KR100376285B1 - Process for preparing Photochromic plastic lens - Google Patents

Abstract

The present invention relates to a method of manufacturing a photochromic plastic lens, and more particularly, to a functional group of an aromatic radical polymerizable monomer represented by the following formula (1) and an spirobenzopyran, diarylethene or azobenzene having an absorption wave of 250 nm or more Using a photochromic compound, and a photochromic composition of a specific composition containing a photoinitiator, in the reaction of thermosetting the composition by specifically configuring the temperature and curing time step by step, the refractive index, surface hardness and The present invention relates to a method of manufacturing a photochromic plastic lens having excellent photochromic life and capable of controlling a wide range of refractive indices by a composition change.

In Chemical Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X, Y, Z, k, 1, m, and n are as defined in the detailed description of the invention, respectively.

Description

Process for preparing photochromic plastic lens

The present invention relates to a method of manufacturing a photochromic plastic lens, and more particularly, to a functional group of an aromatic radical polymerizable monomer represented by the following formula (1) and an spirobenzopyran, diarylethene or azobenzene having an absorption wave of 250 nm or more Using a photochromic compound, and a photochromic composition of a specific composition containing a photoinitiator, in the reaction of thermosetting the composition by specifically configuring the temperature and curing time step by step, the refractive index, surface hardness and The present invention relates to a method of manufacturing a photochromic plastic lens having excellent photochromic life and capable of controlling a wide range of refractive indices by a composition change.

[Formula 1]

In Formula 1 above:

R ₁ and R ₂ , which are the same as or different from each other, are H or a C _{1 to} C ₄ alkyl group; R ₃ and R ₄ are the same as R ₁ and R ₂ or are a C ₁ -C ₄ haloalkyl group; R ₅ is H, a C _{1 to} C ₄ alkyl group or ego; Z is a direct bond, , -S- or -O-; Y is a direct bond, -S-, -SO _2- , -OC (= O)-, -C (= O)-, -C (= O) -O-, -OC (= O) -O- or ego; X is H, -O-, -S-, -SO _2- , -C (= O)-or ego; k is an integer of 0 or 1; l is an integer of 1 or 2; m is an integer of 0, 1 or 2; n is 0 or an integer of 1-20.

The term "photochromic property" refers to a property of changing color under the influence of multicolored light or monochromatic light, and means a property of changing color before and after light irradiation. The photochromic compound is a compound having an intramolecular conjugated structure, and the color is expressed or lost as the structure is changed at a specific range of wavelengths and the refractive index is changed. This photochromic characteristic shows the repeatability of recording and erasing, and is effective for transmitting information. Thus, the optical discoloration characteristics can be used for an optical lens, a filter, a switch, and the like to achieve the function of recording and erasing by a specific range of wavelengths.

On the other hand, the technique which hardens | cures an acryl-type compound, a methacryl type compound, and the compound which has an unsaturated aliphatic substituent by radical polymerization and uses for a polymer substrate or a lens is known. Therefore, since the polymer obtained by the radical polymerization by containing a photochromic compound in the radically polymerizable monomer exhibits photochromic properties, it can be used to produce a molded article such as a photochromic polymer substrate or a lens.

Accordingly, some photochromic resin compositions containing photochromic compounds to impart photochromic properties while containing radically polymerizable monomers to enable molding are currently known. It is possible to manufacture photochromic molded articles having a function of erasing, and researches on this are being conducted in various ways.

As an example, US Pat. No. 5,708,064 discloses ethoxylated bisphenol A dimethacrylate, polyoxyethylene dimethacrylate, 1,3-diisopropenylbenzene, 2-phenoxyethyl methacrylate, polyethylene glycol 200 BACKGROUND OF THE INVENTION A method for producing a photochromic lens by thermosetting a high refractive photochromic resin composition comprising dibenzoate, triphenyl phosphate, diisopropyl peroxydicarbonate, and t-butylperoxy isopropanol carbonate is known. However, the manufactured lens has a low refractive index of 1.55 or less and has a problem that it is difficult to produce a uniform thin film.

In addition, US Patent No. 5,910,516 discloses a radically polymerizable monomer containing bisphenol A-based (meth) acryl, a spiroxazine-based or full-gid photochromic compound having an absorption wave of 400 nm or more, and a spectral characteristic at 400 nm or more. BACKGROUND OF THE INVENTION A method of producing a photochromic cured product from a photochromic resin composition composed of photoinitiators is known. This curing method can be cured in a short time, it is known that the cured material exhibits photochromic properties. However, since it is manufactured using bisphenol A-based (meth) acryl as a radical polymerizable monomer, the material does not have a high refractive index, and because it uses a compound that causes photopolymerization at 400 nm or more, the curing reaction is not efficient and the inconvenience of using a filter is inconvenient. There is this. In addition, since photochromic resins have low heat resistance and surface hardness, and poor photochromic repeatability, the variable color life is very short, and thus optical recording products manufactured using the photochromic resins have poor heat resistance and mechanical properties and have short recording-reproducing, making them practical. There is a problem.

Accordingly, there is an urgent need for the development of a photochromic resin composition having a new composition having high refractive index, excellent heat resistance and surface hardness, long photochromic repeat life and excellent processability.

The present inventors have tried for many years to solve the above problems. As a result, photochromic selected from diarylethene-based, spiro-benzopyran-based, and diazo-based systems having absorption waves of 250 nm or more in the aromatic radical polymerizable monomer [Korean Patent No. 357685] developed and patented by the researchers. The present invention was completed by finding that a photochromic molded article prepared using a photochromic resin composition containing a certain amount of a compound and a photoinitiator has excellent physical properties such as transparency, refractive index, photochromic repeatability, hardness, and heat resistance.

Accordingly, the present invention is very excellent in surface hardness, refractive index and photochromic repeatability, using a photochromic resin composition that can be effectively applied to functional optical lenses, filters, imaging, display devices or optical integrated devices, optical disks or optical recording media, etc. It is an object to provide a method of manufacturing a photochromic plastic lens.

1 shows photochromic properties of a high refractive photochromic plastic lens (Example 2) prepared using the photochromic resin composition of the present invention.

Figure 2 shows a photochromic image (Example 5) prepared using the photochromic resin composition of the present invention.

The present invention is 100 parts by weight of at least one monomer selected from the aromatic radical polymerizable monomer represented by the following formula (1); 0.001 to 90 parts by weight of at least one photochromic compound selected from diarylethene-based, spirobenzopyran-based and diazo-based having an absorption wave of 250 nm or more; And a photochromic resin composition containing 0.1 to 10 parts by weight of a photoinitiator,

30 minutes to 360 minutes at room temperature to 70 ℃ to start the decomposition reaction of the initiator, 110 to 180 minutes at 70 to 80 ℃, 110 to 130 minutes at 85 to 95 ℃, 110 to 130 ℃ After maintaining for 30 to 240 minutes, a method of manufacturing a photochromic plastic lens is characterized by performing a thermosetting process by temperature control consisting of a process of natural cooling.

Formula 1

In Chemical Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X, Y, Z, k, 1, m and n are the same as defined above.

The present invention will be described in more detail as follows.

The present invention contains an aromatic radical polymerizable monomer represented by Formula 1, a specific photochromic compound having an absorbing wave of 250 nm or more, and a photoinitiator in a predetermined content ratio, and thus have excellent surface hardness, refractive index, photochromic repeatability, and the like. The present invention relates to a method of manufacturing a photochromic plastic lens using a photochromic resin composition that can be effectively applied to an optical lens, a filter, an imaging, a display device or an optical integrated device, an optical disk, or an optical recording medium.

Hereinafter, the respective composition components constituting the photochromic resin composition according to the present invention will be described in detail.

The compound represented by Chemical Formula 1 contained as an aromatic radical polymerizable monomer was developed by the present researchers [Korean Patent No. 357685], and has excellent optical properties, high heat resistance, high surface hardness and refractive index, and radical polymerization by light or heat. This is a possible characteristic.

The compound represented by Chemical Formula 1 can be easily prepared and used by a known method. For example, hydroxyethyl methacrylate (HEMA) and triethylamine (TEAM) were added and stirred while dissolving in 60 ml of solvent, and then 4,4'-oxybis (benzoyl chloride) (DEDCh) was dissolved in dichloromethane. Was stirred at 0 ° C. for 30 minutes, and the reaction solution was stirred at room temperature for 2 hours and at 45 ° C. for 5 hours, and then washed with water and purified to obtain 4,4′-oxybis (benzoyl (2-methacryloethyl) Esters) are prepared. The 4,4'-oxybis (benzoyl chloride) (DEDCh) used at this time is prepared by the chloride reaction of 4,4'-oxy (benzoic acid) with thionyl chloride by a known method. In addition, 4,4'-bis (benzoyl chloride) sulfone, 4,4'-bis (benzoyl chloride) sulfide and various structures of bis (benzoyl chloride) derivatives are substituted for 4,4'-oxybis (benzoyl chloride). It may be used to prepare a compound represented by the formula (1) of various structures.

In the compound represented by Formula 1, preferably,

In the compound represented by the above formula (1), the ester compound of sulfur-containing diphenyl sulfide is suitable for high refractive index low dispersion. In addition, the urethane poly (meth) acrylic ester compound is excellent in impact resistance and surface hardness, is colorless, transparent, lightweight, and has excellent weather resistance, which is preferable for optical element materials such as plastic eyeglass lenses and camera lenses.

In addition, in the photochromic resin composition according to the present invention, as the aromatic radical polymerizable monomer, one or more compounds represented by Formula 1 may be used together with another radical polymerizable monomer.

Examples of radically polymerizable monomers that can be used together with the compound represented by Formula 1 are as follows:

Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, butanediol dimethacrylate, hexamethylene dimethacrylate, bisphenol A dimethacrylate, 2,2-bis ( 4-methacryloyloxyethoxy-3,5-dibromophenyl) propane, 2,2-bis (4-methacryloyloxyethoxyphenylpropane, 2,2-bis (4-methacrylo) Monooxyethoxyphenyl) propane, 2,2-bis- (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytriethoxyphenyl) propane, 2, 2-bis (4-methacryloyloxypentaethoxyphenyl) propane, bis-4-vinylbenzyl ether, bis-4-vinylbenzyl sulfide, 1,2- (p-vinylbenzyloxy) ethane, 1,2 -(p-vinylbenzylthio) ethane, bis- (p-vinylbenzyloxyethyl) sulfide and the like.

Other radically polymerizable monomers that may be used are:

Moreover, in this invention, 1 or more types of comonomer which has an unsaturated group can be added and copolymerized to the said aromatic radically polymerizable monomer. Examples of comonomers that can be used include NK55 (manufactured by Nippon Oil Holding Co., Ltd .; mixed compositions such as aromatic dimethacrylate, α-methylstyrene, tetraethylene glycol dimethacrylate, isopropenylbenzene, tribromophenyl acrylate), CR39 ( Bisallylethylene glycol carbonate), (alpha) -methylstyrene, styrene, polyethyleneoxy methacrylate or its acrylate, polyethyleneoxy diacrylate, alkylene triacrylate, etc.

On the other hand, the photochromic compound contained in the photochromic resin composition according to the present invention is selected from diarylethene-based, spirobenzopyran-based and diazo-based having an absorption wave of 250 nm or more.

Diarylethene-based compound to be used as the photochromic compound of the present invention may be represented by the following formula (2) and (3).

In Formula 2 above:

R ₂₁ represents a bond, -O-, a C ₁ -C ₃ alkylene group, or a C ₁ -C ₃ alkylene group substituted with fluorine; R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ are the same as or different from each other and are a hydrogen atom, a fluorine group, an aldehyde group, a carboxylic acid group, a substituted or unsubstituted C ₁ -C ₂₂ alkyl group or an alkylene group, An alkyleneoxyalkyl ester group or a substituted or unsubstituted phenyl group; X ₂ and Y ₂ , which are the same as or different from each other, represent —O—, —S— or —N (CH ₃ ) —; Z ₂₁ and Z ₂₂ , which are the same as or different from each other, represent —CH ₂ —, —CHF—, —CF ₂ — or —C (═O) —.

In Formula 3 above:

R ₃₁ represents a hydrogen atom, a C _{1 to} C ₂₂ alkyl group, a fluorine group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted phenylalkyl group; R ₃₂ represents a C ₁ -C ₂₂ alkylene group unsubstituted or substituted with fluorine; R ₃₃ represents a C ₁ to C ₃ alkylene group unsubstituted or substituted with a bond line, -O-, or fluorine; R ₃₄ is the same as R ₃₁ or represents a C ₁ to C ₂₂ alkylene or alkyleneoxyalkyl ester group which is unsubstituted or substituted with fluorine, and the alkylene group or alkyleneoxyalkylester group described above is a methacryl group, an acryl group and It may be substituted with one or more substituents selected from difluoroacryl group and the like; R ₃₅ is the same as R ₃₂ or represents a C ₁ to C ₂₂ alkyleneoxy group unsubstituted or substituted with fluorine; X ₃ and Y ₃ , which are the same as or different from each other, represent —O—, —N— or —S—; Z ₃₁ and Z ₃₂ , which are the same as or different from each other, represent —CH ₂ —, —CHF—, —CF ₂ — or —C (═O) —; o, p, q and r are numbers representing mole fractions, satisfying o + p + q + r = 1 and representing rational numbers less than 0 or 1 respectively.

More specifically exemplified by the diaryl ethene-based compound represented by Formulas 2 and 3 are as follows:

The spiro benzopyran compound to be used as the photochromic compound of the present invention may be represented by the following formula (4).

In Formula 4 above:

R ₄₁ represents a substituted or unsubstituted C ₁ -C ₂₂ alkyl or alkenyl group, or a substituted or unsubstituted phenyl or phenylalkyl group, wherein the substituent is a halogen atom including fluoride, a hydroxy group, a glycidoxy group, an amine group, One or more functional groups selected from vinyl group, epoxy group, (meth) acryl group, amino group, mercapto and the like; R ₄₂ and R _43, the same as or different from each other, represent a hydrogen atom, a halogen atom, a cyano group, a substituted amino group, a nitro group, or a substituted or unsubstituted C ₁ -C ₁₀ alkyl or alkoxy group; R ₄₄ represents a hydrogen atom, a hydroxy group, -R ₄₁ group, -OR ₄₁ group,-(R ₄₅ ) _n -Z ₄₅ group (wherein R ₄₅ is a substituted or unsubstituted C ₁ -C ₂₂ alkylene group with a carbon chain It may include one or more heteroatoms selected from oxygen, sulfur, nitrogen, etc., wherein Z ₄₅ is a halogen atom, hydroxy group, glycidoxy group, amine group, vinyl group, epoxy group, (meth) acrylic group, amino group or mercap Functional groups such as earthenware, and n represents an integer of 0 to 20; X ₄ is a divalent linking group —C (═O) —, —S—, —SO ₂ —, —C≡C—, —O—, —C (R ₄₆ ) ₂ —, —C (R ₄₆ ) = C (R ₄₆ )-, -N = N- or -NR _46- , wherein R ₄₆ is each independently selected from the substituents defined for R ₄₁ , R ₄₂ and R ₄₃ as defined above.

More specifically exemplified spirobenzopyran compound represented by the formula (4) is as follows:

In addition, the photochromic compound to be used in the present invention may include a diazo compound and a polymer thereof represented by the following formula (5).

In Formula 5 above:

R ₅₁ and R ₅₂ , which are the same as or different from each other, represent a cyan group, a nitro group, an amine group, a substituted or unsubstituted C ₁ -C ₂₂ alkyl or alkenyl group, or a substituted or unsubstituted phenyl or phenylalkyl group, wherein a substituent Represents one or more functional groups selected from a halogen atom including fluoride, a hydroxy group, a glycidoxy group, an amine group, a vinyl group, an epoxy group, a (meth) acryl group, an amino group and a mercapto group.

The photochromic compounds exemplified above are well-known compounds, and can be easily prepared and used by known methods. [US Pat. 4,342,688; Applied photochromic polymer system (Ed. C. B. McARDLE) 1992; Macromolecules, 1998, 31, 5726 (Eunkyoung Kim, et.al); Tetrahedrom Letter, 1998, 39, 8861 (Eunkyoung Kim, et. Al); Eun-Kyung Kim J. Korean Society for Imaging Science, 1997, 3, 17. (Eunkyoung Kim et. Al); Macromolecules, 1999, 32, 4588; N. Tanio and M. Irie, Jpn, J. Appl. Phys. 1994, 33, 1550; N. Tanio and M. Irie, Jpn. J. Appl. Phys. 1994, 33, 1550; Y. Nakayama, K. Hayashi, and M. Irie, J. Org. Chem. 1990, 55, 2592; M. Irie, O. Miyatake and K. Uchida, J. Am. Chem. Soc. 1992, 114, 8715; K. Matsuda and M. Irie, Chem. Lett. 2000, 16; M. Tanaka, Y. Ishizyka, M. Matsumoto, and T. Nakamura, Chem. Lett. 1987, 1307; V. Krongaug, J. Kiwi, and M. Graetgel, J. Photochem. 1980, 13, 89].

On the other hand, the photoinitiator contained in the photochromic resin composition according to the present invention is capable of photopolymerization by decomposition into radicals by irradiation of light, for example, 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide ( BPO), Diisopropyl peroxydicarbonate (IPP), tertiary butylhydroperoxide (TBPO), other thermosetting initiators, or Irgacure (from Ciba-Geigy; 1-hydroxyhexylphenylketone, benzophenone, 2-hydroxy- 1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, fluorinated diaryl titanocene, etc.), 2,2-bis Known photoinitiators such as (hydroxymethyl) propionic acid (DMPA) or mixtures thereof can be used.

The photochromic resin composition of the present invention as described above is mixed with 100 parts by weight of the monomer mixture containing the aromatic radical polymerizable monomer represented by the above formula (1) and, if necessary, 0.001 to 90 parts by weight of the specific photochromic compound and It is manufactured by adding 0.5-5 weight part of photoinitiators after stirring. In addition, it is possible to control various physical properties such as the refractive index of the photochromic resin composition prepared by appropriately adjusting the content within the usable content range according to the intended use and product properties required.

In addition to the above-mentioned essential components, an aliphatic unsaturated compound, an organic solvent, and the like may be added to adjust the thickness of the thin film and to control the viscosity. In addition, a polymerization catalyst for promoting the polymerization reaction, an ultraviolet absorber for improving weather resistance, and an anti-coloring agent may be added. It may be included, such additives can be used by those skilled in the art.

The photochromic resin prepared by the photopolymerization method or the thermal polymerization method using the photochromic resin composition according to the present invention is characterized by excellent transparency, surface hardness and wear resistance and high refractive index. Therefore, the photochromic molded article can be manufactured using the photochromic resin composition of the present invention. The photochromic molded article is excellent in transparency, refractive index, hardness, and heat resistance, and has excellent photochromic repeatability. The present invention can be effectively applied to filters, imaging, display elements, optical integrated elements, optical discs, or optical recording media.

The photochromic resin composition of the present invention may be coated on a glass plate, ITO, silicon wafer, other support, and may also be molded through photocuring and / or thermosetting in various molds. When thermally cured, it is cured for 3 to 48 hours depending on the amount of the composition and the content of the initiator. For example, when benzoyl peroxide (BPO) is used as the photoinitiator, the photocuring conditions are made at -20 to 120 ° C, and the curing is preferably performed for 30 seconds to 2 hours using a UV lamp, an ultraviolet curing machine, a xenon lamp, or the like. Do. As another example, as the polymerizable monomer represented by Formula 1, X = SO ₂ , n = 2 methacrylate monomer (88 g), diarylethene-based photochromic compound (8 g), Igacure 184 photoinitiator (2 g) and tetrahydrofuran solvent (8 g) in the case of photopolymerization, curing with an ultraviolet curing machine for 5 minutes at room temperature to produce a thin film having a thickness of 3 ㎛, refractive index 1.65, surface pencil hardness 3H. The prepared thin film exhibits variable chromaticity by UV / visible light, and the thin film does not decompose even after being left at room temperature for one year, and exhibits photochromic property. The thin film exhibits a refractive index change of 0.002 by UV / visible light.

Using the photochromic resin composition, a photochromic molded article, for example, a plastic lens, a photochromic film, a photochromic thin film, a photochromic image, or the like can be produced by a conventional manufacturing method.

On the other hand, the present invention is characterized by a method of manufacturing a plastic lens as a photochromic molded article, the photochromic plastic lens is made by injecting a photochromic resin composition having a composition as described above in the mold and then thermosetting do. At this time, the thermosetting conditions are carried out by varying the temperature step by step, first to maintain the decomposition reaction of the initiator to start 30 minutes to 360 minutes at room temperature ~ 70 ℃, 110 ~ 180 minutes at 70 ~ 80 ℃, the temperature is raised 110-130 minutes at 85-95 degreeC, the temperature was heated up again, it hold | maintained at 110-130 degreeC for 30-240 minutes, and then cooled naturally.

The photochromic film is prepared by a photocuring reaction by injecting a photochromic resin composition into a glass mold and irradiating ultraviolet rays for 30 seconds to 2 hours. In addition, the photochromic thin film is manufactured by irradiating ultraviolet rays for 30 seconds to 2 hours after coating a substrate such as a silicon wafer. The photochromic film or the photochromic thin film may perform a photocuring reaction using a UV lamp, an ultraviolet curing machine or a xenon lamp at -20 to 120 ° C. The photochromic film or the photochromic thin film thus prepared may have ultraviolet light. When irradiated, the color changes to red, and when the visible light is irradiated, the color changes to colorless and can be repeatedly controlled by an ultraviolet / visible light source.

A photochromic image is a mask image recorded on a photochromic film on a substrate. The photochromic resin composition is coated on a silicon wafer, a transparent plastic substrate, an ITO or a glass substrate, and cured by ultraviolet or heat to prepare a photochromic film. . Here, a mask of a specific shape is covered with ultraviolet light so that the mask image is recorded on the photochromic film. Subsequently, when the mask is removed, the substrate is dipped in a solvent, and then dried, and the unevenness of the mask image (recording portion) appears. Irradiating the substrate with ultraviolet rays generates red recording marks, and when irradiated with He-Ne laser again, the recording-erasing repeatability disappears. The masking image is rewritable and the uneven portion can be kept stable for more than one year. At this time, the ultraviolet rays are irradiated for 30 seconds to 2 hours, further cured at 60 to 140 ° C. for 1 to 18 hours, and after masking them, the ultraviolet rays are irradiated for 30 seconds to 2 hours to produce an image. As the substrate, a silicon wafer, a transparent plastic substrate, ITO, glass, or the like may be used.

Hereinafter, the present invention will be described in more detail with reference to the following Preparation Examples and Examples, but the present invention is not limited thereto.

In addition, the performance evaluation performed in the following Example was performed by the following test method.

<Test method>

(1) Heat resistance: measured using TGA (Thermo Gravimetry Analysis) and DSC (Differential Scanning Calorimetry).

(2) Surface hardness: pencil hardness using a pencil scraping tester.

(3) Photochromic: measured by ultraviolet spectroscopy.

(4) Refractive index: In the case of a thin film, it was measured at room temperature using a prism coupler, and molded products having a thickness of 2 mm or more were measured at 20 ° C using a "DR-A1" refractor manufactured by ATAGO.

(5) Absorption rate (%): It is immersed in water for 48 hours at room temperature, and the absorption rate is measured from the weight change after that.

(6) Transmittance: A test piece having a thickness of 2 mm was prepared, and the transmittance of 400 to 800 nm was measured by UV / Vis spectrum. In this case, the transmittance value summarizes the transmittance of 600 nm.

The following Production Example 1 and Production Example 2 are merely examples for the synthesis of the radical polymerizable monomer used in the present invention, and other monomers can be easily produced and used by known production methods.

Preparation Example 1

4,4'-dihydroxydiphenylsulfone (80.8 g) and H ₂ O (200 mL) were added to a 500 mL three-bar pressure glass reactor equipped with a stirrer, separator funnel and thermometer, followed by 1.6 mol of KOH. After adding and stirring and dissolving, dichloromethane (150 mL) and benzyltrimethylammonium chloride (BTAC) catalyst (11.15 g, 0.06 mol) were added to dissolve completely. The temperature in the reactor was set in the range of 0 to 5 ° C., 50 ml of dichloromethane was added to the separating funnel, and then 0.84 mol of 2-hydroxymethacryloyl chloroformate was mixed and slowly added dropwise. After completion of the dropping, the reaction was continued by stirring while gradually raising the temperature in the reactor to room temperature. The reaction time was generally 5 to 6 hours, and when it became a transparent reactant, it was repeatedly washed with distilled water and neutralized. After decolorizing with activated carbon, dried over anhydrous magnesium sulfate, and dichloromethane of the filtered mother liquor was evaporated to obtain the target compound.

Refractive Index (n _D ²⁰ ): 1.5319

IR (KBr): 29.53, 1454, 1380 cm ^-1 (-CH ₃ ), 1730 cm ^-1 (-C = O), 1635 cm ^-1 (> C = C <), 1600, 1498 cm ^-1 (> C = C <ar), 1320, 1296, 1250 cm ⁻¹ (∋COC∈).

¹ H-NMR (300 MHz, CDCl ₃ , ppm) 2.04 (s, -CCH ₃ = CH ₂ , 6H), 5.73 (d, 2H), 6.32 (d, trans, 2H), 6.98-7.01 (d, 4H ), 7.04-7.08 (d, 4H).

Preparation Example 2

In the preparation method according to Preparation Example 1, 4,4'-dihydroxydiphenyl sulfide was used instead of 4,4'-dihydroxydiphenyl sulfone to prepare the target compound.

Melting point (mp): 90-91 ° C

Elemental analysis: C ₂ 0H ₁₈ O ₅ (338.3)

Theoretical calculations: C 70.99%, H 5.36%, O 23.64%

Measured value: C 70.50%, H 5.40%, O 22.27%

IR (KBr): 29.53, 1454, 1380 cm ^-1 (-CH ₃ ), 1730 cm ^-1 (-C = O), 1635 cm ^-1 (> C = C <), 1600,1498 cm ^-1 (> C = C <ar), 1320, 1296, 1250 cm ^-1 (∋COC∈)

Refractive index (n _D ²⁰ ): 1.5382.

Example 1 Preparation of Photochromic Resin Composition

The photochromic resin composition was prepared with the composition and content as shown in Table 1 below, and the refractive index of each of the photochromic resin compositions was measured.

Each photochromic resin composition was able to change the refractive index (n _D ²⁰ ) to 1.52 to 1.59 by the composition and the content change.

sample Photochromic resin composition component (weight part) Solvent (part by weight) Refractive Index (n _D ²⁰ ) Radically polymerizable monomer Comonomer Photochromic compound Initiator One Monomer 1 (80) Monomer 7 (20) - PC 1 (0.01) AIBN (2.5) - 1.5537 2 Monomer 1 (10) Monomer 14 (15) Monomer 7 (55) α-methylstyrene (20) PC 6 (0.3) AIBN (2.4) - 1.5340 3 Monomer 7 (60) Monomer 13 (20) α-methylstyrene (20) PC 3 (0.005) BPO (2.5) - 1.5367 4 Monomer 7 (60) Monomer 8 (10) Monomer 9 (15) α-methylstyrene (15) PC 3 (0.05) AIBN (2.5) - 1.5610 5 Monomer 1 (33.5) Monomer 9 (2.2) Monomer 10 (44.3) α-methylstyrene (20) PC 4 (0.01) AIBN (2.5) - 1.5583 6 Monomer 1 (15) Monomer 14 (10) Monomer 7 (50) α-methylstyrene (20) PC 1 (5) AIBN (2.5) - 1.5714 7 Monomer 1 (5) monomer 9 (8) divinylbenzene (5) - PC 4 (10) AIBN (2.5) - 1.5876 8 Monomer 1 (0.5) monomer 14 (10) monomer 13 (66) - PC 3 (10) AIBN (2) THF (24) 1.5677 9 Monomer 1 (1) monomer 14 (1) monomer 13 (65) - PC 3 (10) I184 (2) THF (24) 1.5678 10 Monomer 1 (1) monomer 14 (1) monomer 13 (65) - PC 4 (10) AIBN (2) THF (24) 1.5573 11 Monomer 1 (1) monomer 14 (1) monomer 13 (65) - PC 4 (10) I184 (2) THF (16) DCE (8) 1.5519 12 Monomer 1 (5) Monomer 14 (5) Monomer 7 (33) Monomer 9 (20) Monomer 11 (20) α-methylstyrene (15) PC 2 (2) BPO (1.5) - 1.5638

(continue)

sample Photochromic resin composition component (weight part) Solvent (part by weight) Refractive Index (n _D ²⁰ ) Radically polymerizable monomer Comonomer Photochromic compound Initiator 13 Monomer 7 (50) Monomer 9 (20) Monomer 10 (5) Monomer 11 (10) α-methylstyrene (15) PC 10 (0.3) AIBN (2.0) I184 (1.5) - 1.5629 14 Monomer 1 (5) Monomer 13 (65) Monomer 10 (0.5) - PC 4 (10) I184 (2) THF (24.5) 1.5510 15 Monomer 1 (0.5) monomer 13 (10) - PC 1 (5) AIBN (1) THF (24.5) 1.5373 16 Monomer 14 (5) Monomer 10 (0.5) Monomer 15 (10) Monomer 16 (20) Monomer 17 (10) Monomer 9 (30) - PC 1 (4.5) I184 (1) THF (20) 1.5610 17 Monomer 14 (5) Monomer 10 (0.5) Monomer 15 (10) Monomer 16 (20) Monomer 17 (10) Monomer 9 (30) - PC 1 (4.5) AIBN (1) THF (20) 1.5612 18 Monomer 14 (20) Monomer 10 (0.5) Monomer 15 (15) Monomer 16 (15) Monomer 17 (20) Monomer 9 (30) - PC 1 (4.5) I184 (2) THF (15) DCE (10) 1.5632 19 Monomer 1 (5) Monomer 13 (65) Monomer 10 (0.5) - PC 10 (5) I184 (2) THF (29.5) 1.5710 20 Monomer 1 (5) Monomer 13 (65) Monomer 10 (0.5) - PC 11 (10) BPO (2) THF (24.5) 1.5510 I184: photoinitiator Irgacure 184 (Ciba-Geigy) DCE: 1,2-dichloroethane

Example 2 Preparation of Plastic Lens by Thermosetting Method

The photochromic resin composition prepared in Example 1 was placed in a mold made of a glass mold and a silicone gasket, and thermally cured to prepare a plastic lens, and the polymerization temperature was controlled by the following steps:

Room temperature → temperature increase rate 0.3 ℃ / min and maintain 180 minutes at 60 ℃ → temperature increase rate 0.125 ℃ / min and maintain 180 minutes at 75 ℃ → temperature increase rate 0.125 ℃ / minute to 120 minutes at 90 ℃ → heating rate 0.25 The temperature is raised to 120 ° C./min and held at 120 ° C. for 120 minutes. → Naturally cooled to 60 ° C.

division Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 ^* Comparative sample Refractive Index (n _D ²⁰ ) 1.6045 1.6153 1.5995 1.6572 1.6572 1.4995 Ash (ν _D ) 36 43.2 59.1 Specific gravity (g / cm 3) 1.30 1.22 1.29 1.37 Glass transition temperature (℃) 146 130 5% by weight loss temperature (℃) 265 259 312 Pencil hardness (H) 6H 6H 6H 5H 6H 2H Transmittance (%), 2-3mm / 600nm 98% 89% 93% 89% 89% 92% Water Absorption (%) 24 ℃ / 24hr 0.26% 0.15% 0.14% 0.21% 0.15% 0.16% Photochromic λ _max (nm) 530 nm 545 nm 565 nm 560 nm 560 nm None Exterior transparent transparent transparent transparent transparent transparent ^* Comparative sample: manufactured from optical resin CR39 (bisallyl ethylene glycol carbonate)

According to Table 2, the photochromic resin composition of the present invention is transparent, has a high pencil hardness, and has excellent transmittance and absorption, and thus, it can be seen that it is suitable for a high refractive lens.

In addition, the photochromic properties of the produced photochromic plastic lens is shown in Figure 1 attached. According to FIG. 1, although the absorption wave is 400 or less before ultraviolet irradiation, when the ultraviolet ray having a wavelength of 250 nm or more is irradiated, the plastic lens becomes red and a new absorption band appears in the visible region to show discoloration by light. This property is reversible.

Example 3: Preparation of Photochromic Film

The photochromic resin composition of Sample 9 prepared in Example 1 was placed in a 200 μm glass mold, and irradiated with ultraviolet rays for 5 minutes to prepare a photochromic film.

The refractive index of the prepared optical film was 1.6573, and when exposed to visible light having a wavelength of 400 nm or more, it is discolored within 1 minute, and again irradiated with ultraviolet light, it is colored within 1 minute, and red / colorless according to repeated exposure of ultraviolet / visible light. Photo discoloration was confirmed. These photochromic cycles were possible over 10,000 times, and the result was stable for more than 6 months after storage in the dark.

Example 4 Preparation of Photochromic Thin Film

The photochromic resin composition of Sample 11 prepared in Example 1 was spin-coated on a silicon wafer, and irradiated with ultraviolet rays for 5 minutes to prepare a photochromic thin film having a surface average roughness of 2 nm or less and a thickness of 3 μm.

The prepared photochromic thin film was found to be changed to red when irradiated with ultraviolet rays, thereby generating a new absorption wave at 560 nm. Such a red thin film is stable in a dark room, and returns to a colorless thin film when irradiated with visible light having a wavelength of 400 nm or more. The refractive index change according to the photochromic color is 0.0015, and the photochromic color and the refractive index change can be repeatedly controlled by an ultraviolet / visible light source.

Example 5: Preparation of Photochromic Image

Photochromic resin compositions of Samples 11, 14, and 16 prepared in Example 1 were prepared on a glass substrate, and a photochromic image was prepared by recording a mask image.

First, in the case of the photochromic resin composition of Sample 11, the photochromic resin composition was coated on a glass substrate, irradiated with ultraviolet rays for 10 minutes, and then exposed to room light for 1 hour. Subsequently, a photochromic image in which a mask image was recorded on the photochromic film was prepared by covering the mask and irradiating ultraviolet light for 1 minute. In this case, the prepared photochromic image is as shown in FIG.

In the case of the photochromic resin composition of Sample 14, the photochromic resin composition was coated on a glass substrate, and cured in an oven at 80 ° C. for 8 hours after ultraviolet irradiation for 2 minutes. Subsequently, the mask was cooled and irradiated with ultraviolet rays for 1 minute to prepare a photochromic image in which a mask image was recorded on the photochromic film.

In the case of the photochromic resin composition of Sample 16, the photochromic resin composition was coated on a glass substrate, and irradiated with ultraviolet rays for 3 minutes, then covered with a mask and further irradiated with ultraviolet rays for 2 minutes. Thereafter, the mask was removed, the substrate was dipped in an organic solvent, and then taken out and dried to prepare a photochromic image in which a mask image was recorded on the photochromic film.

Irradiating the photochromic images made from the photochromic resin compositions of Samples 11, 14, and 16 with ultraviolet light produced a red recording mark, and when irradiated with a He-Ne laser, the recording mark disappeared. This recording-erasing was repeatable and rewritable, and the uneven portion was stable for more than one year.

As described above, the photochromic resin composition according to the present invention can control the refractive index by changing its composition and content. Photochromic molded articles produced using the resin composition of the present invention could be effectively applied to functional optical lenses, filters, imaging, display elements or optical integrated elements, optical discs or optical recording media. In addition, it can be seen that the photochromic molded article is excellent in transparency, refractive index, hardness, abrasion resistance and heat resistance, and is capable of recording / erasing of an image directly through photocuring and is very stable even for long term storage.

Claims (7)

100 parts by weight of at least one monomer selected from aromatic radical polymerizable monomers represented by Formula 1; 0.001 to 90 parts by weight of at least one photochromic compound selected from diarylethene-based, spirobenzopyran-based and diazo-based having an absorption wave of 250 nm or more; And a photochromic resin composition containing 0.1 to 10 parts by weight of a photoinitiator, 30 minutes to 360 minutes at room temperature to 70 ℃ to start the decomposition reaction of the initiator, 110 to 180 minutes at 70 to 80 ℃, 110 to 130 minutes at 85 to 95 ℃, 110 to 130 ℃ Method of manufacturing a photochromic plastic lens characterized in that the manufacturing by performing a thermosetting process by temperature control consisting of a process of naturally cooling after maintaining for 30 to 240 minutes: Formula 1 In Formula 1 above: R ₁ and R ₂ , which are the same as or different from each other, are H or a C _{1 to} C ₄ alkyl group; R ₃ and R ₄ are the same as R ₁ and R ₂ or are a C ₁ -C ₄ haloalkyl group; R ₅ is H, a C _{1 to} C ₄ alkyl group or ego; Z is a direct bond, , -S- or -O-; Y is a direct bond, -S-, -SO _2- , -OC (= O)-, -C (= 0)-, -C (= 0) -O-, -OC (= 0) -O- or ego; X is H, -O-, -S-, -SO _2- , -C (= O)-or ego; k is an integer of 0 or 1; l is an integer of 1 or 2; m is an integer of 0, 1 or 2; n is 0 or an integer of 1-20. The aromatic radical polymerizable monomer of claim 1 is an aromatic dimethacrylate, α-methylstyrene, tetraethylene glycol dimethacrylate, isopropenylbenzene, tribromophenyl acrylate, At least one comonomer having an unsaturated group selected from styrene, polyethyleneoxy methacrylate or its acrylate, polyethyleneoxy diacrylate, bisallylethylene glycol carbonate, and alkylene triacrylate is contained together. Method of manufacturing a photochromic plastic lens. The method of claim 1, wherein the diarylethene-based photochromic compound is at least one selected from the compounds represented by Formulas 2 and 3: [Formula 2] In Formula 2 above: R ₂₁ represents a bond, -O-, a C ₁ -C ₃ alkylene group, or a C ₁ -C ₃ alkylene group substituted with fluorine; R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ are the same as or different from each other and are a hydrogen atom, a fluorine group, an aldehyde group, a carboxylic acid group, a substituted or unsubstituted C ₁ -C ₂₂ alkyl group or an alkylene group, An alkyleneoxyalkyl ester group or a substituted or unsubstituted phenyl group; X ₂ and Y ₂ , which are the same as or different from each other, represent —O—, —S— or —N (CH ₃ ) —; Z ₂₁ and Z ₂₂ , which are the same as or different from each other, represent —CH ₂ —, —CHF—, —CF ₂ — or —C (═O) —; [Formula 3] In Formula 3 above: R ₃₁ represents a hydrogen atom, a C _{1 to} C ₂₂ alkyl group, a fluorine group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted phenylalkyl group; R ₃₂ represents a C ₁ -C ₂₂ alkylene group unsubstituted or substituted with fluorine; R ₃₃ represents a C ₁ to C ₃ alkylene group unsubstituted or substituted with a bond line, -O-, or fluorine; R ₃₄ is the same as R ₃₁ or represents a C ₁ to C ₂₂ alkylene or alkyleneoxyalkyl ester group which is unsubstituted or substituted with fluorine, and the alkylene group or alkyleneoxyalkylester group described above is a methacryl group, an acryl group and May be substituted with one or more substituents selected from difluoroacryl groups; R ₃₅ is the same as R ₃₂ or represents a C ₁ to C ₂₂ alkyleneoxy group unsubstituted or substituted with fluorine; X ₃ and Y ₃ , which are the same as or different from each other, represent —O—, —N— or —S—; Z ₃₁ and Z ₃₂ , which are the same as or different from each other, represent —CH ₂ —, —CHF—, —CF ₂ — or —C (═O) —; o, p, q and r are numbers representing mole fractions, satisfying o + p + q + r = 1 and representing rational numbers less than 0 or 1 respectively. The method of manufacturing a photochromic plastic lens according to claim 3, wherein the diarylethene-based photochromic compound is at least one compound selected from the following. The method of claim 1, wherein the spirobenzopyran-based photochromic compound is at least one selected from the compounds represented by the following formula (4): [Formula 4] In Formula 4 above: R ₄₁ represents a substituted or unsubstituted C ₁ -C ₂₂ alkyl or alkenyl group, or a substituted or unsubstituted phenyl or phenylalkyl group, wherein the substituent is a halogen atom including fluoride, a hydroxy group, a glycidoxy group, an amine group, One or more functional groups selected from a vinyl group, an epoxy group, a (meth) acryl group, an amino group and a mercapto group; R ₄₂ and R _43, the same as or different from each other, represent a hydrogen atom, a halogen atom, a cyano group, a substituted amino group, a nitro group, or a substituted or unsubstituted C ₁ -C ₁₀ alkyl or alkoxy group; R ₄₄ represents a hydrogen atom, a hydroxy group, -R ₄₁ group, -OR ₄₁ group,-(R ₄₅ ) _n -Z ₄₅ group (wherein R ₄₅ is a substituted or unsubstituted C ₁ -C ₂₂ alkylene group with a carbon chain It may include one or more heteroatoms selected from oxygen, sulfur, nitrogen, etc., wherein Z ₄₅ is a halogen atom, hydroxy group, glycidoxy group, amine group, vinyl group, epoxy group, (meth) acrylic group, amino group or mercap A functional group of earthenware, n is an integer of 0 to 20); X ₄ is a divalent linking group —C (═O) —, —S—, —SO ₂ —, —C≡C—, —O—, —C (R ₄₆ ) ₂ —, —C (R ₄₆ ) = C (R ₄₆ )-, -N = N- or -NR _46- , wherein R ₄₆ is each independently selected from the substituents defined for R ₄₁ , R ₄₂ and R ₄₃ as defined above. The method of manufacturing a photochromic plastic lens according to claim 5, wherein the spirobenzopyran-based photochromic compound is a compound selected from the following. The method of claim 1, wherein the diazo photochromic compound is at least one selected from a compound represented by Formula 5 and a polymer thereof: [Formula 5] In Formula 5 above: R ₅₁ and R _52, the same as or different from each other, represent a cyan group, a nitro group, an amine group, a substituted or unsubstituted C ₁ -C ₂₂ alkyl or alkenyl group, or a substituted or unsubstituted phenyl or phenylalkyl group, wherein a substituent Represents one or more functional groups selected from a halogen atom including fluoride, a hydroxy group, a glycidoxy group, an amine group, a vinyl group, an epoxy group, a (meth) acryl group, an amino group and a mercapto group.