JP2010168462A - Aromatic polycarbonate resin composition and eyeglass lens - Google Patents

Abstract

[PROBLEMS] To improve the performance of ultraviolet absorbers of 380 nm or less of ultraviolet absorbers, to achieve good ultraviolet cutting ability even with a small amount of addition, and to reduce defects during molding, and the resin composition An eyeglass lens formed from an object is provided.
(1) (4) 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine An aromatic polycarbonate resin composition containing 001 to 0.1 parts by weight.
[Selection figure] None

Description

  The present invention relates to a polycarbonate resin composition and a spectacle lens formed from the resin composition, which are excellent in transparency, capable of reducing the molding defect rate, and suppressed discoloration during molding. In particular, the present invention relates to a polycarbonate resin composition in which the amount of ultraviolet absorber added is small even when the light transmittance at 380 nm is kept low.

  Polycarbonate resin has a high refractive index and excellent properties such as transparency and impact resistance, and has recently been widely used as a material for lenses, particularly for eyeglass lenses. Glasses made of polycarbonate resin are thinner and lighter than conventional glass lenses and plastic lenses such as cast polymerization, as shown in Patent Document 1, because of their extremely high impact strength, and are therefore safe and highly functional. As eyeglass lenses, they have come to be used in vision correction lenses, sunglasses, protective glasses, and the like.

  The spectacle lens is required to cut a wavelength of 380 nm or less, in particular, in order to reduce damage to the eyeball or the like due to ultraviolet rays. Conventionally, as in Patent Document 2, an ultraviolet absorber has been added to an aromatic polycarbonate resin. However, conventional UV absorbers for aromatic polycarbonate resins are molecularly designed for the purpose of suppressing discoloration of the aromatic polycarbonate resin itself by ultraviolet rays, and the absorption wavelength is maximized in the vicinity of 290 nm. It was necessary to increase the amount of addition in order to achieve the purpose.

  Eyeglass lenses are molded using various molding methods such as extrusion compression molding, injection compression molding, injection extrusion molding, injection press molding, etc. In any method, molten aromatic polycarbonate resin is placed in the mold. Molded by cooling and solidification. In the case of increasing the UV absorber for the purpose of 380 nm cut, not only the UV absorber volatilized in the mold at the time of molding adheres to the mold, but also the mold adheres to the molded product. There was a problem of significantly reducing the yield.

  Furthermore, generally, when an ultraviolet absorber is added to an aromatic polycarbonate resin, it is melt-kneaded in advance and pelletized and used for molding. When the amount of UV absorber added is large even at the pelletization stage, the UV absorber that has volatilized adheres to the vent portion of the extruder, and it is often necessary to stop production and clean due to a decrease in degassing efficiency. Will occur.

JP 2001-288289 A JP 2006-154783 A

  An object of the present invention is to increase the performance of ultraviolet absorbers of 380 nm or less of ultraviolet absorbers so that a good ultraviolet cutting ability can be achieved even with a small amount of addition, and a polycarbonate resin capable of reducing defects during molding and It is providing the spectacle lens formed from this resin composition.

  In order to achieve the above object, the inventors of the present invention can achieve the object of the present invention by enhancing the absorption capacity of the UV absorber used in the polycarbonate resin at around 380 nm and minimizing discoloration caused by the UV absorber. I found.

That is, according to the present invention,
1. (1) (2) 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine 0.001-0. An aromatic polycarbonate resin composition containing 1 part by weight,
2. The aromatic polycarbonate resin composition according to item 1, further comprising 0.001 to 0.1 parts by weight of (3) a phosphorus-based stabilizer with respect to 100 parts by weight of the polycarbonate resin,
3. The spectacle lens formed from the resin composition according to the preceding item 1, and the spectacle lens according to the preceding item 3, wherein the light transmittance at 4.380 nm is 10% or less,
Is provided.

  The spectacle lens obtained from the polycarbonate resin composition of the present invention can protect the eyeball by cutting ultraviolet rays of 380 nm or less, can reduce defects during molding, and is excellent in molding heat resistance. The industrial effects that it produces are exceptional.

Hereinafter, the present invention will be described in detail.
The polycarbonate resin used in the present invention is an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor. Specific examples of the dihydric phenol used here include, for example, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl). ) Ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2- Bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) Bis (hydroxyaryl) alkanes such as lopan, 1,1-bis (hydroxyphenyl) cyclopentane, bis (hydroxyphenyl) cycloalkanes such as 1,1-bis (hydroxyphenyl) cyclohexane, 4,4′-dihydroxy Dihydroxy ethers such as diphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxys such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide Diaryl sulfides, 4,4'-dihydroxydiphenyl sulfoxide, dihydroxy diaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyls Hong, dihydroxy diaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone. These dihydric phenols may be used alone or in combination of two or more.

  Among the dihydric phenols, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferably used as the main dihydric phenol component, particularly 70 mol% or more, particularly 80 mol in the total dihydric phenol component. % Or more is preferably bisphenol A. Most preferred is an aromatic polycarbonate resin in which the dihydric phenol component is substantially bisphenol A.

  The basic means for producing the polycarbonate resin will be briefly described. In the solution method using phosgene as a carbonate precursor, the reaction of a dihydric phenol component and phosgene is usually performed in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In addition, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used for promoting the reaction, and a terminal terminator such as an alkyl-substituted phenol such as phenol or p-tert-butylphenol is used as a molecular weight regulator. It is desirable to use it. The reaction temperature is preferably 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more.

  In the transesterification method (melting method) using a carbonic acid diester as a carbonate precursor, a predetermined proportion of a dihydric phenol component and a carbonic acid diester are stirred with heating in the presence of an inert gas, and the resulting alcohol or phenols are distilled. It is a method to make it come out. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. The reaction is carried out while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, a normal transesterification reaction catalyst can be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and the like, and diphenyl carbonate is particularly preferable.

The molecular weight of the polycarbonate resin used in the present invention is preferably 1.7 × 10 ^{4 to} 3.0 × 10 ⁴ , particularly preferably 2.0 × 10 ^{4 to} 2.6 × 10 ⁴ in terms of viscosity average molecular weight. Eyeglass lenses are precision molded, and it is important to accurately transfer the mirror surface of the mold to give the specified curvature and power. A low-viscosity resin with good melt flow is desirable, but if it is too low The impact strength that is characteristic of polycarbonate resin cannot be maintained. Here, for the viscosity average molecular weight (M) of the polycarbonate resin, the specific viscosity (η _sp ) obtained from a solution of 0.7 g of the polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer is inserted into the following equation. It is what I asked for.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  2,4,6-Tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine used in the present invention is a compound having a maximum wavelength in the vicinity of 360 nm. expressed.

  A mixture of the present compound can be used, but preferably the purity is 60% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, and most preferably 99% by weight or more. Further, it can be used in combination with other ultraviolet absorbers, but it is desirable not to exceed the content of the present compound. If the purity is low or the content of other ultraviolet absorbers is large, it is difficult to reduce defects during molding.

  Content of this compound is 0.001-0.1 weight part with respect to 100 weight part of polycarbonate resin, Preferably it is 0.005-0.05 weight part, More preferably, it is 0.02-0. 04 parts by weight. When the content is small, the ability to cut ultraviolet rays of 380 nm or less is lowered. When the content is large, not only is it difficult to reduce defects during molding, but the molded product is colored and cannot be used as a spectacle lens.

  Examples of the phosphorus stabilizer used in the present invention include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl mono Phenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) Pentaellis Tall diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, benzenephosphone Diethyl acetate, dipropyl benzenephosphonate, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, Examples thereof include bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite. These can be used alone or in combination of two or more. Among these, a phosphorus-based heat stabilizer having a 2,4-di-tert-butylphenyl skeleton is preferably used.

  Preferably, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di -Tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert -Butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite are used, particularly preferably tetrakis (2,4-di-tert -Butylphenyl) -4,4'-biphenylenediphosphonite is used.

  The amount of these phosphorus heat stabilizers is preferably 0.001 to 0.1 parts by weight, more preferably 0.008 to 0.08 parts by weight, particularly preferably 100 parts by weight of the polycarbonate resin. Is 0.01 to 0.05 parts by weight.

The polycarbonate resin composition of the present invention may be blended with a fatty acid ester release agent in order to improve the releasability from the mold of the resin molded product of the spectacle lens during melt molding.
Examples of the fatty acid ester release agent include esters of monohydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms, polyhydric alcohols having 1 to 25 carbon atoms, and 10 to 30 carbon atoms. At least one mold release agent selected from the group consisting of partial esters or total esters with saturated fatty acids is used.

  Specific examples of the ester of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, and stearyl stearate is preferable.

  Specific examples of partial esters or total esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetra All esters or parts of dipentaerythritol such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate Examples include esters.

These release agents are used alone or in combination of two or more. In particular, a mixture of a monohydric alcohol fatty acid ester compound and a triglyceride compound is preferably used.
Among the fatty acid esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used. In particular, a mixture of stearic acid triglyceride and stearyl stearate is preferably used.

  The compounding amount of the release agent is preferably 0.05 to 0.5 parts by weight, more preferably 0.08 to 0.4 parts by weight, particularly preferably 0.1 to 100 parts by weight of the polycarbonate resin. -0.3 parts by weight. When the blending amount is less than 0.05 parts by weight, good releasability cannot be obtained, and when it exceeds 0.5 parts by weight, the discoloration of the spectacle lens is deteriorated.

  A hindered phenolic antioxidant may be blended with the polycarbonate resin composition of the present invention. Examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N , N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinna Id), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1 , 1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, etc. Is mentioned. These can be used alone or in combination of two or more. Among these, a hindered phenol antioxidant having a pentaerythritol skeleton is preferably used. In particular, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferable.

  The amount of these hindered phenolic antioxidants is preferably 0.01 to 0.3 parts by weight, more preferably 0.02 to 0.25 parts by weight, based on 100 parts by weight of the polycarbonate resin. Particularly preferred is 0.03 to 0.2 parts by weight.

  In the polycarbonate resin composition of the present invention, when molded into a spectacle lens, a bluing agent can be blended to counteract the yellowishness of the lens based on the polycarbonate resin or the ultraviolet absorber. Any bluing agent can be used without any problem as long as it is used for polycarbonate resin. In general, anthraquinone dyes are easily available and preferred.

  Specific examples of the bluing agent include the general name Solvent Violet 13 [CA. No. (Color Index No) 60725; Trade name “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], general name Solvent Violet 31 [CA. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33 [CA. No. 60725; Trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Blue 94 [CA. No. 61500; trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation, generic name Solvent Violet 36 [CA. No. 68210; Trade name “Macrolex Violet 3R” manufactured by Bayer, Inc., generic name Solvent Blue 97 [trade name “Macrolex Blue RR” manufactured by Bayer, Inc.], and generic name SolventBlue 45 [CA. No. 61110; trade name “Tetrazole Blue RLS” manufactured by Sand Corp.] is a typical example. These bluing agents are preferably blended in the polycarbonate resin at a concentration of 0.3 to 1.2 ppm. If a too large amount of bluing agent is added, the absorption of the bluing agent becomes stronger, resulting in a lens with a reduced luminous transmittance. In particular, in the case of eyeglass lenses for vision correction, there are thick and thin portions, and the change in lens thickness is large. Resulting in a lens with a significantly inferior appearance.

  In the polycarbonate resin of the present invention, other heat stabilizers, antistatic agents, flame retardants, heat ray shielding agents, fluorescent whitening agents, pigments, light diffusing agents, reinforcing fillers are also included within the range not impairing the object of the present invention. Other resins and elastomers can be blended.

As the sulfur-based heat stabilizer, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), Examples include dilauryl-3, 3′-thiodipropionate, dimyristyl-3, 3′-thiodipropionate, distearyl-3, 3′-thiodipropionate, and pentaerythritol-tetrakis (3- Lauryl thiopropionate), pentaerythritol-tetrakis (3-myristyl thiopropionate), dilauryl-3, 3'-thiodipropionate, dimyristyl-3, 3'-thiodipropionate. Particularly preferred is pentaerythritol-tetrakis (3-laurylthiopropionate). The thioether compounds are commercially available from Sumitomo Chemical Co., Ltd. as Sumilizer TP-D (trade name), Sumilizer TPM (trade name), and the like, and can be easily used.
As content of the sulfur type heat stabilizer in polycarbonate resin, 0.001-0.2 weight part is preferable with respect to 100 weight part of polycarbonate resin.

  The spectacle lens referred to in the present invention is not particularly limited, and at the time of molding, both the convex surface and concave surface of the lens are optically finished by transfer of the glass mold surface, and a finish lens that is molded to a desired power Both the convex surface and the semi-finished lens are optically finished in the same manner as the finish lens and the concave surface side is optically finished in accordance with a desired power level. The semi-finished lens is ground or cut by a curve generator or an NC-controlled cutting tool or the like according to the necessary concave surface processing, and is subjected to smoothing (fining) as necessary, and this cutting or grinding and smoothing ( The finished surface was polished using a polishing dish with a polishing agent and a polishing cloth or a polishing tool having flexibility, mirror-finished and optically finished, and then the finish lens was also polished Semi-finished lenses are also cleaned, inspected for scratches and foreign matter, and dyeing process to color the lens as desired, hard coat to form a hardened film to cover the ease of scratching plastic lenses Shipped as a finished product through a processing process, a film formation process of an anti-reflection film that reduces the surface reflection of the lens and improves the transmittance Those used in each user is common.

Hereinafter, the present invention will be described in more detail with reference to examples. In addition, a part is a weight part, and evaluation was implemented by the following method.
Foreign matter defect: A foreign matter having a diameter of 10 μm or more was regarded as defective.
Optical failure: A product that deviated from the frequency of -2.0 ± 0.1 was regarded as defective.
Color difference defect: A thing in which yellowing was confirmed was regarded as defective.

[Examples 1-4, Comparative Examples 1-2]
The blends in Table 1 were sufficiently mixed with a tumbler and then pelletized at 290 ° C. with a 30 mmφ vented twin screw extruder. The obtained pellets were dried at 120 ° C. for 4 hours and molded by an injection molding machine (cylinder temperature 350 ° C., 1 minute cycle) to obtain a molded plate having a length of 90 mm × width 50 mm × thickness 2 mm. The molded plate was measured for light transmittance at 380 nm with a spectrophotometer U-4100 manufactured by Hitachi, Ltd.

  In addition, an extrusion compression molding method in which pellets separately plasticized and melted at 350 ° C. are poured into a mold set at a temperature of 200 ° C. and cooled at a room temperature of 23 ° C. for about 10 minutes under a pressure of about 1700 psi. An eyeglass lens molded article having a diameter of 80 mm, a heel thickness of 9 mm, and a power of -2.0 was prepared. 10,000 eyeglass lenses were molded at each level, and each defect was detected.

Each symbol shown in Table 1 represents the following compound.
PC1: aromatic polycarbonate resin having a viscosity average molecular weight of 23,000 L1: mixture of alkyl monoester and triglycerin (SL900A manufactured by Riken Vitamin)
A1: Phosphorus stabilizer (P-EPQ manufactured by Clariant Japan)
U1: 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5 triazine (T-712 manufactured by ADEKA)
U2: 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol) -2-ylphenol] (LA-31 manufactured by ADEKA)
H1: Brewing agent (Mayorex Violet B from Bayer)

  The polycarbonate resin composition of the present invention is useful as a spectacle lens.

Claims (4)

  (1) (2) 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine 0.001-0. An aromatic polycarbonate resin composition containing 1 part by weight.   Furthermore, the aromatic polycarbonate resin composition of Claim 1 which contains 0.001-0.1 weight part of (3) phosphorus stabilizer with respect to 100 weight part of polycarbonate resin.   An eyeglass lens formed from the resin composition according to claim 1.   The spectacle lens according to claim 3, wherein the light transmittance at 380 nm is 10% or less.