Polyurethane resin composition, preparation method therefor and optical material prepared therefrom

Abstract

An implementation relates to a polyurethane resin composition, a preparation method therefor and an optical material prepared therefrom, the polyurethane resin composition comprising an isocyanate compound, a thiol compound and a dye, wherein the dye comprises a first dye having a maximum absorption wavelength in a wavelength range of 610-670 nm, and a cured product, which is manufactured from the polyurethane resin composition and has a thickness of 2 mm and a power of 0.00 diopters, has a b* value of less than 0.84, measured by a CIE Lab colorimeter. The implementation can provide an optical material having a required level of color.

Description

Polyurethane resin composition, method for manufacturing the same, and optical material manufactured therefrom

[0001] An embodiment relates to a polyurethane resin composition capable of realizing an optical material that displays a color capable of giving a comfortable and sophisticated feeling to the user, and a method for manufacturing the same.

[0002] Examples of optical materials include plastic lenses, prisms, optical fibers, substrates for information recording media (e.g., optical discs), and optical filters. Among these optical materials, plastic lenses are lighter than glass lenses and offer superior impact resistance and ease of dyeing, leading to an increasing share of the eyeglass lens market recently.

[0003] The above plastic lenses are manufactured using polycarbonate resin, acrylic resin, cycloolefin polymer, polyurethane resin, etc. However, due to the influence of additives such as UV absorbers or heat treatment processes, the manufactured plastic lenses may appear yellowish. Plastic lenses that appear yellowish in this way give the user a deteriorated appearance rather than a fresh and comfortable one. Accordingly, attempts are being made to reduce the yellowness of plastic lenses by introducing dyes such as red, yellow, and green to prevent the lenses from appearing yellow, but there are limitations in controlling the yellowness to the required level.

[0004] Meanwhile, the plastic lens containing the above-mentioned polyurethane resin is manufactured through a process of reacting an isocyanate compound with an active hydrogen compound, such as a polyol compound or a thiol compound. In this process, conventionally, dyes, additives, etc., were mixed with the isocyanate compound and reacted with the active hydrogen compound to control the yellowness of the plastic lens; however, this method has the problem of reduced process efficiency and economic feasibility due to the decrease in the long-term stability of the isocyanate compound.

[0005] [Prior Art Literature]

[0006] [Patent Literature]

[0007] (Patent Document 1) Republic of Korea Published Patent No. 2017-0090494

[0008] The embodiment aims to provide a polyurethane resin composition capable of realizing an optical material that exhibits a color giving a comfortable and sophisticated feeling to the user by introducing a specific dye.

[0009] In addition, the embodiment aims to provide a method for manufacturing a polyurethane resin composition that can efficiently produce a polyurethane resin composition having long-term storage stability by improving the process of introducing a specific dye.

[0010] Another embodiment aims to provide an optical material manufactured from the above-mentioned polyurethane resin composition.

[0011] According to an embodiment, to solve the above problem, a polyurethane resin composition comprising an isocyanate compound, a thiol compound, and a dye is provided, wherein the dye comprises a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm, and the polyurethane resin composition has a b* value of less than 0.84 according to CIE Lab colorimeter measurement of a cured product having a thickness of 2 mm and a degree of 0.00 diopters prepared from the polyurethane resin composition.

[0012] According to another embodiment, a method for preparing a polyurethane resin composition is provided, comprising: (1) a step of preparing a first formulation including an isocyanate compound; and (2) a step of preparing a second formulation including a thiol compound and a dye, wherein the dye includes a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm, and the cured product obtained by the curing reaction of the first formulation and the second formulation has a thickness of 2 mm and a degree of 0.00 diopters, and a b* value of less than 0.84 according to CIE Lab colorimeter measurement.

[0013] According to another embodiment, an optical material is provided that is manufactured from a polyurethane resin composition comprising an isocyanate compound, a thiol compound, and a dye, wherein the dye comprises a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm, and has a thickness of 2 mm and a degree of 0.00 diopters, and has a b* value of less than 0.84 according to CIE Lab colorimeter measurement.

[0014] Since the polyurethane resin composition according to the embodiment includes a dye (first dye, second dye and / or third dye) that exhibits a maximum absorption wavelength in a specific wavelength range, when an optical material is manufactured using the polyurethane resin composition, an optical material exhibiting a required level of color (in particular, a b* value) can be obtained. Accordingly, the embodiment can provide an optical material exhibiting a color that gives the user a comfortable and sophisticated feeling.

[0015] In addition, since the polyurethane resin composition according to the embodiment is manufactured by mixing the dye with a thiol compound rather than an isocyanate compound, it has excellent long-term storage stability, allowing for the efficient and economical provision of an optical material that exhibits a required level of color.

[0016] The invention is described below through embodiments. The embodiments disclosed below are not limited to the contents disclosed below and may be modified in various forms as long as the essence of the invention is not altered.

[0017] In this specification, the description that one component is formed above or below another component, or is connected or coupled to one another, includes both direct formation, connection, or coupling between these components and indirect formation, connection, or coupling through the interposition of another component. Furthermore, it should be understood that the criteria for the "above" and "below" of each component may vary depending on the direction in which the object is observed.

[0018] In this specification, the use of the word “comprising” is intended to specify certain characteristics, regions, steps, processes, elements, and / or components, and unless specifically stated otherwise, it does not exclude the presence or addition of other characteristics, regions, steps, processes, elements, and / or components.

[0019] All numbers and expressions indicating the amounts of components, reaction conditions, etc. described in this specification shall be understood to be modified by the term "about" in all cases unless otherwise specified.

[0020] In this specification, terms such as "first," "second," etc. are used to describe various components, and said components are not to be limited by said terms. These terms are used for the purpose of distinguishing one component from another.

[0021]

[0022] Polyurethane resin composition

[0023] The polyurethane resin composition according to an embodiment is a polyurethane resin composition comprising an isocyanate compound, a thiol compound, and a dye, wherein the dye comprises a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm, and the b* value according to CIE Lab colorimeter measurement of a cured product having a thickness of 2 mm and a degree of 0.00 diopters prepared from the polyurethane resin composition is less than 0.84. Specifically, the polyurethane resin composition may be a polythiourethane resin composition, and more specifically, a polythiourethane resin composition for manufacturing optical materials. Each component included in such a polyurethane resin composition is specifically described as follows.

[0024]

[0025] isocyanate compounds

[0026] The isocyanate compound included in the polyurethane resin composition according to the embodiment is a compound having an isocyanate group (-NCO) and forms a cured product by crosslinking with the thiol compound. As such an isocyanate compound, a conventionally known compound having an isocyanate group (-NCO) may be used. Specifically, the isocyanate compound may be a diisocyanate compound having two isocyanate groups (-NCO).

[0027] For example, the above isocyanate compounds include xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, hydrogenated xylylene diisocyanate (H6XDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, dimethylphenylene diisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-Methylenebis(phenylisocyanate) (MDI), 1,2-Bis(isocyanatomethyl)benzene, 1,3-Bis(isocyanatomethyl)benzene, 1,4-Bis(isocyanatomethyl)benzene, 1,2-Bis(isocyanatoethyl)benzene, 1,3-Bis(isocyanatoethyl)benzene, 1,4-Bis(isocyanatoethyl)benzene, α,α,α',α'-Tetramethylxylylenediisocyanate, Bis(isocyanatomethyl)naphthalene, Bis(isocyanatomethylphenyl)ether, Norbornene diisocyanate (NBDI), Bis(isocyanatomethyl)sulfide, Bis(isocyanatoethyl)sulfide, Bis(isocyanatopropyl)sulfide, It may include one or more selected from the group consisting of 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-dithian, 2,5-diisocyanatomethyl-1,4-dithian, and 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione.

[0028] The above isocyanate compound may have a weight-average molecular weight (Mw) of 150 to 510 g / mol. Specifically, the weight-average molecular weight (Mw) of the above isocyanate compound may be 160 to 450 g / mol, 170 to 400 g / mol, 175 to 350 g / mol, or 180 to 300 g / mol. As the weight-average molecular weight (Mw) of the above isocyanate compound is within the above range, the crosslinking density and viscosity of the polyurethane resin composition can be controlled to a required level, thereby improving processability (moldability).

[0029] The content of the above isocyanate compound is not particularly limited, but considering the processability of the polyurethane resin composition and the physical properties of the optical material, it may be 30 to 70 weight%, 40 to 60 weight%, or 45 to 55 weight% based on the total weight of the polyurethane resin composition.

[0030]

[0031] thiol compounds

[0032] The thiol compound included in the polyurethane resin composition according to the embodiment is a compound having a thiol group (-SH). Specifically, the thiol compound may be a polythiol compound having two or more (e.g., two to four) thiol groups (-SH).

[0033] For example, the above thiol compounds are 1,9-dimercapto-3,7-dithianonan, 1,13-dimercapto-3,7,11-trithiatodecane, glycol di(3-mercaptopropionate), 1,4-dithiane-2,5-diylmethanethiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithioctane, 2-mercaptomethyl-1,5-dimercapto-3-thiopentan, trimethylolpropane tri(3-mercaptopropionate), 5,9-di(mercaptoethyl)-1,12-dimercapto-3,7,10-trithiadodecane, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(mercaptoacetate), It may include one or more selected from the group consisting of 4,7-bis(mercaptomethyl)-3,6,9-trithioundecane-1,11-dithiol, 4,8-bis(mercaptomethyl)-3,6,9-trithioundecane-1,11-dithiol, and 5,7-bis(mercaptomethyl)-3,6,9-trithioundecane-1,11-dithiol.

[0034] The thiol compound may have a weight-average molecular weight (Mw) of 200 to 3,000 g / mol. Specifically, the weight-average molecular weight (Mw) of the thiol compound may be 250 to 2,500 g / mol, 300 to 2,000 g / mol, 350 to 1,500 g / mol, or 400 to 1,000 g / mol.

[0035] More specifically, the thiol compound may include a first thiol compound and a second thiol compound distinguished by the presence or absence of an ester group and a weight-average molecular weight (Mw). For example, the first thiol compound may not have an ester group and may have a weight-average molecular weight (Mw) of 200 to 1,500 g / mol, 210 to 1,400 g / mol, or 220 to 1,300 g / mol. Additionally, the second thiol compound may have an ester group at the terminal end and may have a weight-average molecular weight (Mw) of 400 to 3,000 g / mol, 450 to 2,500 g / mol, or 500 to 2,000 g / mol.

[0036] The content of the above thiol compound is not particularly limited, but considering the processability of the polyurethane resin composition and the physical properties of the optical material, it may be 30 to 70 weight%, 40 to 60 weight%, or 45 to 55 weight% based on the total weight of the polyurethane resin composition.

[0037]

[0038] dyes

[0039] The dye included in the polyurethane resin composition according to the embodiment is a specific dye that controls the yellowness (YI) of the optical material produced from the polyurethane resin composition. Specifically, the dye includes a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm. Since the dye includes the first dye, the yellowness (YI) is controlled to a required level, thereby enabling the realization of an optical material that exhibits a color that gives the user a comfortable and sophisticated feeling.

[0040] In particular, in the embodiment, by optimizing the combination and ratio of dye(s) that exhibit a maximum absorption wavelength in a specific wavelength range, when manufacturing an optical material with a polyurethane resin composition containing said dye(s), an optical material with a color (specifically, b* value) controlled to a required level can be provided.

[0041] Specifically, the dye may optionally further include a second dye and a third dye in addition to the first dye.

[0042] For example, according to an embodiment, the dye may further include a second dye that exhibits a maximum absorption wavelength in the wavelength range of 540 to 590 nm.

[0043] In addition, according to an embodiment, the dye may further include a third dye that exhibits a maximum absorption wavelength in the wavelength range of 450 to 495 nm.

[0044] When an optical material is manufactured using a polyurethane resin composition further comprising the second dye and / or the third dye, it may be possible to realize an optical material having a yellowness (YI) and / or b* value that is difficult or impossible to achieve within a limited dye content.

[0045] The maximum absorption wavelength of the above dye can be confirmed by preparing a dye sample by dissolving the dye in toluene at a concentration of 1 ppm, measuring the absorption spectrum of the prepared dye sample with a commonly known spectrophotometer, and detecting the peak using UV Solutions Plus dedicated software.

[0046] The first dye is not particularly limited as long as it is a commonly known dye that exhibits a maximum absorption wavelength in the range of 610 to 670 nm (e.g., 615 to 660 nm, 620 to 650 nm, 625 to 640 nm, or 628 to 632 nm). Specifically, the first dye may include one or more selected from the group consisting of Solvent blue 104, Solvent blue 63, Acid blue 1, Acid blue 7, Acid blue 5, Acid blue 90, Acid blue 25, Acid blue 112, and Direct blue 86.

[0047] The second dye is not particularly limited as long as it is a commonly known dye that exhibits a maximum absorption wavelength in the range of 540 to 590 nm (e.g., 545 to 585 nm, 550 to 580 nm, 555 to 575 nm, or 560 to 570 nm). Specifically, the second dye may include one or more selected from the group consisting of Solvent violet 13, Acid red 52, Acid violet 43, Acid violet 48, Solvent violet 59, and Direct violet 51.

[0048] The third dye is not particularly limited as long as it is a commonly known dye that exhibits a maximum absorption wavelength in the range of 450 to 495 nm (e.g., 455 to 495 nm, 460 to 490 nm, 465 to 485 nm, or 470 to 480 nm). Specifically, the third dye may include one or more selected from the group consisting of Solvent red 135, Solvent red 179, Acid red 52, Direct red 28, and Reactive red 31.

[0049] The content of the first dye is not particularly limited, but may be 0.05 to 1 ppm, 0.07 to 1 ppm, 0.09 to 0.9 ppm, 0.1 to 0.85 ppm, 0.15 to 0.8 ppm, or 0.2 to 0.75 ppm based on the total weight of the polyurethane resin composition.

[0050] The content of the second dye is not particularly limited, but may be 0.1 to 1.5 ppm, 0.15 to 1.3 ppm, 0.2 to 1 ppm, 0.3 to 0.9 ppm, 0.35 to 0.8 ppm, or 0.4 to 0.7 ppm based on the total weight of the polyurethane resin composition.

[0051] The content of the third dye is not particularly limited, but may be 0.05 to 1 ppm, 0.07 to 0.8 ppm, 0.1 to 0.7 ppm, 0.15 to 0.6 ppm, 0.15 to 0.5 ppm, or 0.2 to 0.4 ppm based on the total weight of the polyurethane resin composition.

[0052] According to an embodiment, the total content (x+y) of the first dye (x) and the second dye (y) may be 0.40 to 0.85 ppm based on the total weight of the polyurethane resin composition. Specifically, the total content (x+y) may be 0.50 to 0.85 ppm, 0.60 to 0.85 ppm, 0.70 to 0.85 ppm, 0.71 to 0.85 ppm, 0.71 to 0.84 ppm, 0.75 to 0.83 ppm, or 0.77 to 0.81 ppm based on the total weight of the polyurethane resin composition.

[0053] According to an embodiment, the mixing ratio (x:y) of the first dye (x) and the second dye (y) may be a weight ratio of 1:1 to 9. Specifically, the mixing ratio (x:y) may be a weight ratio of 1:1 to 8, a weight ratio of 1:1 to 7, a weight ratio of 1:1 to 6, or a weight ratio of 1:1 to 5.

[0054] According to an embodiment, the mixing ratio (x:y:z) of the first dye (x), the second dye (y), and the third dye (z) may be a weight ratio of 1 to 6 : 1 to 6 : 1 to 6. Specifically, the mixing ratio (x:y:z) may be a weight ratio of 1 to 5 : 1 to 5 : 1 to 5, a weight ratio of 1 to 3 : 1 to 3 : 1 to 3, or a weight ratio of 1 to 2 : 1 to 2 : 1 to 2.

[0055]

[0056] The polyurethane resin composition according to the embodiment may further include one or more additives selected from the group consisting of catalysts, ultraviolet absorbers, heat stabilizers, and release agents.

[0057] The above catalysts may include dialkyl tin halide catalysts such as dibutyl tin dichloride and dimethyl tin dichloride; dialkyl tin dicarboxylate catalysts such as dimethyl tin diacetate, dibutyl tin dioctanoate and dibutyl tin dilaurate; dialkyl tin diallkoxide catalysts such as dibutyl tin dibutoxide and dioctyl tin dibutoxide; dialkyl tin dithioalkoxide catalysts such as dibutyl tin di(thiobutoxide); dialkyl tin oxide catalysts such as di(2-ethylhexyl) tin oxide, dioctyl tin oxide, and bis(butoxydibutyl tin) oxide; or dialkyl tin sulfide catalysts such as dibutyl tin sulfide, but are not limited thereto.

[0058] The above-mentioned ultraviolet absorbers may include benzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, cyanoacrylate-based compounds, oxanilide-based compounds, etc., but are not limited thereto.

[0059] The above-mentioned heat stabilizers may include metal fatty acid salt compounds, phosphorus compounds, lead compounds, organotin compounds, etc., but are not limited thereto.

[0060] The above release agent may be a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group; a silicone-based nonionic surfactant having a dimethylpolysiloxane group, a hydroxyalkyl group, or a phosphate ester group; a quaternary alkyl ammonium salt such as trimethylcetylammonium salt, trimethylstearyl, dimethylethylcetylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, diethylcyclohexadodecylammonium salt, etc.; or an acidic phosphate ester, etc., but is not limited thereto.

[0061] The content of the above additive can be appropriately controlled within a range that does not affect the physical properties of the polyurethane resin composition and the optical material.

[0062]

[0063] As the polyurethane resin composition according to the embodiment includes the aforementioned dyes (first dye, second dye and / or third dye), the cured product thereof can have its b* value controlled to a specific range, thereby providing an optical material that exhibits a required level of color. Specifically, a cured product (flat cured product specimen) prepared from the polyurethane resin composition according to the embodiment, having a thickness of 2 mm and a degree of 0.00 diopters, exhibits a b* value of less than 0.84 when measured with a CIE Lab colorimeter. Specifically, the cured product may have a b* value measured by a CIE Lab colorimeter of 0.82 or less, 0.80 or less, 0.78 or less, 0.76 or less, 0.75 or less, 0.72 or less, 0.70 or less, 0.68 or less, 0.66 or less, or 0.64 or less (e.g., 0.50 to 0.83, 0.55 to 0.81, 0.60 to 0.77, 0.62 to 0.74, or 0.63 to 0.69).

[0064] In addition, a cured product (flat cured product specimen) manufactured from a polyurethane resin composition according to an embodiment, having a thickness of 2 mm and a degree of 0.00 diopters, may have an L* value of 95.55 or less, 95.35 or less, 95.05 or less, 94.99 or less, 94.95 or less, 94.90 or less, 94.87 or less, 94.85 or less, 94.80 or less, 94.70 or less, 94.60 or less, or 94.55 or less (e.g., 94.00 to 95.55, 94.35 to 95.00, 94.45 to 94.95, 94.55 to 94.90, or 94.75 to 94.85). In addition, when the above cured material is measured with a CIE Lab colorimeter, the a* value may be -0.60 or less, -0.62 or less, -0.65 or less, -0.67 or less, -0.70 or less, -0.72 or less, -0.74 or less, -0.76 or less, -0.78 or less, or -0.80 or less (e.g., -0.82 to -0.60, -0.81 to -0.62, -0.79 to -0.64, -0.77 to -0.66, or -0.76 to -0.65).

[0065] The above CIE Lab colorimeter is a color space coordinate defined by the CIE (Commission International d'Eclairage), where L* values ​​represent brightness (0~100: 0 is black, 100 is white), a* values ​​represent green-red (based on 0, + is red, - is green), and b* values ​​represent yellow-blue (based on 0, + is yellow, - is blue).

[0066] As the L*, b*, and a* values ​​of the cured product prepared from the above polyurethane resin composition are each controlled within the above ranges, the cured product can exhibit a low yellowness (YI). Therefore, when manufacturing an optical material (e.g., eyeglass lenses) using the above polyurethane resin composition, it is possible to provide an optical material that exhibits a color that gives the user a comfortable and sophisticated feeling.

[0067] Specifically, a cured product (flat-plate cured product specimen) manufactured from a polyurethane resin composition according to an embodiment, having a thickness of 2 mm and a degree of 0.00 diopters, may have a yellowness (YI) of 1.30 or less. Specifically, the yellowness of the cured product may be 1.25 or less, 1.20 or less, 1.15 or less, 1.13 or less, 1.10 or less, 1.08 or less, 1.05 or less, 1.00 or less, 0.99 or less, 0.98 or less, 0.96 or less, 0.93 or less, 0.90 or less, 0.85 or less, 0.80 or less, 0.75 or less, or 0.70 or less (e.g., 0.65 to 1.30, 0.70 to 1.20, 0.75 to 1.00, or 0.85 to 0.95).

[0068] Meanwhile, the polyurethane resin composition according to the embodiment has a b* value change index (I) according to Formula 1 below. v ) exhibits a value of 0.95 to 1.1, indicating excellent long-term storage stability. Specifically, the above b* value change index (I v ) may be 0.96 to 1.05, 0.97 to 1.03, 0.98 to 1.01, or 0.99 to 1.

[0069] [Equation 1]

[0070] I v = I v2 / I v1

[0071] In the above Equation 1,

[0072] I v1 is the b* value according to CIE Lab colorimeter measurement of a cured product (thickness 2 mm and degree 0.00 diopter) prepared from the above polyurethane resin composition stored at room temperature for 30 minutes, and

[0073] I v2b* is the value according to CIE Lab colorimeter measurement of a cured product (thickness 2 mm and degree 0.00 diopter) prepared from the above polyurethane resin composition stored at room temperature for 180 days.

[0074]

[0075] Method for manufacturing a polyurethane resin composition

[0076] A method for manufacturing a polyurethane resin composition according to an embodiment is characterized by first mixing a dye with a thiol compound rather than an isocyanate compound, thereby enabling the efficient manufacturing of a polyurethane resin composition with excellent long-term storage stability. Specifically, a method for manufacturing a polyurethane resin composition according to an embodiment comprises: (1) a step of manufacturing a first mixture containing an isocyanate compound; and (2) a step of manufacturing a second mixture containing a thiol compound and a dye, wherein the dye includes a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm, and the cured product obtained by the curing reaction of the mixture of the first mixture and the second mixture has a thickness of 2 mm and a degree of 0.00 diopters, and the b* value according to CIE Lab colorimeter measurement is less than 0.84.

[0077] The method for manufacturing this polyurethane resin composition is explained step by step as follows.

[0078]

[0079] (1) Preparation of the first mixture

[0080] A method for preparing a polyurethane resin composition according to an embodiment includes the step of preparing a first mixture containing an isocyanate compound. Specifically, the first mixture may be prepared by introducing the isocyanate compound and an additive into a container and undergoing a process of stirring and dissolving at room temperature. Since the descriptions of the isocyanate compound and the additive are the same as those described above, a detailed description thereof is omitted.

[0081] In the above stirring process, the stirring speed is not particularly limited, but considering the manufacturing efficiency of the first mixture, it may be 100 to 400 rpm, 150 to 350 rpm, or 200 to 300 rpm.

[0082] For example, xylylene diisocyanate (XDI) as an isocyanate compound, and a catalyst, a release agent, and a UV absorber as additives can be introduced into the container and stirred and dissolved to prepare a first mixture.

[0083]

[0084] (2) Preparation of the second mixture

[0085] A method for preparing a polyurethane resin composition according to an embodiment includes the step of preparing a second mixture comprising a thiol compound and a dye. Specifically, the second mixture can be prepared by adding the thiol compound and the dye to a container and undergoing a process of stirring and dissolving at room temperature. The description of the thiol compound and the dye is omitted as it is the same as described above.

[0086] In the above stirring process, the stirring speed is not particularly limited, but considering the manufacturing efficiency of the second mixture, it may be 100 to 400 rpm, 150 to 350 rpm, or 200 to 300 rpm.

[0087] For example, a second mixture can be prepared by adding a mixture of a first thiol compound and a second thiol compound as a thiol compound, and a first dye and a second dye as dyes into the container, stirring, and dissolving. Additionally, the third dye may optionally be added to the container.

[0088] The above dye is mixed with a thiol compound having superior long-term storage stability compared to an isocyanate compound to obtain the second formulation, thereby enabling the embodiment to produce a polyurethane resin composition with superior long-term storage stability.

[0089]

[0090] A method for manufacturing a polyurethane resin composition according to an embodiment may further include a step of mixing the first mixture and the second mixture. The mixing may be performed by undergoing a stirring process that is generally known at room temperature. Additionally, the mixing may be performed at the time of manufacturing an optical material through a curing reaction, while the first mixture and the second mixture are stored separately. For example, the polyurethane resin composition according to an embodiment may refer to a two-component resin composition before the first mixture and the second mixture are mixed, or a mixture in which the first mixture and the second mixture are mixed.

[0091]

[0092] Meanwhile, according to an embodiment, the b* value of the cured product with a thickness of 2 mm and a degree of 0.00 diopters, obtained by the curing reaction of the mixture of the first mixture and the second mixture, is less than 0.84, the L* value is 95.55 or less, the a* value is -0.60 or less, and the yellowness (YI) is 1.30 or less, as described above, so a detailed explanation of these is omitted.

[0093]

[0094] Optical materials

[0095] The optical material according to the embodiment is an optical material manufactured from a polyurethane resin composition comprising an isocyanate compound, a thiol compound, and a dye, wherein the dye comprises a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm, and the b* value according to the CIE Lab colorimeter measurement of the optical material having a thickness of 2 mm and a degree of 0.00 diopters is less than 0.84.

[0096] Specifically, the optical material according to the embodiment is obtained by performing a curing reaction of the polyurethane resin composition described above, and since it is manufactured using the polyurethane resin composition described above, it can display a color that gives the user a comfortable and sophisticated feeling.

[0097] The conditions for curing the polyurethane resin composition to manufacture the above optical material are not particularly limited, but can be performed at 110 to 140 ℃ (starting temperature: 15 to 25 ℃) for 17 to 25 hours.

[0098] The above optical material may additionally undergo physical or chemical treatments, such as anti-reflective treatment, anti-fogging treatment, antistatic treatment, hardcoat treatment, and surface polishing, as needed.

[0099] The optical material according to this embodiment may be an eyeglass lens.

[0100]

[0101] The embodiments will be explained in more detail through the following examples. However, the scope of the embodiments is not limited to these examples.

[0102]

[0103] [Example 1]

[0104] A. Preparation of Polyurethane Resin Composition

[0105] 1) Preparation of the first mixture

[0106] A first formulation was prepared by mixing and dissolving 100 parts by weight of xylylene diisocyanate, 0.01 parts by weight of dimethyl tin dichloride as a catalyst, 0.1 parts by weight of acidic phosphate ester (manufactured by Johoku Chemical Industry Co., Ltd., JP-506H) as a release agent, and 0.5 parts by weight of an ultraviolet absorber (manufactured by Cipro Chemical Co., Ltd., Sisov 701, absorption wavelength: 340 nm).

[0107] 2) Preparation of the second mixture

[0108] A second formulation was prepared by mixing and dissolving 0.06 parts by weight of Solvent blue 104 (first dye, maximum absorption wavelength: approximately 630 nm) and 0.01 parts by weight of Solvent violet 13 (second dye, maximum absorption wavelength: approximately 550 nm) with respect to 100 parts by weight of a thiol compound. At this time, a mixture of 4,7-bis(mercaptomethyl)-3,6,9-trithioundecane-1,11-dithiol, 4,8-bis(mercaptomethyl)-3,6,9-trithioundecane-1,11-dithiol, and 5,7-bis(mercaptomethyl)-3,6,9-trithioundecane-1,11-dithiol was used as the thiol compound.

[0109] 3) Mixing the first mixture and the second mixture

[0110] A polyurethane resin composition was prepared by mixing the first mixture and the second mixture in a weight ratio of 50.52 to 49.48.

[0111] B. Manufacturing of Optical Materials

[0112] The prepared polyurethane resin composition was degassed under stirring conditions for 0.5 to 1 hour, degassed again under standing conditions for 0.5 to 1 hour, and then injected into a mold. A curing reaction was carried out for about 20 hours at a starting temperature of 15 to 25 ℃ and a maximum temperature of 110 to 140 ℃ to produce an optical material (flat cured material) with a degree of 0.00 diopters and a center thickness of 2 mm.

[0113]

[0114] [Examples 2 to 6]

[0115] An optical material was prepared through the same process as in Example 1, except that the ratio of Solvent blue 104 (first dye) and Solvent violet 13 (second dye) included in the polyurethane resin composition was adjusted as shown in Table 1 below.

[0116]

[0117] [Example 7]

[0118] An optical material was prepared through the same process as in Example 1, except that Solvent blue 104 (first dye) was used alone as the dye mixed with the thiol compound.

[0119]

[0120] [Example 8]

[0121] An optical material was prepared through the same process as in Example 1, except that Solvent red 135 (third dye, maximum absorption wavelength: about 470 nm) was additionally mixed as a dye to be mixed with the thiol compound.

[0122]

[0123] [Comparative Examples 1 to 7]

[0124] An optical material was prepared through the same process as in Example 1, except that the ratio of Solvent blue 104 (first dye) and Solvent violet 13 (second dye) included in the polyurethane resin composition was adjusted as shown in Table 1 below.

[0125]

[0126] Classification 1st Dye (x) 2nd Dye (y) 3rd Dye (z) x Total Content (ppm) x+y Total Content (ppm) x+y+z Total Content (ppm) x:y Mixing Ratio (Weight Ratio) x:y:z Mixing Ratio (Weight Ratio) Example 1 0.425 0.425 - 0.425 0.85 - 1:1 - Example 2 0.355 0.355 - 0.355 0.71 - 1:1 - Example 3 0.142 0.568 - 0.142 0.71 - 1:4 - Example 4 0.101 0.609 - 0.101 0.71 - 1:6 - Example 5 0.160 0.640 - 0.160 0.80 - 1:4 - Example 60.1140.686-0.1140.80-1:6-Example 70.700--0.700----Example 80.2330.2330.2330.2330.4660.699-1:1:1Comparative Example 10.3000.300-0.3000.60-1:1-Comparative Example 20.1200.480-0.1200.60-1:4-Comparative Example 30.0860.514-0.0860.60-1:6-Comparative Example 40.0600.540-0.0600.60-1:9-Comparative Example 50.0460.554-0.0460.60-1:12-Comparative Example 60.0380.562-0.0380.60-1:15-Comparative Example 70.0700.630-0.0700.70-1:9-

[0127]

[0128] [Test Example 1]

[0129] The optical materials prepared in each of the examples and comparative examples were analyzed using a UV-VIS Spectrophotometer Lambda 365 to determine the yellowness (Yellow Index, YI), L* value, a* value, and b* value, respectively, and the results are shown in Table 2 below.

[0130]

[0131] Classification Yellowness (YI) L*a*b* Example 1 1.07 94.55 -0.8 10.68 Example 2 0.88 95.01 -0.75 0.76 Example 3 0.97 94.93 -0.65 0.76 Example 4 0.91 94.90 -0.63 0.73 Example 5 0.71 94.86 -0.67 0.64 Example 6 0.80 94.84 -0.65 0.68 Example 71.22 94.77 -0.68 0.83 Example 81.20 94.88 -0.68 0.80 Comparative Example 11.12 94.87 -0.71 0.86 Comparative Example 21.1194.83-0.660.84 Comparative Example 31.1394.85-0.630.84 Comparative Example 41.1894.89-0.640.87 Comparative Example 51.1894.90-0.620.86 Comparative Example 61.1894.90-0.630.86 Comparative Example 71.2294.70-0.570.86

[0132]

[0133] Referring to Table 2 above, it can be confirmed that by manufacturing an optical material (eyeglass lens) using the polyurethane resin composition according to the present invention, the b* value is controlled within the required range, and an optical material with low yellowness (YI) is manufactured.

[0134]

[0135] [Test Example 2]

[0136] The polyurethane resin compositions prepared in each of the examples were stored at room temperature for 30 minutes and 180 days, respectively (specifically, the second formulation included in the polyurethane resin composition was prepared and stored / the first formulation was prepared by mixing with the second formulation without storage), and the curing reaction in Example 1 was carried out to prepare the optical materials, respectively. The b* values ​​of the prepared optical materials were confirmed in the same manner as in Test Example 1 above, and the b* value change index (I according to Formula 1 below) v ) was calculated, and the results are shown in Table 3 below.

[0137] [Equation 1]

[0138] I v = I v2 / I v1

[0139] In the above Equation 1,

[0140] I v1 is the b* value according to CIE Lab colorimeter measurement of an optical material (cured product) prepared from a polyurethane resin composition stored at room temperature for 30 minutes, and

[0141] I v2 b* is the value according to CIE Lab colorimeter measurement of the optical material (cured product) prepared from the above polyurethane resin composition stored at room temperature for 180 days.

[0142]

[0143] Classification I v1 (Store for 30 minutes) v2 (Stored for 180 days) v2 / I v1 Example 10.680.681.00 Example 20.760.761.00 Example 30.760.771.01 Example 40.730.741.01 Example 50.640.651.02 Example 60.680.681.00 Example 70.900.911.01 Example 81.041.051.01

[0144]

[0145] Referring to Table 3 above, it can be seen that the polyurethane resin composition according to the present invention has excellent long-term storage stability, and therefore, the optical material manufactured using it shows almost no change in the b* value.

Claims

1. A polyurethane resin composition comprising an isocyanate compound, a thiol compound, and a dye, wherein The above dye comprises a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm, and A polyurethane resin composition having a thickness of 2 mm and a degree of 0.00 diopters, prepared from the above polyurethane resin composition, wherein the b* value according to CIE Lab colorimeter measurement is less than 0.

84.

2. In Paragraph 1, A polyurethane resin composition comprising a second dye that exhibits a maximum absorption wavelength in the wavelength range of 540 to 590 nm.

3. In Paragraph 2, A polyurethane resin composition in which the mixing ratio (x:y) of the first dye (x) and the second dye (y) is a weight ratio of 1:1 to 9.

4. In Paragraph 2, A polyurethane resin composition in which the total content of the first dye and the second dye is 0.40 to 0.85 ppm based on the total weight of the polyurethane resin composition.

5. In Paragraph 2, A polyurethane resin composition further comprising a third dye in which the above dye exhibits a maximum absorption wavelength in the wavelength range of 450 to 495 nm.

6. In Paragraph 5, A polyurethane resin composition in which the mixing ratio (x:y:z) of the first dye (x), the second dye (y), and the third dye (z) is a weight ratio of 1 to 6 : 1 to 6 : 1 to 6.

7. In Paragraph 1, The index of change in the b* value according to Equation 1 below (I v Polyurethane resin composition having ) 0.95 to 1.1: [Equation 1] I v = I v2 / I v1 In the above Equation 1, I v1 is the b* value according to CIE Lab colorimeter measurement of the cured product prepared from the above polyurethane resin composition stored at room temperature for 30 minutes, and I v2 b* is the value according to CIE Lab colorimeter measurement of the cured product prepared from the above polyurethane resin composition stored at room temperature for 180 days.

8. In Paragraph 1 A polyurethane resin composition having a yellow index of 1.30 or less of the cured product.

9. In Paragraph 1 A polyurethane resin composition further comprising one or more selected from the group consisting of a catalyst, a UV absorber, a heat stabilizer, and a release agent.

10. (1) A step of preparing a first formulation comprising an isocyanate compound; and (2) The step of preparing a second mixture containing a thiol compound and a dye, and The above dye comprises a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm, and A method for preparing a polyurethane resin composition, wherein the cured product, having a thickness of 2 mm and a degree of 0.00 diopters, obtained by a curing reaction of a mixture of the first formulation and the second formulation, has a b* value of less than 0.84 according to CIE Lab colorimeter measurement.

11. An optical material prepared from a polyurethane resin composition comprising an isocyanate compound, a thiol compound, and a dye, wherein The above dye comprises a first dye that exhibits a maximum absorption wavelength in the wavelength range of 610 to 670 nm, and An optical material having a thickness of 2 mm and a power of 0.00 diopters, having a b* value of less than 0.84 according to CIE Lab colorimeter measurements.

12. In Paragraph 11, An optical material in which the above optical material is an eyeglass lens.