KR20210115296A - Optical composition for blocking near-infrared ray and laser - Google Patents

Abstract

The present invention provides an optical composition for blocking electromagnetic waves and a method for preparing an optical lens for blocking near-infrared rays using the same, in which the optical composition for blocking electromagnetic waves comprises: (1) at least one of polyisocyanate compounds; (2) at least one of polythiol compounds; and (3) a near-infrared absorbent of a dimonium-based compound having a near-infrared absorptive power which is less than 70% of a transmittance in the vicinity of 800 to 1200 nm. The optical lens obtained from the optical composition of the present invention can effectively block electromagnetic waves in an ultraviolet wavelength of 400 nm or less and a near-infrared wavelength region of 800 to 1200 nm or a laser wavelength region of 1064 nm.

Description

Optical composition for blocking near-infrared ray and laser

The present invention relates to an optical resin composition capable of blocking electromagnetic waves in an ultraviolet wavelength of 400 nm or less and a near-infrared wavelength region of 800 to 1200 nm or a laser wavelength region of 1064 nm, and a method for manufacturing the same.

Glasses or sunglasses made of the optical composition not only correct eyesight, but also protect the eyes from harmful rays such as ultraviolet rays or infrared rays. When ultraviolet light passes through the human lens, it denatures the protein and induces vision loss. Therefore, if the eye is not protected from UV rays, it can cause various eye inflammations and cause serious damage to the conjunctiva and cornea. Recently, the frequency of cataracts is increasing even among the young generation in their 20s and 40s because the UV rays are getting stronger due to the destruction of the ozone layer. The biggest reason is thought to be that the frequency of exposure to UV rays has increased as the younger generation has increased outdoor activities such as mountain climbing, fishing, and jogging.

On the other hand, near infrared ray (NIR) refers to the infrared wavelength (800 nm to 1200 nm) closest to the radiant heat of the sun, and refers to a ray that transmits a heat wavelength only to an object without heating the air. Near-infrared rays focus on the eye and are known to damage the retina by increasing the intensity by 100,000 times.

Also, among various lasers, the Nd-YAG (Q switched) laser is a near-infrared (1,064 nm) laser, which cannot naturally protect (reflect) people's eyes, such as blinking, and has a very high risk of danger. As reported in Aviat Space Environ Med (2003 Sep; 74 (9): 947-52), there were 10 representative cases of laser eye injuries in the US military between 1984 and 2000, in which the patient suffered retinal damage, Most of them used a Q-switched Neodynium:Nd-YAG (Nd:Nd-YAG) laser with a wavelength of 1064 nm, and the accident occurred in various places, including indoors and outdoors.

In sunglasses for blocking infrared and ultraviolet rays, a method of adding an infrared absorber for blocking infrared transmission or an ultraviolet absorber for blocking ultraviolet transmission is applied (for example, Japanese Patent Laid-Open No. 2007-271744, No. 1200) -007871). In particular, Japanese Patent Publication No. 5166482 discloses an optical resin composition capable of blocking near-infrared rays with transmittance of about 5% or less in a wavelength region of 800 to 1000 nm, which is a near-infrared region. In such technical literature, polycarbonate resin is applied to a phthalocyanine dye (A) in a wavelength range of 800 nm to 850 nm, a phthalocyanine dye (B) in a wavelength range of 950 nm to 1000 nm, and a wavelength range of 875 nm to 925 nm. A method for manufacturing an optical lens, characterized in that the phthalocyanine-based dye (C) is mixed in a specific ratio, melted and injected together with the resin, and an optical lens manufactured therefrom are disclosed.

According to the Japanese Patent Publication No. 5166482, diethylene glycol bis-allyl carbonate (CR-39), polymethyl methacrylate (PMMA), Methyl methacrylate (MMA) and the like are exemplified, and polycarbonate (PC) is particularly preferable. However, diethylene glycol bis-allyl carbonate (CR-39) presented in these known documents is a thermosetting resin, and its properties are different from that of polycarbonate (PC), which is a thermoplastic resin. I can't do it, but I'm just referring to it on an equal footing with other thermoplastic resins.

Polythiourethane, a thermosetting resin, is a resin that can be cured at a low temperature of 120 to 130 ° C. When a phthalocyanine-based near-infrared absorber is applied, it is very limited compared to the entire infrared absorption region (800-1200 nm).

On the other hand, in Korea Patent Laid-Open Publication No. 10-2010-0014582, a 780-2500 nm infrared absorbing polyurethane resin-based spectacle lens development technology was developed by adding a dimonium compound, which is a thermally stabilized absorbent to block infrared and ultraviolet rays. However, the components of urethane materials are limited to polyols.

In addition, a technique of expanding the absorption range of 780 to 2500 nm using a dimonium-based absorbent has been disclosed, but it is limited to a polyurethane lens composed of a polyol having a low refractive index.

Polycarbonate (PC), a thermoplastic resin, is a resin that can be melted at a high temperature of 250 ° C. or higher, but there is a risk that phthalocyanine-based materials known as near-infrared absorbers may be thermally decomposed when injection-molded with such a thermoplastic resin. In addition, the absorbent has a disadvantage in that it is difficult to be uniformly distributed in the molten high-viscosity resin of polycarbonate whose molecular weight has already been determined. Therefore, in order to prepare an optical resin composition for blocking infrared rays using a phthalocyanine system, it is necessary to cure the phthalocyanine system through a mold polymerization reaction, which is a mold injection method, at a relatively low temperature at which the phthalocyanine system is not thermally decomposed. In addition, it is required to heat-set the absorbent by mixing it with the liquid monomer for polymer so that it can be uniformly mixed with the composition of the monomer for thermosetting resin.

A high refractive lens using polythiol that can improve refractive index by using a dimonium-based absorbent is required. In addition, for the diffusion of safety glasses for lasers for user safety, it is necessary to supplement the disadvantage of durability deterioration due to scratches as an existing coating method by developing a lens with an absorbent with a high absorption rate of 1064 nm wavelength.

A lens composed of diisocyanate and polyol can function as a near-infrared blocking urethane lens to which a dimonium compound is added, but cannot function as a high-refractive lens with a refractive index of 1.60 or higher. Therefore, while blocking near-infrared rays, a polyurethane lens that requires a high refractive index of 1.60 or more rather than a coating method is still in demand.

As a result of closely studying the above problems, the present inventors confirmed that certain dimonium compounds were stable to some polythiol compounds and that the near-infrared blocking function was maintained even after curing. In addition, it was confirmed that it was particularly excellent in blocking the wavelength of 1064 nm and exhibited even the Nd YAG laser blocking function, thereby enabling the invention of a lens composition and a lens having a high refractive index of 1.60 or more.

The present invention provides an optical composition for blocking electromagnetic waves,

(1) at least one of polyisocyanate compounds; and

(2) at least one polythiol compound; and

(3) a near-infrared absorber of a dimonium-based compound having a transmittance of less than 70% near-infrared absorption in the vicinity of 800 to 1200 nm; it relates to an optical composition for blocking electromagnetic waves, including.

In the present invention, the dimonium-based compound is preferably a dye having a minimum value of a spectral transmittance curve of less than 5% transmittance within a wavelength region of (1) 400 nm, and (2) a wavelength region of 800 nm to 1200 nm. do. In addition, the dimonium-based compound is preferably a dye having a maximum value of the spectral transmittance curve of an optical density of 4 or more (= transmittance 0.01% or less) at a single wavelength of 1064 nm.

In the present invention, the polyisocyanate compound is xylylene diisocyanate (XDI), 2,5(6)-bis(isocyanatemethyl)-bicyclo[2,2,1]heptane (NBDI), 1,6-hexamethylenedi It is preferably at least one selected from the group consisting of isocyanate (HDI) and isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI) and biurets of aliphatic isocyanates.

In addition, in the present invention, the polythiol compound is [1,4]dithiane-2,5-diyl-dimethanol, (2,5-dimethyl-[1,4]-dithiane-2,5-diyl ) It is preferably at least one selected from the group consisting of dimanethiol, 2,2'-([1,4]-yatian-2,5diyl)diethanethiol.

In the present invention, the content of the near-infrared absorber may be in the range of 0.01 to 0.5% by weight based on the optical composition.

Furthermore, the molar ratio of the functional group of NCO/SH in the functional group (-NCO) of the polyisocyanate and the functional group (-SH) of the polythiol may be in the range of 0.5 to 1.5.

According to the method of the present invention, there is provided a sunglasses (glasses) lens that can effectively block the near-infrared wavelength region of 800 nm to 1200 nm, along with ultraviolet rays of 400 nm or less contained in sunlight emitting electromagnetic waves, It can effectively protect your eyes from infrared rays.

In addition, it is possible to provide an optical composition and lens capable of effectively blocking the Nd YAG laser wavelength, that is, blocking the wavelength of 1064 nm with an absorption capacity of 4 or more optical density.

1 is a representative UV-VIS-NIR absorption spectrum of the near-infrared blocking lens obtained in Example 1, when using an absorbent 1000 ppm, EXP-1) shows a transmittance curve, EXP-2) shows an absorbance curve .
FIG. 2 is a representative UV-VIS-NIR absorption spectrum of the near-infrared blocking lens obtained in Example 2, when diisocyanate is different among the components of the near-infrared blocking lens used in FIG. 1, and when 1000 ppm of the absorbent is used, EXP-3) shows the transmittance curve and EXP-4) is a graph showing the absorbance curve evaluation result.
3 is a representative UV-VIS-NIR absorption spectrum of the near-infrared blocking lens obtained in Comparative Example, different from the components of the near-infrared blocking lens used in FIGS. In case EXP-5) shows the transmittance curve, EXP-6) is a graph showing the evaluation result of the absorbance curve.

Hereinafter, the present invention will be described in detail with reference to the drawings, along with various embodiments.

In general, a polyurethane-based optical lens is obtained by mixing liquid (I) polyisocyanate and liquid (II) polythiol, which are polyurethane components, and degassing to obtain a uniform optical composition, and then heat curing in a desired glass mold. Manufactured by mold release. As such, the reason for separately preparing the liquid phase (I) and liquid phase (II) is that the functional group (-NCO) of the isocyanate and the functional group (-SH) of the polythiol easily polymerize when mixed, so it must be stored separately. . In addition, this is because the resin in the form of a lens can be obtained by mixing the two liquids during lens polymerization, injecting them directly into the mold, and then polymerization by the curing program. Therefore, it is necessary to prepare and store liquid (I) and liquid (II) separately.

In addition, the polyurethane-based optical lens for blocking near-infrared rays includes a solid near-infrared absorber mixed with one or more pigments in addition to liquid (I) polyisocyanate and liquid (II) polythiol. However, since the near-infrared absorber is a solid, it is necessary to prepare a uniform absorbent solution by uniformly mixing the absorbent with the polyisocyanate used in the liquid phase (I) in advance.

In the present invention, as described above, (1) at least one of polyisocyanate compounds; and (2) an optical composition comprising a near-infrared absorber having a near-infrared absorption ability, (3) by adding at least one of polythiol compounds as liquid (II) to prepare a final optical composition for blocking electromagnetic waves. However, as will be described later, the final optical composition for shielding electromagnetic waves of the present invention is from the beginning (1) a polyisocyanate compound; (2) polythiol compounds; And (3) it may be prepared by sequentially mixing the near-infrared absorber.

In the present invention, examples of the polyisocyanate compound used as the compound of the liquid phase (I) may be subdivided into aliphatic polyisocyanate, cycloaliphatic polyisocyanate, and aromatic polyisocyanate, and each example is as follows:

i) ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexanedi Isocyanate, decamethylene diisocyanate, burenediisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-Undae cattriisocyanate, 1,3, 6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, bis(isocyanateethyl)carbonate, Bis(isocyanate ethyl) ether, 1,4-butylene glycol dipropyl ether-W, W'-diisocyanate, ridine diisocyanate methyl ester, ridine triisocyanate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate , 2-isocyanate propyl-2,6-diisocyanate hexanoate, xylylene diisocyanate, bis (isocyanate ethyl) benzene, bis (isocyanate propyl) benzene, α, α, α', α'-tetramethylxylylenedi Isocyanate, bis(isocyanatebutyl)benzene, bis(isocyanatemethyl)naphthalene, bis(isocyanatemethyl)diphenyl ether, bis(isocyanateethyl)phthalate, mesitylylenetriisocyanate, 2,6-di(isocyanatemethyl)furan, etc. of aliphatic polyisocyanates,

ii) isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexyl Methane diisocyanate, bis(4-isocyanate-n-butylidene)pentaerythritol, dimer acid diisocyanate, 2-isocyanatemethyl-3-(3-isocyanatepropyl)-5-isocyanatemethyl-bicyclo-2, 2, 1-Heptane, 2-isocyanatemethyl-3-(3-isocyanatepropyl)-6-isocyanatemethyl-bicyclo-[2,2,1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatepropyl)- 5-isocyanatemethyl-bicyclo-[2,2,1]-heptane, 2-isocyanatemethyl-3-(3-isocyanatepropyl)-6-isocyanatemethyl-bicyclo-[2,2,1]-heptane, 2-isocyanatemethyl-3-(3-isocyanatepropyl)-5-(2-isocyanatemethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatemethyl-3-(3-isocyanatepropyl)- 6-(2-isocyanatemethyl-bicyclo-2, 2, 1-heptane, 2-isocyanatemethyl-3-(3-isocyanatepropyl)-5-(2-isocyanatemethyl-bicyclo-2, 2, 1- alicyclic polyisocyanates such as heptane, 2-isocyanatemethyl-3-(3-isocyanatepropyl)-6-(2-isocyanatemethyl-bicyclo-2,2, 1-heptane;

iii) Phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthaline Diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl, 4 ,4'-diisocyanate, bis(isocyanatephenyl)ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, Polymelic MDI, naphthaline triisocyanate, diphenyl Methane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5,2',4',6', -Pentisocyanate, phenyl isocyanate methyl isocyanate, phenyl isocyanate ethyl isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diisocyanate Phenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofuran diisocyanate, carbazole diisocyanate, ethyl carbazole diisocyanate, dichlorocarba Aromatic polyisocyanates, such as zoldi isocyanate, etc.

The polyisocyanate compound used in the present invention is xylylene diisocyanate (XDI), 2,5(6)-bis(isocyanatemethyl)-bicyclo[2,2,1]heptane (NBDI), 1,6-hexamethylene It is preferably at least one selected from the group consisting of diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H12MDI) and biuret of aliphatic isocyanate. Further, in the present invention, as the polythiol compound used as the compound of liquid phase (II), there are the following compounds:

In addition to 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, trimethylolpropane tris(mercaptopropionate), and pentaerythritoltetrakis(mercaptopropionate), 2,3- Bis(2-mercaptoethylthio)propane-1-thiol, 2-(2-mercaptoethylthio)-3-[2-(3-mercapto-2-(2-mercaptoethylthio)-propylthio ]ethylthio-propane-1-thiol, 2-(2-mercaptoethylthio)-3-{2-mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio ]Propylthio}-propane-1-thiol, trimethylolpropane tris(mercaptopropionate, trimethylolethane tris(mercaptopropionate), glycerol tris(mercaptopropionate), trimethylolchlorotris(mer captopropionate), trimethylolpropane tris(mercaptoacetate), trimethylolethane tris(mercaptoacetate, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakismercaptoacetate, [1,4] Dithian-2-yl-methanethiol, 2-(2-mercapto-ethylsulfanyl)-propane-1,3-dithiol, 2-([1,4]dithiane-2ylmethylsulfanyl)- Ethanethiol, 3-(3-mercapto-propionylsulfanyl)-propionic acid 2-hydroxylmethyl-3-(3-mercapto-propionyloxy)-2-(3-mercapto-propionyloxy) Methyl)-propyl ester, 3-(3-mercapto-propionylsulfanyl)-propionic acid 3-(3-mercapto-propionyloxy)-2,2-bis-(3-mercapto-propionyl) Oxymethyl)-propyl ester, (5-mercaptomethyl-[1,4]dithian-2-yl)-methanethiol, 1,3-bis(2-mercaptoethylthio)propane-2-thiol (MET ), (3,6,10,13-tetrathiapentadecane-1,8,15-trithiol) (SET), 2- (2-mercaptoethylthio) propane-1,3-dithiol (GMT) One or two selected from the group consisting of polythiol compounds such as , 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane (DMDDU) may be used. have.

Preferred polythiol compounds in the present invention are [1,4]dithiane-2,5-diyl-dimethanol (CET) (compound of formula (1)), (2,5-dimethyl-[ 1,4]-dithiane-2,5-diyl)dimethanethiol (CMET) (compound of formula (2)), 2,2'-([1,4]-yathian-2,5-diyl)diethane thiol (CDET) (compound of formula (3)):

(1)

(One)

(2)

(2)

(3)

(3)

On the other hand, in the present invention, the molar ratio of the functional group of NCO/SH in the functional group (-NCO) of the polyisocyanate used as the liquid phase (I) and the functional group (-SH) of the polythiol used as the liquid phase (II) is in the range of 0.5 to 1.5. It is preferable to use Furthermore, in order to further improve the physical properties of the optical lens, a molar ratio of 0.9 to 1.1 is preferable, and it is more preferable to use a molar ratio of 1.0.

In the case of polythiol, a resin with a high refractive index of 1.60 to 1.62 (nD) or higher can be obtained by using only CET, but this high refractive index is not required for all lenses. Therefore, the polythiol used in the present invention does not need to be particularly limited to CET.

As the infrared absorber used in the present invention, an infrared absorber that absorbs infrared light over a wavelength range of 780 to 2500 nm may be selected, and a known infrared absorbing dye may be adopted, for example, the following may be mentioned:

(1) N,N,N',N'-tetrakis(p-substituted phenyl)-p-phenylenediamine derived through oxidation from N,N,N',N'-tetrakis(p-substituted) a compound in the form of a salt consisting of a phenyl)-p-phenylene cation and a corresponding anion;

(2) N,N,N',N'-tetraarylquinone diimonium salts;

(3) Bis-(p-dialkylaminophenyl)[N,N-bis(p-dialkylaminophenyl)p-aminophenyl]aminium salt.

However, the present inventors, as an infrared absorber, are stable to some polythiol compounds among known dimonium compounds and maintain a near-infrared blocking function even after curing, a dimonium compound that absorbs near-infrared over the wavelength range of 800 to 1200 nm. Confirmed. In addition, it was confirmed that this compound exhibited even Nd YAG laser blocking function due to its excellent blocking ability at a wavelength of 1064 nm, and it was confirmed that it was suitable for lens compositions and lenses having a high refractive index of 1.60 or more.

The dimonium-based compound preferably used in the present invention is a compound of the following formula (4) using a phenylenediamine intermediate (US20040137367A1, KR100603897B1):

(4)

(4)

Among the dimonium compounds having a representative structure of Formula (4), the compound having the most stability to heat is one in which the substituent R is a branched alkyl group. Specific examples of the branched alkyl group include 1-methylethyl group (isopropyl group), 1,1-dimethylethyl group (t-butyl group), 1-methylpropyl group (sec-butyl), 1,1-dimethylpropyl group, 2 -Methylpropyl group (isobutyl group), 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group (isoamyl group), 1 ,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl, and an alkyl group having 1 to 10 carbon atoms are preferable. Among them, 2-ethylbutyl group and the like are preferred. can be heard

X is an anion necessary for neutralization of charge, and when X is a divalent anion, 1 mole is required, and when X is a monovalent anion, 2 moles are required. Such anions are selected from organic acid anions or inorganic anions. As a specific example of an organic acid anion, Organic carboxylate ions, such as an acetate ion, a lactate ion, a trifluoroacetate ion, a propionate ion, a benzoate ion, an oxalate ion, a succinate ion, and a stearate ion; Methanesulfonate ion, toluenesulfonate ion, naphthalenemonosulfonate ion, naphthaleneisophonate ion, chlorobenzsulfonate ion, chlorobenzsulfonate ion, nitrobenzenesulfonate ion, dodecylbenzenesulfonate ion, benzene sulfonate ions, organic sulfonate ions such as ethanesulfonate ions, and the like.

Examples of the inorganic anion include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion; Thiocyanate ion, hexafluoroantimonic acid ion, perchlorate ion, periodate ion, nitrate ion, tetrafluoroborate ion, hexafluorophosphate ion, molybdate ion, tungstate ion, titanate ion, vanadata ion , phosphate ion, borate ion and perchlorate ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion and hexafluoroantinate ion are preferable.

Among the anions, for example, perchlorate ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, trifluoromethanesulfonate ion and toluenesulfonate ion and the like are preferable.

In particular, preferred in the present invention are compounds in the form of salts of the formula (5):

(5)

(5)

The content of the near-infrared absorber included in the optical composition is in the range of 0.01 to 0.5% by weight, preferably in the range of 0.02 to 0.1% by weight, more preferably in the range of 0.03 to 0.08% by weight, based on the optical composition. If the content of the near-infrared absorbent is less than this range, there is a problem in the near-infrared absorption ability, and if it exceeds this range, it is uneconomical.

In the present invention, when the content of the diinonium-based compound of Formula (5) is based on the optical composition, when a lens is manufactured using an optical composition existing within the above range, the dimonium-based compound is (1) 400 nm It will be possible to act as a dye having a minimum value of the spectral transmittance curve of less than 5% transmittance within the wavelength region of , and (2) the wavelength region of 800 nm to 1200 nm.

In addition, the dimonium-based compound will be able to act as a dye having the maximum value of the spectral transmittance curve with an optical density of 4 or more (= transmittance 0.01% or less) even at a single wavelength of 1064 nm.

Meanwhile, a polarization function, a dimming function, or a combination of these functions may be additionally provided to the optical lens prepared from the optical composition for blocking electromagnetic waves obtained in the present invention.

It is necessary to evaluate whether the optical lens manufactured by the present invention has suitable physical properties as a near-infrared blocking spectacle lens. As each physical property value, (1) refractive index (nD), (2) transmittance (T %), (3) optical density (OD), etc. were evaluated by the following apparatus or test method.

(1) Refractive index (nD): It was measured at 20° C. using an ABBE refractometer, which is a 1T model by ATAGO.

(2) Near-infrared blocking and transmittance (T %): A test piece prepared on a plate with a lens thickness of 1.2 mm was tested with a SHIMADZU, UV/Vis-NIR spectrophotometer UV-3600 analyzer from the absorption spectrum of the lens to the visible light region (400 to 800). nm) was directly measured.

(3) Optical Density (OD): This was measured in terms of optical density (OD), which is the absorbance for each wavelength, using a UV/VIS Spectrometer to evaluate the blocking performance for this light.

Absorbance: A = log(I ₀ /I ) = -log(I/I ₀ ) = -logT = OD

Permeability (I ₀ /I) %T (transmittance) Absorption rate (%) A (absorbance), OD One 100 0 0 0.1 10 90% One 0.01 One 99% 2 0.001 0.1 99.9% 3 0.0001 0.01 99.99% 4

A brief look at the manufacturing method of a representative optical lens is as follows.

The monomer constituting the polyisocyanate and the near-infrared absorber are mixed in a specific ratio, and the monomer constituting the polythiol is mixed thereto in a specific ratio, and the mixture is stirred. Then, each specific amount of an internal release agent, an organic dye, a curing catalyst and the like is added to the obtained mixture. Then, using the finally obtained polyurethane optical resin composition, a polyurethane optical lens is obtained by polymerization and lens manufacturing processes conventional in the art. Then, processing, washing, annealing, vacuum deposition, etc. are performed on the lens to a specific diameter as necessary to obtain a coated lens.

Synthesis example

(1) tertiary amine derivative synthesis; (N1,N1'-(1,4-phenylene)bis(N4,N4-di-sec-butyl-N1-(4-(di-sec-butylamino)phenyl)benzene-1,4-diamine))

3.8 g of N.N,N',N'-tetrakis(aminophenyl)-p-phenylenediamine was dissolved in 30 ml of DMF. 21 g of isobutyl bromide and 15 g of potassium carbonate were added, and the mixture was stirred at 80° C. for 1 hour, at 90° C. for 7 hours and at 130° C. for 1 hour.

When the reaction was completed, it was cooled to room temperature, the insoluble solid was filtered off and washed with 30 ml of iso-propanol. The filtered filtrate was cooled to 0-5° C. and stirred for 1 hour to form crystals. The resulting crystals were washed with 10 ml methanol and dried at 60° C. to obtain 4.2 g of a light brown solid.

(2) Diimonium salt synthesis (Formula 5)

1 g of the tertiary amine synthesized above was added to 10 ml of DMF, and the internal temperature of the reaction was raised to 60° C. and dissolved. Here, 0.78 g of silver hexafluoroantimonate was slowly added to the solution in 10 ml of DMF at 60° C. for 5 minutes, followed by stirring at 60° C. for 0.5 hours. The internal temperature of the reaction was lowered to 20° C., and silver metal generated according to the reaction was filtered. 10ml of purified water was slowly added to the filtered reaction filtrate and stirred for 15 minutes. The resulting black crystals were filtered and washed thoroughly with 50 ml of water. After drying at 60° C. for 1 day, a final 0.81 g of dimonium hexafluoroantimonate salt was prepared.

(Example)

Example 1

30 g of 1,3-(isoanthomethyl) cyclohexane (1,3-BIC) and 0.062 g of a near-infrared absorber (corresponding to about 1000 ppm of the total weight of isocyanate and polythiol) The mixture is stirred for 40 minutes to obtain a liquid (I) polyisocyanate and near-infrared absorber mixture to obtain a liquid (I) compound. Subsequently, as a polythiol compound, 32.81 g of CET is mixed and stirred at a pressure of 10 torr or less for 40 minutes to obtain a liquid (II) polythiol. Then, 56.48 g of the liquid (I) mixture was mixed with the obtained liquid (II) mixture, and 0.25 g of a release agent (acid phosphate ester commercially available as 'ZELEC UN' by DUPONT) ((4000 ppm of total isocyanate and polythiol weight) (corresponding to ), and stirred for about 40 minutes at a pressure of 10 torr or less.

Finally, 0.044 g of catalyst (corresponding to about 700 ppm of total isocyanate and polythiol weight) (dibutyltin chloride) is mixed and stirred at a pressure of 10 torr or less for about 20 minutes to finally obtain an optical resin composition. Put the obtained composition into an adhesive-tape glass mold and program it in advance (room temperature to 35℃ 4 hours, 35 to 50℃ 5 hours, 50 to 75℃ 4.5 hours, 75 to 90℃ 5 hours, 90℃3 Time keeping, 90~130℃ 2 hours, 130℃ 1.5 hours keeping, 130~70℃ 1 hour cooling), after curing in an oven, release to obtain a lens. The results of UV-Vis-NIR analysis of the obtained near-infrared blocking lens are shown in FIG. 1 .

1 is an analysis result of a typical UV-VIS-NIR absorption spectrum of a near-infrared blocking lens. The Y-axis represents transmittance (T%) and absorbance (Abs=OD), and the X-axis represents the wavelength (nm). In the graph of FIG. 1 , the transmittance curve of (EXP-1) shows that UV rays of 400 nm or less were blocked even without the UV absorber.

In addition, the visible light of 400~800nm is partially blocked and the transmittance is 10~20% or more, so that it can be seen with the naked eye. If the transmittance of visible light is 0%, it is good that the transmittance is high because the eyes cannot be seen when the lens is worn. However, since there is a side effect of blocking visible light when a large amount of the near-infrared absorber is added, it is necessary to add it in an appropriate range.

The absorbance curve of (EXP-2) in the graph of FIG. 1 shows an optical density (OD) of 4 or more at a wavelength of 1064 nm.

Example 2

Except that 31.86 g of bononene diisocyanate (NBDI) was used instead of 1,3-BIC in Example 1, the remaining components and procedures were the same as in Example 1.

The results of UV-Vis-NIR analysis of the obtained near-infrared blocking lens are shown in FIG. 2 . The transmittance curve of EXP-3 of FIG. 2 is similar to the transmittance curve of EXP-1 of FIG. 1, even without a UV absorber, ultraviolet rays below 400 nm are blocked, and visible light of 400 to 800 nm is partially blocked, and 800 to 1200 nm indicates that most of them are blocked.

The absorbance curve of (EXP-4) in the graph of FIG. 1 also shows an optical density (OD) of 4 or more at a wavelength of 1064 nm (EXP-2) of FIG. 1 .

Comparative Example 1

As a comparative example, the infrared absorber described in Korean Patent Laid-Open Publication No. 10-2010-0014582 cannot be applied to a polyurethane-based resin with high refractive index, which is a resin of a currently common spectacle lens.

High refractive index resin (MR-8 manufactured by Mitsui Chemicals, Refractive index 1.60) 0.1 parts by weight of an infrared absorber (Compound 5) was added to 100 parts by weight to prepare a lens.

The UV-Vis-NIR analysis result of the obtained lens (thickness 3 mm) is shown in FIG.

The EXP-5 transmittance curve of FIG. 3 shows that it is not blocked in the wavelength region of 800 to 1200 nm, and the absorbance curve of EXP-6 shows that the optical density at the wavelength of 1064 nm is significantly lower.

In Table 1, physical properties such as refractive index, transmittance, and optical density were measured according to the above-described measuring method for lens properties according to each monomer composition of Examples 1 and 2 and Comparative Example 1, and the results are summarized.

Transmittance below 400 nm (%) 400~800nm Transmittance(%) 800-1200 nm Transmittance (%) 1064 nm optical density (OD) refractive index (n _d ) Example 1 0 23.7 0.5 4.1 1.6174 Example 2 0.1 25.2 0.2 3.8 1.6142 Comparative Example 1 0.1 89.0 84 0.1 1.6014

In Examples 1 and 2, the lenses with a refractive index of 1.60 or more had a visible light transmittance of 23% or more, making it possible to recognize objects more transparently than using sunglasses. It is possible to block more than 99.9% even without adding. The transmittance of 800 to 1200 nm in the near-infrared region is also 0.5% or less. In particular, at a wavelength of 1064 nm, the optical density is at most 3.8 to 4.1, and on average, it has an absorption rate of 99.99% or more, so that an efficient lens can be provided to the user of the Nd YAG laser device.

When the 1.60 resin commercialized in Comparative Example 1 was applied, the absorption function of the near-infrared absorber was significantly lowered to about 89% in transmittance in a wavelength range of 800 to 1200 nm. It is determined that the near-infrared absorption function is lowered because the dimonium-based compound reacts with polythiols other than alicyclic polythiols.

(Granting additional function of optical lens)

This invention is not limited to said embodiment. For example, in the polyurethane resin substrate of the present invention, in addition to polarizing functions (function for minimizing reflected light on the surface of a non-metallic object that transmits light only at a specific angle), dimming functions (ambient environment and space) It will be possible to give a function that can automatically control the illuminance in consideration of the utilization rate). Furthermore, especially in the case of an optical lens, it may be possible to provide a vision correction function.

Claims (7)

An optical composition for blocking electromagnetic waves, comprising:
(1) at least one of polyisocyanate compounds; and
(2) at least one polythiol compound; and
(3) a near-infrared absorber of a dimonium-based compound having a transmittance of less than 70% near-infrared absorption in the vicinity of 800 to 1200 nm;
Including, an optical composition for blocking electromagnetic waves. According to claim 1, wherein the dimonium-based compound is a dye having a minimum value of the spectral transmittance curve of less than 5% transmittance within a wavelength range of (1) 400 nm, and (2) a wavelength range of 800 nm to 1200 nm. , An optical composition for blocking electromagnetic waves. The optical composition for blocking electromagnetic waves according to claim 1, wherein the dimonium-based compound is a dye having a maximum value of a spectral transmittance curve of an optical density of 4 or more (= transmittance 0.01% or less) at a single wavelength of 1064 nm. 4. The polyisocyanate compound according to any one of claims 1 to 3, wherein the polyisocyanate compound is xylylenediisocyanate (XDI), 2,5(6)-bis(isocyanatemethyl)-bicyclo[2,2,1]heptane. (NBDI), at least one selected from the group consisting of biuret of 1,6-hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI) and aliphatic isocyanate, electromagnetic waves An optical composition for blocking. 4. The method according to any one of claims 1 to 3, wherein the polythiol compound is [1,4]dithiane-2,5-diyl-dimethanol, (2,5-dimethyl-[1,4]-dithiol) At least one selected from the group consisting of an-2,5-diyl)dimethanol, 2,2'-([1,4]-yatian-2,5-diyl)diethanethiol, an optical composition for blocking electromagnetic waves. The optical composition for blocking electromagnetic waves according to any one of claims 1 to 3, wherein the content of the near-infrared absorber is in the range of 0.01 to 0.5% by weight based on the optical composition. The method for blocking electromagnetic waves according to any one of claims 1 to 3, wherein the molar ratio of the functional group of NCO/SH in the functional group (-NCO) of the polyisocyanate and the functional group (-SH) of the polythiol is in the range of 0.5 to 1.5. optical composition.

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