dihydric phenol compound represented by the following general formulas (1) and (2).
A high refractive index optical lens characterized by being molded from a polycarbonate resin, (R in the formula represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, A is, -S -, - SO -, - SO 2 - a, X represents a halogen atom, p, q are each The dihydric phenol represented by the general formula (1) is in the range of 10 to 95 mol% of the total dihydric phenol, and the co-polycarbonate resin has a viscosity average molecular weight of 13,000. When it is 〜25,000, an optical lens having a high refractive index can be produced more suitably.

 Hereinafter, the configuration of the present invention will be described.

The specific co-polycarbonate resin production method of the present invention is the same as the conventional polycarbonate resin production method except that the dihydric phenol compounds of the general formulas (1) and (2) are used. It is manufactured by a solution method such as the method.

That is, in the interfacial polymerization method, the above-mentioned general formulas (1) and (2)
By adding a dihydric phenol compound and a molecular weight regulator, and reacting these with phosgene. Get.
In the pyridine method, the dihydric phenolic compound and the molecular weight regulator (1) and (2) are dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is blown to obtain a co-polycarbonate resin directly. Is the way.

In the above method, the compound represented by the general formula (1) or (2)
Depending on the type of dihydric phenol and its usage ratio,
In some cases, the solubility of these compounds in an inert solvent is insufficient. In this case, in particular, the reaction of the dihydric phenol of the general formula (1) with phosgene is first carried out, A dihydric phenol may be added.

Preferred as the dihydric phenolic compound represented by the general formula (1) of the present invention are specifically 1,1-bis (4-hydroxyphenyl) -1-phenylethane,
Bis (4-hydroxyphenyl) diphenylmethane, 1,
An example is 1-bis (4-hydroxyphenyl) -1-phenylpropane. Preferred examples of the dihydric phenolic compound represented by the general formula (2) include bis (4-hydroxyphenyl) sulfide and bis (4
-Hydroxy-3,5-dibromophenyl) sulfide,
Bis (4-hydroxy-3,5-dimethylphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dibromophenyl) sulfone, bis (4-hydroxy-3,5-dimethyl) Phenyl)
Sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxy-3,5-dibromophenyl)
Sulfoxide, bis (4-hydroxy-3,5-dimethylphenyl) sulfoxide and the like are exemplified.

The above-mentioned dihydric phenol of the formula (1) is in the range of 10 to 95 mol%, preferably 30 to 80 mol%, based on all dihydric phenols used. If the dihydric phenol of the general formula (1) is less than 10 mol%, it is difficult to produce a co-polycarbonate resin by a solution method, and if it exceeds 95 mol%, the fluidity becomes poor and the moldability is poor. Becomes

Examples of the molecular weight regulator or terminal terminator used in the present invention include ordinary terminal terminators such as phenol, Pt-butylphenol, and tribromophenol. Long-chain alkyl-substituted phenols, long-chain alkyl acid chlorides and the like can be used, specifically, octyl phenol,
Long-chain alkyl-substituted phenols such as norylphenol, laurylphenol, palmitylphenol and stearylphenol; long-chain alkyl esters of hydroxybenzoic acid such as octyl hydroxybenzoate, lauryl hydroxybenzoate, noryl hydroxybenzoate and stearyl hydroxybenzoate; caprin Aliphatic acid chlorides such as acid chloride, lauric chloride, myristic chloride, palmitic chloride, stearic chloride, cerotic chloride; capric acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Examples thereof include aliphatic acids such as cerotic acid. The amount used is
It is in the range of 7 to 1 mol, preferably 5 to 2 mol, per 100 mol of the dihydric phenol used, and it is naturally possible to use two or more kinds of terminal terminators in combination.

Solvents inert to the reaction include dichloromethane, 1,2
-Dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride,
Chlorinated hydrocarbons such as monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ether compounds such as diethyl ether can be used, and two or more of these organic solvents are mixed. It can also be used. If desired, a solvent having an affinity for water such as ethers, ketones, esters, and nitriles other than those described above may be used as long as the mixed solvent system is not completely compatible with water.

Further, as the polymerization catalyst, trimethylamine, triethylamine, tributylamine, tripropylamine,
Tertiary amines such as trihexylamine, tridecylamine, N, N-dimethylcyclohexylamine, pyridine, quinoline and dimethylaniline; quaternary amines such as trimethylbenzylammonium chloride, tetramethylammonium chlorand and triethylbenzylammonium chloride Ammonium salts and the like.

The polycarbonate resin of the present invention is produced with the above components as essential components, and the branching agent is used in an amount of 0.01 to 3 mol%, particularly 0.1 to 3 mol% based on the dihydric phenol compound.
A branched polycarbonate can be used in combination within the range of 1.0 mol%. Such branching agents include phloroglysin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-
Tri (4-hydroxyphenyl) heptene-2,1,3,5
-Tri (2-hydroxyphenyl) benzol, 1,1,1
-Tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3 Polyhydroxy compounds exemplified by 2,5-triisopropylbenzene and the like, and 3,3-bis (4-
(Hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-bromoisatin and the like are exemplified.

The refractive index of the co-polycarbonate resin produced in the above-mentioned production method is selected from the range of 1.605 to 1.650 by changing the ratio of the dihydric phenols represented by the general formulas (1) and (2). The moldability is determined mainly by the molecular weight and the ratio of the dihydric phenols represented by the general formulas (1) and (2). It is also preferable to use as. Further, the viscosity average molecular weight of the co-polycarbonate resin of the present invention is 13,000 to 25,000, preferably
It is preferable to select from the range of 15,000 to 23,000 from the viewpoint of mechanical strength and fluidity.

Using the co-polycarbonate resin of the present invention described above, the optical lens of the present invention is manufactured by injection molding, compression molding, vacuum molding, or other means, but the injection molding method is most often used due to its mass productivity. The conditions in the present invention include a molding temperature of 280 to 320 ° C and a mold temperature of 80 to 120.
C. and a method of maintaining the pressure at 800 to 1500 kg / cm ² are preferable.

The accuracy of a molded lens is represented by its dimensional accuracy and surface characteristics. If these accuracy are poor, optical distortion increases.

When the co-polycarbonate resin of the present invention is used, a lens with small optical distortion can be easily obtained under the above conditions.

The co-polycarbonate resin of the present invention has an antioxidant, a light stabilizer,
A coloring agent, a release agent, an antistatic agent, and the like may be appropriately used in combination.

[Examples] Hereinafter, specific examples will be described with reference to examples and comparative examples.

REFERENCE EXAMPLE 1 3.7 kg of sodium hydroxide was dissolved in water 42, and the mixture was kept at 20 ° C. and 1,1-bis (4-hydroxyphenyl) -1 was dissolved.
3.7 kg of phenylethane (= BPAP), 4.2 kg of bis (4-hydroxyphenyl) sulfide (= TDP) and 8 g of hydrosulfite were dissolved.

To this, methylene chloride (= MC) 28 was added, and with stirring, 184 g of p-tert-butylphenol (= PTBP) was added, and then 3.8 kg of phosgene was blown in for 60 minutes.

After the phosgene blowing was completed, the mixture was vigorously stirred to emulsify the reaction solution. After the emulsification, 8 g of triethylamine was added, and stirring was continued for about 1 hour to carry out polymerization.

The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the water was washed repeatedly until the pH of the wash became neutral.After that, 35 isopropanol was added to precipitate the polymer. I let it. The precipitate is filtered and then dried under vacuum,
A white powdery co-polycarbonate resin was obtained.

The co-polycarbonate resin was extruded with a vented 40 mm extruder at a temperature of 260 to 280 ° C to obtain pellets.

Table 1 shows the viscosity average molecular weight determined from the intrinsic viscosity of the pellets in the MC solution and the flow value (Q value) determined using the elevated flow tester.

Reference Example 2 In Reference Example 1, 2.8 kg of BPAP, 4.9 kg of TDP, TPBP
Table 1 shows the same results except that 326 g of lauryl p-oxybenzoate was used in place of.

Reference Example 3 In Reference Example 1, 4.6 kg of BPAP, 4 kg of bis (4-hydroxyphenyl) sulfone (= BPS) instead of TDP,
Table 1 shows the same results except that 253 g of p-octylphenol was used instead of PTBP.

Reference Example 4 In Reference Example 1, 3.4 kg of bis (4-hydroxyphenyl) diphenylmethane (= BPDK) was used instead of BPAP, and TDP was used.
Table 1 shows the same results except that 5.6 kg of BPS was used instead of BP and 445 g of stearyl p-oxybenzoate was used instead of PTBP.

Reference Example 5 In Reference Example 1, 4.5 kg of BPDK and TDP were used instead of BPAP.
Table 1 shows the same results except that 4.2 kg and 372 g of stearic acid chloride were used instead of PTBP.

Reference Example 6 Table 1 shows the same results as in Reference Example 1, except that 9.3 kg of BPAP alone was used as the dihydric phenol.

Reference Example 7 In Reference Example 4, BPDK was used alone as a dihydric phenol at 11.3 kg, and instead of stearyl p-oxybenzoate.
Table 1 shows the same results except that PTBP178g was used.

 The description in Table 1 is as follows.

· M _v: 0.5g / dl viscosity-average molecular weight measured by 25 ° C. in methylene chloride solution.・ Q value: Flow tester, 1mmφ × 10m at 280 ℃, 160kg / cm ² load
Measure the amount of molten resin flowing out from the mL nozzle (× 10 ^-2 cc / sec)
Displayed in units.

BPAP: 1,1-bis (4-hydroxyphenyl) -1-phenylethane. -BPDK: bis (4-hydroxyphenyl) diphenylmethane. -TDP: bis (4-hydroxyphenyl) sulfide. BPS: bis (4-hydroxyphenyl) sulfone. -PTBP: p-tert-butylphenol. -POBR: lauryl p-oxybenzoate.・ POP: p-octylphenol. -POBS: Stearyl p-oxybenzoate.・ SAC: Stearic acid chloride. Examples 1 to 5 and Comparative Examples 1 and 2 Using the co-polycarbonate resin pellets obtained in Reference Examples 1 to 7, using a lens mold, resin temperature 300 ° C., mold temperature 90 ° C., holding pressure 1000 kg / cm. ² at outer 50 mm, by molding the lens thickness 3 mm, was determined visually by photoelastic photo optical distortion of moldability, lenses. As the injection molding machine, Neomat 350/120 manufactured by Sumitomo Heavy Industries, Ltd. was used. Also,
The measurement of the refractive index was performed by separately forming molded pieces each having a thickness of 0.8 mm and a size of 10 mm × 5 mm by an injection molding machine and using an Atago Abbe refractometer 2T.

 Table 2 shows the test results.

[Functions and Effects of the Invention] As described above, the optical lens using the co-polycarbonate resin of the present invention has a high refractive index, and has good moldability, and thus has small optical distortion.

Therefore, there is no optical distortion in injection molding with good productivity,
High refractive index lenses can be provided, and by using them for lenses such as microscopes, cameras, telescopes, copiers and other optical devices and glasses, etc., not only can the lens system be made compact and lightweight, but also aberrations such as spherical surfaces can be reduced. It has the advantage of keeping it small.

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Claims (3)

(57) [Claims] 1. A high refractive index optical lens obtained by molding a co-polycarbonate resin produced using a dihydric phenol compound represented by the following general formulas (1) and (2). . (R in the formula represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, A is, -S -, - SO -, - SO 2 - a, X represents a halogen atom, p, q are each It represents an integer of 0 to 2.) 2. The high refractive index optical lens according to claim 1, wherein the dihydric phenol represented by the general formula (1) is in the range of 10 to 95 mol% of the total dihydric phenol. 3. A high refractive index optical lens according to claim 1, wherein said co-polycarbonate resin has a viscosity average molecular weight of 13,000 to 25,000.