KR102003056B1 - Plastic tinted lenses and manufacturing method thereof - Google Patents

Abstract

One embodiment relates to a plastic colored lens and a method of manufacturing the same, wherein the plastic colored lens is excellent in heat resistance and colorability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a plastic colored lens,

One embodiment relates to a plastic colored lens and a method of manufacturing the same, wherein the plastic colored lens is excellent in heat resistance and colorability.

The optical material using plastic is lightweight and does not break easily and is excellent in dyability compared with an optical material made of an inorganic material such as glass. Therefore, plastic materials of various resins are widely used as optical materials such as spectacle lenses and camera lenses . In recent years, as demand for users demanding higher performance and convenience has increased, research on optical materials having properties such as high transparency, high refractive index, high Abbe's number, low specific gravity, high heat resistance and high impact resistance has been continued .

Meanwhile, UV-A of 320 to 380 nm in the wavelength of ultraviolet light is transmitted to the retina through the cornea and the lens to cause a chemical reaction of the lens with the harmful wavelength reaching the retina, thereby causing eye diseases such as cataract and scleritis. In this way, a colored lens is proposed as a method for shielding harmful rays coming into the eye. The colored lens is used not only for protecting eyes from harmful light rays but also for various purposes such as correction of color vision abnormality, beauty, fashion, sports, or relief of eye diseases.

The dyeing method of the colored lens includes various methods such as a coloring method using a dye solution, a coloring method using vacuum deposition, a coloring method using fusion, a coloring method using infiltration, and a coloring method using melting (Korean Patent Laid- 0006401). The coloring method using the dye liquid is a coloring method in which a lens is immersed in a high-temperature dye liquid to widen molecular spacing of the plastic lens so that dye molecules penetrate, and is used as a typical coloring method of a plastic lens. However, there is a problem in that the quality of a colored lens manufactured by various manufacturing conditions such as the kind and concentration of the dye, the immersion temperature and the time is different. Particularly, since the coloring property and the heat resistance of the lens are in a trade-off relationship with each other, a lens which satisfies both excellent heat resistance which does not cause deformation of the lens in the coloring step and excellent coloring property without color imbalance, there was.

Korean Patent Publication No. 2016-0006401

Therefore, one embodiment is to provide a method for producing a plastic colored lens excellent in heat resistance and coloring property regardless of the kind and content of the dye used for coloring, and a plastic colored lens manufactured from the method.

One embodiment is made from a polymerizable composition comprising a polyisocyanate compound and a polythiol compound,

Wherein the Tr of the following formula (1) is from 0.95 to 3.25, and the LB of the following formula (2) is from 0.11 to 0.89:

[Equation 1]

In the above equation (1)

Tg is the glass transition temperature (占 폚) of the lens before coloring,

Tb is a coloring process temperature (占 폚)

&Quot; (2) "

In Equation (2)

T _i is the average transmittance (%) for a wavelength range of 380 to 780 nm of a pre-tinted lens made of a sample having a diameter of 75 mm and a thickness of 2 mm,

T _j is the average transmittance (%) for a wavelength range of 380 to 780 nm of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm.

Another embodiment includes (1) mixing a polyisocyanate compound and a polythiol compound to prepare a polymerizable composition;

(2) molding the polymerizable composition to produce a lens; And

(3) coloring the lens to produce a colored lens,

Wherein the tinted lens has a Tr of 0.95 to 3.25 and a LB of 0.11 to 0.88 in the following equation (1): " (1) "

[Equation 1]

In the above equation (1)

Tg is the glass transition temperature (占 폚) of the lens before coloring,

Tb is a coloring process temperature (占 폚)

&Quot; (2) "

In Equation (2)

T _i is the average transmittance (%) for a wavelength range of 380 to 780 nm of a pre-tinted lens made of a sample having a diameter of 75 mm and a thickness of 2 mm,

T _j is the average transmittance (%) for a wavelength range of 380 to 780 nm of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm.

The plastic colored lens of the embodiment can be applied to various fields requiring no colored unevenness, excellent in appearance, excellent in coloring property, and excellent in heat resistance. Specifically, the heat resistance and the coloring property of the plastic lens produced according to the kind of the polyisocyanate and the polythiol as raw materials and the temperature condition in the coloring step are different. The Tr calculated by the formula (1) and the LB calculated by the formula (2) It is possible to provide a plastic colored lens excellent in heat resistance and coloring property of the lens as described above by adjusting the glass transition temperature of the pre-colored lens, the coloring step temperature, and the like so as to satisfy the numerical value range.

One embodiment is made from a polymerizable composition comprising a polyisocyanate compound and a polythiol compound,

Wherein the Tr of the following formula (1) is from 0.95 to 3.25, and the LB of the following formula (2) is from 0.11 to 0.89:

[Equation 1]

In the above equation (1)

Tg is the glass transition temperature (占 폚) of the lens before coloring,

Tb is a coloring process temperature (占 폚)

&Quot; (2) "

In Equation (2)

T _i is the average transmittance (%) for a wavelength range of 380 to 780 nm of a pre-tinted lens made of a sample having a diameter of 75 mm and a thickness of 2 mm,

T _j is the average transmittance (%) for a wavelength range of 380 to 780 nm of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm.

Polymerizable  Composition

The polymerizable composition includes a polyisocyanate compound and a polythiol compound.

The polythiol compound may be a conventional one used for the synthesis of polythiourethane. Examples of the polythiol compound include bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, 4-mercaptomethyl 3,6-dithia-1,8-octanethiol, 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 2,2-bis (mercaptomethyl) Dithiol, bis (2-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane, 2- (2-mercaptoethylthio) propane- Bis (2,3-dimercaptopropanel) disulfide, 1,2-bis (2-mercaptopropylthio) propylthio) ethanethiol, bis (2- (2-mercaptoethylthio) -3-mercaptopropylthio) ethane, 2- (2-mercaptoethylthio) -3-mercaptopropane, 2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] propylthio-propane- 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethyl) Ethylthio) propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9,12- tetrathiatetradecane- Dithiol, (S) -3 - ((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4R, 14R) -4,14-bis (mercaptomethyl (R-3-mercapto-2 - ((2-mercaptoethyl) thio) -3,6,9,12,15-pentatihaheptane- Propyl) thio) -2,3-dithiobis (propane-1,2-dithiol), (7R, 11S) (7R, 12S) -7,12-bis (mercaptomethyl) -3,6,9,12,15-pentatiaheptadecane-1,17-dithiol, Dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithia Undecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithia Decane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hexakis (3-mercaptopropionate), 1,1,3,3 (Mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 5-bis (mercaptomethyl) -1,4-dithiane And 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane.

The polyisocyanate compound may be a conventional one used for the synthesis of polythiourethane. Examples thereof include isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, hexamethylene diisocyanate, 2,2- Dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11 Diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) isocyanate, Aliphatic isocyanate compounds such as ethers; Bis (isocyanatomethyl) cyclohexane (hydrogenated m-xylene diisocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 1,2- Cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2,2-dimethyldicyclohexylmethane isocyanate, norbornane diisocyanate (norbornane diisocyanate), norbornane diisocyanate ) Alicyclic isocyanate compounds such as < RTI ID = 0.0 > (Isocyanatoethyl) benzene, bis (isocyanatomethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) (Isocyanatomethyl) diphenyl ether, phenylenediisocyanate, ethylphenylenediisocyanate, isopropylphenylenediisocyanate, dimethylphenylenediisocyanate, diethylphenylenediisocyanate, diisopropylphenylenediisocyanate, trimethylbenzene triisocyanate, Benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, toluene diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, Diisocyanate, bis (isocyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzene Aromatic isocyanate compounds such as glycidyl isocyanate, hexahydrodiphenylmethane-4,4-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate and p-xylene diisocyanate; Bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis ) Bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) Aliphatic isocyanate compounds such as isocyanatomethylthio) ethane and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane; Diphenyl sulfide 2,4-diisocyanate, diphenyl sulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzyl thioether, bis (4- Isomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyl diphenyl disulfide-5,5 Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4- A sulfided aromatic isocyanate compound such as 5-diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate and 4,4-dimethoxydiphenyl disulfide-3,3-diisocyanate; And 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) (Isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanato methyl ) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) (Isocyanatomethyl) -2-methyl-1,3-dithiolane; and the like.

The polymerizable composition may contain a polythiol compound and a polyisocyanate compound in an equivalent ratio of 0.5 to 1.5: 1. Specifically, the polymerizable composition may contain a polythiol compound and a polyisocyanate compound in an equivalent ratio of 0.8 to 1.2: 1.

The polymerizable composition may contain at least one additive selected from the group consisting of a reaction catalyst, an internal mold release agent, a UV stabilizer, a polymerization initiator, a heat stabilizer, a bluing agent, a chain extender, a crosslinking agent, a light stabilizer, . Specifically, the polymerizable composition may further include at least one additive selected from the group consisting of an internal mold release agent, a reaction catalyst, a heat stabilizer, a UV stabilizer, and a blueing agent.

The reaction catalyst is not particularly limited as long as it is a known reaction catalyst that can be used for producing a polythiourethane compound. For example, the reaction catalyst may be a dialkyltin halide such as dibutyltin dichloride, dimethyltin dichloride, etc .; Dialkyltin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctanoate and dibutyltin dilaurate; Dialkyltin dialkoxides such as dibutyltin dibutoxide and dioctyltin dibutoxide; Dialkyltin dithioalkoxides such as dibutyltin di (thiobutoxide); Dialkyl tin oxide products such as di (2-ethylhexyl) tin oxide, dioctyltin oxide, and bis (butoxy dibutyltin) oxide; And dialkyltin sulfides such as dibutyltin sulfide. Specifically, dialkyltin halides such as dibutyltin dichloride and dimethyltin dichloride can be used as the reaction catalyst.

The internal release agent may be a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group or a phosphoric acid ester group; A silicone-based nonionic surfactant having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts such as trimethylcetylammonium salt, trimethylstearyl, dimethylethylcetylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, diethylcyclohexadecylammonium salt and the like; And acidic phosphoric acid esters can be used.

Examples of the ultraviolet stabilizer include benzophenone, benzotriazole, salicylate, cyanoacrylate, oxanilide and the like.

Examples of the polymerization initiator include amine-based, phosphorus-based, organic-alumina-based, organic copper-based, organic gallium, organic zirconium, organic iron-based, organic zinc and organic aluminum.

The heat stabilizer may be selected from the group consisting of metal fatty acid salts, phosphorus-based compounds, lead-based compounds, and organosilicate compounds.

The bluing agent has an absorption band in the wavelength range from orange to yellow in the visible light region and has a function of adjusting the color of the optical material made of the resin. Specifically, the bluing agent may include a material that exhibits blue to violet, but is not particularly limited. The bluing agent may be a dye, a fluorescent whitening agent, a fluorescent pigment, an inorganic pigment or the like, but may be suitably selected in accordance with physical properties and resin color required for the produced optical component. These bluing agents may be used alone or in combination of two or more. The bluing agent is preferably a dye in view of the solubility in the polymerizable composition and the transparency of the resulting optical material. Specifically, the dye may be a dye having a maximum absorption wavelength of 520 to 600 nm, and more specifically, a dye having a maximum absorption wavelength of 540 to 580 nm. Further, in view of the structure of the compound, the dye is preferably an anthraquinone dye. The method of adding the bluing agent is not particularly limited and may be added to the monomer system in advance. Specifically, the method of adding the bluing agent may be a method of dissolving it in a monomer, a method of preparing a master solution containing a high concentration of a bluing agent, and a method of diluting the monomer solution or other additives using the master solution, There are several ways to use it.

Plastic colored lens

A plastic colored lens according to an embodiment may be produced from the polymerizable composition. Specifically, the plastic colored lens can be produced by polymerizing, molding and coloring the polymerizable composition.

First, the polymerizable composition may be degassed under reduced pressure and then injected into a plastic lens molding mold. After being injected into the mold, the polymerization can be usually carried out by gradually heating from a low temperature to a high temperature. In order to control the reaction rate, a reaction catalyst which is usually used in the production of polythiourethane may be added, and specific examples thereof are as exemplified above.

The molded body (plastic lens) can then be separated from the mold. The plastic lens may be in various shapes by changing the mold of the mold used in the production.

Thereafter, a plastic colored lens can be produced by coloring a plastic lens. The coloring is not particularly limited so long as it is a method used for coloring a plastic lens. For example, a dye liquid can be used.

The glass transition temperature (Tg) of the pre-tinted lens may be 70 to 150 占 폚, or 80 to 140 占 폚. Further, the coloring process temperature (Tb) may be 20 to 95 占 폚, or 30 to 95 占 폚.

The Tr calculated by Equation (1) may be 0.95 to 3.25. Specifically, the Tr calculated by Equation (1) may be 1.0 to 3.2, 1.0 to 3.0, 1.0 to 2.8, or 1.0 to 2.7. When the Tr value is within the above-mentioned range, it is possible to provide a plastic colored lens which is excellent in coloring property, is free from color imbalance, has excellent appearance, is excellent in heat resistance, and has no lens deformation even in a coloring step performed at a high temperature.

The average transmittance (Ti) for a wavelength range of 380 to 780 nm of the pre-tinted lens made of the sample of 75 mm in diameter and 2 mm in thickness may be 80 to 99%, or 85 to 95%.

The average transmittance (Tj) for a wavelength range of 380 to 780 nm of a tinted lens made of a sample having a diameter of 75 mm and a thickness of 2 mm may be 1 to 99%, or 5 to 90%.

The LB calculated by Equation (2) may be 0.11 to 0.89. Specifically, the LB calculated by Equation (2) may be 0.15 to 0.89, 0.15 to 0.88, 0.16 to 0.89, 0.18 to 0.89, or 0.2 to 0.88. When the LB value is within the above-mentioned range, it is possible to provide a plastic colored lens which is excellent in colorability, has no color unevenness, has excellent appearance, is excellent in heat resistance, and has no lens deformation even in a coloring step performed at a high temperature.

The standard deviation of the transmittance over a wavelength range of 380 to 780 nm of a tinted lens made of a sample having a diameter of 75 mm and a thickness of 2 mm is 5.0 or less and the standard deviation is a coloration of a sample made of a sample having a diameter of 75 mm and a thickness of 2 mm The standard deviation of the transmittance measured at 5 to 20 points within a radius of 30 mm from the center of the circle of the lens. Specifically, the standard deviation of the transmittance may be 0.1 to 5.0, 0.1 to 4.0, 0.5 to 4.0, 0.5 to 3.5, or 0.6 to 3.2. When the standard deviation of the transmittance is within the above range, it is possible to provide a plastic colored lens excellent in appearance without color imbalance.

The plastic colored lens may have a cylindrical shape with a thickness of 0.1 to 20.0 mm and a diameter of 55 to 95 mm. Specifically, the plastic colored lens may have a cylindrical shape with a thickness of 1.0 to 10.0 mm and a diameter of 65 to 85 mm.

The plastic colored lens can be subjected to surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, anti-reflection treatment, anti-reflection treatment, anti- And / or a chemical treatment such as a dimming treatment, and the like.

Manufacturing method of plastic colored lens

One embodiment comprises (1) preparing a polymerizable composition by mixing a polyisocyanate compound and a polythiol compound;

(2) molding the polymerizable composition to produce a lens; And

(3) coloring the lens to produce a colored lens,

Wherein the tinted lens has a Tr of 0.95 to 3.25 and a LB of 0.11 to 0.88 in the following equation (1): " (1) "

[Equation 1]

In the above equation (1)

Tg is the glass transition temperature (占 폚) of the lens before coloring,

Tb is a coloring process temperature (占 폚)

&Quot; (2) "

In Equation (2)

T _i is the average transmittance (%) for a wavelength range of 380 to 780 nm of a pre-tinted lens made of a sample having a diameter of 75 mm and a thickness of 2 mm,

T _j is the average transmittance (%) for a wavelength range of 380 to 780 nm of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm.

Step (1)

In this step, a polyisocyanate compound and a polythiol compound are mixed to prepare a polymerizable composition.

The polyisocyanate compound and the polythiol compound are as defined in the plastic colored lens.

The polymerizable composition may further comprise at least one additive selected from the group consisting of an internal mold release agent, a reaction catalyst, a heat stabilizer, a UV stabilizer and a bluing agent. The additive is as defined in the plastic colored lens.

Step (2)

In this step, the polymerizable composition is molded to produce a lens.

The lens may be prepared by polymerizing (and curing) the polymerizable composition and molding.

First, the polymerizable composition is degassed under reduced pressure, and then injected into a plastic lens molding mold. Such degassing and mold injection can be carried out, for example, at a temperature range of 10 to 40 占 폚.

After injection into the mold, the polymerization is usually carried out by gradually heating from a low temperature to a high temperature. The temperature of the polymerization reaction may be, for example, 10 to 150 ° C, and specifically 10 to 130 ° C. Further, in order to control the reaction rate, a reaction catalyst ordinarily used in the production of polythiourethane may be added to the polymerizable composition, and the specific types thereof are as exemplified above.

The molded body (plastic lens) can then be separated from the mold.

The plastic lens may be in various shapes by changing the mold of the mold used in the production. Specifically, the plastic lens may be in the form of a spectacle lens, a camera lens, a light emitting diode (LED), or the like.

Step (3)

In this step, the lens is colored to produce a colored lens.

The coloring may be performed by immersing the lens in a dye liquid and washing the lens with water. Specifically, the immersion is performed for 1 to 30 minutes, and the washing may be performed at 20 to 30 ° C. In addition, the water washing can be performed using water.

When the immersion of the lens is performed within the time range, workability and productivity are improved.

The dye liquid may include a solid dye and a solvent. Specifically, the dye liquid may contain 0.1 to 10% by weight of solid dye based on the total weight. When the content of the solid dye in the dye liquid is within the above range, it has an excellent coloring effect to the amount of dye used and is economical and has an excellent coloring property.

The solid dye may be at least one selected from the group consisting of azo type, quinophtalones type, and anthraquinone type dyes. However, various dyes other than the above-mentioned dyes can be used for the solid dye.

The solvent may comprise water or an organic solvent. Specifically, the solvent may be water.

According to the manufacturing method as described above, the standard deviation of the transmittance for a wavelength range of 380 to 780 nm of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm is 5.0 or less, the standard deviation is 75 mm The standard deviation of the transmittance measured from 5 to 20 points within a radius of 30 mm based on the center of the circle of the colored lens made of the specimen having a thickness of 2 mm.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.

The polyisocyanates and polythiols used in the following Examples and Comparative Examples are as shown in Tables 1 and 2 below.

division Chemical structure Chemical name Iso 1

m-xylylene diisocyanate Iso 2

Hydrogenated m-xylylenediisocyanate Iso 3

Hexamethylene diisocyanate Iso 4

Toluene diisocyanate Iso 5

Norbornendi isocyanate

division Chemical structure Chemical name Thiol 1

4-mercaptomethyl-3, 6-dithia-
1,8-octanethiol Thiol 2

4,8-dimercaptomethyl-1,11-
Dimercapto-3,6,9-trithianedecane Thiol 3

Pentaerythritol tetrakis
(3-mercaptopropionate) Thiol 4

Pentaerythritol tetrakis
(2-mercaptoacetate) Thiol 5

2,5-bis (mercaptomethyl) -1,4-dithiane

Example 1.

Polyisocyanate and polythiol were mixed in the composition shown in Table 3 below and 0.03 part by weight of dibutyltin dichloride was used as a reaction catalyst based on 100 parts by weight of total of polyisocyanate and polythiol. 1.5 parts by weight of 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole as an ultraviolet stabilizer and 0.2 parts by weight of Zelec® UN (acidic alkyl phosphate ester release agent, Stepan) .

The polymerizable composition was degassed at 15 < 0 > C and 2 torr for 1 hour and filtered through a 3 [mu] m Teflon filter. The filtered polymerizable composition was injected into a glass mold template assembled by tape. The mold was allowed to stand at 10 DEG C for 5 hours, then heated from 10 DEG C to 120 DEG C at a rate of 5 DEG C / minute and polymerized at 120 DEG C for 20 hours. Then, the specimen having a diameter of 75 mm and a thickness of 2 mm cured in the glass mold mold was further cured at 130 캜 for 4 hours, and then the molded body (plastic lens) was released from the glass mold mold.

Thereafter, the dye solution (manufacturer: BPI Co., product number: 46300, solid content of dye: 1.8 wt%) was heated to 90 캜. Thereafter, the plastic lens was immersed in the heated dye solution for 5 minutes, and then washed with water to prepare a plastic colored lens.

Example  2 to 12 and Comparative Example  1-3.

The polymerizable composition was prepared in the same manner as in Example 1 except that polyisocyanate and polythiol were mixed in the composition shown in the following Table 3 and the dye solution was heated to the temperature shown in Table 4 Respectively.

Iso 1 Iso 2 Iso 3 Iso 4 Iso 5 Thiol 1 Thiol 2 Thiol 3 Thiol 4 Thiol 5 Example 1 - 155.4g - - - - 87.9g - 78.4g - Example 2 - 155.7g - - - - 88.1 g - 77.6 g - Example 3 - - - - 164.9g 111.2 g - - 39.3g - Example 4 - - - - 163.8g 110.7 g - - 39.2 g - Example 5 150.6g - - - - 138.8g - - - - Example 6 148.7g - - - - 139.2 g - - - - Example 7 - - - 139.4 g - - 150.7g - - - Example 8 - 155.4g - - - - - 69.2g - 101.9 g Example 9 - 155.2g - - - - - 68.9g - 102.2 g Example 10 - - 134.6 g - - - 146.7g - - - Example 11 150.3g - - - - - 150.7g - - - Example 12 150.6g - - - - - 149.8g - - - Comparative Example 1 150.5g - - - - 138.5g - - - - Comparative Example 2 - - - 139.2 g - - 151.3g - - - Comparative Example 3 - - 134.8g - - - 146.4g - - -

Experimental example. Property measurement

The plastic colored lenses of Examples 1 to 12 and Comparative Examples 1 to 3 were measured for glass transition temperature, color unevenness and deformation. The measurement results are shown in Tables 4 and 5.

(1) Glass transition temperature

The glass transition temperature (Tg, ° C) of the plastic colored lens was measured using a thermal expansion analyzer (TMA Q400, TA) under the peening method (load of 50 g, pin wire 0.5 mmφ, heating rate 10 ° C./min) Respectively.

(2) Refractive index and Abe number

(NE) at 20 캜 using an Abbe's refractometer DR-M4 (ATAGO).

(3) Tr

Tr was calculated by the following formula (1) using the glass transition temperature (Tg, 占 폚) and the coloring process temperature (Tb, 占 폚) measured by the method of the above item (1).

[Equation 1]

(4) Average transmittance and Colorability  evaluation

A plastic tinted lens with a diameter of 75 mm and a thickness of 2 mm or a plastic lens sample before tinting was measured using a UV-visible (Perkin Elmer, Lamda 365 model) in the thickness direction to measure the visible light range from 380 nm to 780 nm The permeability was measured.

Specifically, the transmittance from 380 nm to 780 nm in the visible light region was measured at 10 points (1.0 mm intervals) within a radius of 30 mm from the center of the circle of the lens specimen. Then, the calculated transmittance was calculated by arithmetically averaging the measured transmittance as an average transmittance. LB was calculated from the following equation (2) using the average transmittance (Tj) of the plastic colored lens and the average transmittance (Ti) of the plastic lens before being colored.

&Quot; (2) "

Also, the standard deviation (S) of the average transmittance measured for each point of the plastic colored lens was calculated. When the S value was 5.00 or more, it was judged that there was color unevenness.

(5) Deformation of lens before and after tinting

The lenses were observed with a naked eye under a mercury lamp, and it was judged that they were deformed when microscopic dimensional changes and surface curvature were detected.

Tg (占 폚) Tb (占 폚) Tr Tj (%) Ti (%) LB Transmittance
Standard deviation (S) Example 1 107.4 90 1.19 30.4 91.2 0.67 0.84 Example 2 107.2 40 2.68 72.6 91.1 0.2 0.91 Example 3 102.5 90 1.14 28.7 91.6 0.69 0.78 Example 4 101.7 40 2.54 69.8 91.2 0.23 0.82 Example 5 84.9 80 1.06 11.1 89.5 0.88 0.61 Example 6 84.6 40 2.12 54.3 89.4 0.39 0.73 Example 7 137.3 90 1.53 45.7 86.7 0.47 3.12 Example 8 104.3 90 1.16 27.6 91.6 0.7 0.68 Example 9 104.1 40 2.6 66.7 91.4 0.27 0.71 Example 10 83.7 40 2.09 51.9 87.5 0.41 1.12 Example 11 102.4 90 1.14 18.7 89.2 0.39 0.94 Example 12 102.6 40 2.57 59.7 88.7 0.79 0.96 Comparative Example 1 84.8 90 0.94 8.5 89.4 0.9 5.14 Comparative Example 2 137.6 40 3.43 80.3 86.8 0.07 8.94 Comparative Example 3 83.5 90 0.93 8.1 87.3 0.91 6.03

Refractive index Abe number Color imbalance Presence of deformation Example 1 1.5994 41 none X Example 2 1.5996 41 none X Example 3 1.6024 41 none X Example 4 1.6015 41 none X Example 5 1.6644 32 none X Example 6 1.6647 32 none X Example 7 1.6782 29 none X Example 8 1.6031 42 none X Example 9 1.6029 42 none X Example 10 1.629 39 none X Example 11 1.6693 32 none X Example 12 1.6691 32 none X Comparative Example 1 1.6643 32 has exist O Comparative Example 2 1.6784 28 has exist X Comparative Example 3 1.6293 39 has exist O

As shown in Tables 4 and 5, Examples 1 to 12 having Tr of 0.95 to 3.25 and LB of 0.11 to 0.89 showed no color imbalance and excellent coloring property and did not deform the lens even in a high temperature coloring process. On the other hand, in Comparative Examples 1 to 3 in which Tr and LB were out of the above range, there was a problem that color unevenness occurred or lens deformation occurred during the coloring process.

Claims (12)

A process for producing a polymerizable composition, which is produced from a polymerizable composition comprising a polyisocyanate compound and a polythiol compound,
The Tr of the following formula (1) is 0.95 to 3.25, the LB of the following formula (2) is 0.11 to 0.89,
The standard deviation of the transmittance for a wavelength range of 380 to 780 nm of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm is 0.1 to 5.0,
Wherein the standard deviation is a standard deviation of a transmittance measured at 5 to 20 points within a radius of 30 mm with respect to a center of a circle of a colored lens made of a specimen having a diameter of 75 mm and a thickness of 2 mm,
[Equation 1]

In the above equation (1)
Tg is the glass transition temperature (占 폚) of the lens before coloring,
Tb is a coloring process temperature (占 폚)
&Quot; (2) "

In Equation (2)
T _i is the average transmittance (%) for a wavelength range of 380 to 780 nm of a pre-tinted lens made of a sample having a diameter of 75 mm and a thickness of 2 mm,
T _j is the average transmittance (%) for a wavelength range of 380 to 780 nm of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm.
The method according to claim 1,
Wherein the Tr is 1.0 to 3.0,
Wherein the LB is from 0.15 to 0.88.
delete The method according to claim 1,
And the standard deviation of the transmittance is 0.1 to 4.0.
(1) mixing a polyisocyanate compound and a polythiol compound to prepare a polymerizable composition;
(2) molding the polymerizable composition to produce a lens; And
(3) coloring the lens to produce a colored lens,
Wherein the colored lens has a Tr of 0.95 to 3.25 in the following formula (1), an LB of 0.11 to 0.88 in the following formula (2)
The standard deviation of the transmittance for a wavelength range of 380 to 780 nm of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm is 0.1 to 5.0,
Wherein the standard deviation is a standard deviation of a transmittance measured at 5 to 20 points within a radius of 30 mm based on a circle center of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm :
[Equation 1]

In the above equation (1)
Tg is the glass transition temperature (占 폚) of the lens before coloring,
Tb is a coloring process temperature (占 폚)
&Quot; (2) "

In Equation (2)
T _i is the average transmittance (%) for a wavelength range of 380 to 780 nm of a pre-tinted lens made of a sample having a diameter of 75 mm and a thickness of 2 mm,
T _j is the average transmittance (%) for a wavelength range of 380 to 780 nm of a colored lens made of a sample having a diameter of 75 mm and a thickness of 2 mm.
6. The method of claim 5,
Wherein the polymerizable composition further comprises at least one additive selected from the group consisting of an internal mold release agent, a reaction catalyst, a heat stabilizer, a UV stabilizer and a bluing agent.
6. The method of claim 5,
And the step (3) is carried out in the step of immersing and washing the lens with the dye liquid.
8. The method of claim 7,
Wherein the dye liquid comprises a solid dye and a solvent.
9. The method of claim 8,
Wherein the dye liquid comprises from 0.1 to 10% by weight of a solid dye based on the total weight of the dye liquid,
Wherein the solid dye is at least one selected from the group consisting of azo type, quinophtalone type and anthraquinone type dyes.
9. The method of claim 8,
Wherein the solvent comprises water or an organic solvent.
8. The method of claim 7,
The immersion is performed for 1 to 30 minutes,
Wherein the water washing is performed at 20 to 30 占 폚.
delete