KR20070096317A - Photochromic spirooxazine derivatives, preparation method thereof, and articles comprising the same - Google Patents

Abstract

Photochromic spirooxazine derivatives are provided to increase life length and coloration/decoloration speed of the photochromic layer without using additional UV stabilizer, so that the derivatives are applicable to various articles. The photochromic spirooxazine derivatives represented by the formula(1) are provided, wherein R1 and R2 are each independently hydrogen, hydroxyl group, C1-C5 alkyl group, C1-C5 alkoxy group, C1-C5 hydroxy alkyl group, pyrolidinyl group, imidazolidinyl group, oxazolidinyl group, furanyl group, dioxolanyl group, thiophenyl group, piperidinyl group, piperazinyl group, pyrimidyl group, pyranyl group, dioxanyl group, thiopyranyl group, dimethyl amine group, diethyl amine group, methyl ethyl amine group, methyl propyl amine group, ethyl propyl amine group, halogen group or -L-P; at least one of R3 to R5 is -L-P; P is UV stabilizing group; L is a linker for connecting spirooxazine core to P; and m and n are each independently an integer from 1 to 4. A preparation method of the photochromic spirooxazine derivatives comprises the steps of: (a) reacting the linker compound with UV stabilizer, and reacting the linker-UV stabilizer conjugated compound with spirooxazine compound; (b) reacting the spirooxazine compound with the linker compound, and reacting the spirooxazine-linker conjugated compound with the UV stabilizer; or (c) reacting the indole compound as a precursor of spirooxazine compound with the linker compound, reacting the resulting compound with nitroso compound to prepare linker-bound spirooxazine compound, and reacting the linker-bound spirooxazine compound with UV stabilizer.

Description

Spirooxazine derivatives having photochromic properties, preparation methods thereof, and photochromic dyes including the same {PHOTOCHROMIC SPIROOXAZINE DERIVATIVES, PREPARATION METHOD THEREOF, AND ARTICLES COMPRISING THE SAME}

The present invention relates to a spirooxazine derivative having a photochromic property, a method for preparing the same, and a photochromic dye including the same, and more particularly, the use of a separate UV stabilizer is required because of excellent coloration / decoloration rate and weather resistance. The present invention relates to a spirooxazine derivative having no photochromic property, a preparation method thereof, and a use thereof.

Photochromism refers to a phenomenon in which the spectral characteristics of a molecule or crystal are reversibly changed by light or light of a specific wavelength, and thus color change occurs visually. In general, photochromic compounds are colored when exposed to ultraviolet rays and become inherently pale when blocked with light or irradiated with visible light.

Among the photochromic compounds, spirooxazine is colored by ring-opening when the CO ring opens when irradiated with UV, and conversely, when the UV is removed, CO is ringed again so that ring is closed by ring-closing. It returns to the structure of and is colorless.

The photochromic compound may be contained in the polymer coating composition to form a photochromic layer on the surface of the lens to control the color of the lens surface depending on whether light is irradiated. However, in order to apply a photochromic compound to a product, it must exhibit high transmittance in the absence of ultraviolet light, have low transmittance or high coloring ability in sunlight, and have appropriate coloration and kinetics. In addition, when the lens is tinted or decolorized, the selected color tone should preferably be maintained, the performance should be maintained in a certain temperature range, and long term use should be possible.

On the other hand, the polymer constituting the photochromic layer changes color or cracks with time, and degradation occurs due to heat or light, which gradually loses its original properties. To avoid this problem, most polymeric products essentially include one or more additives of antioxidants, UV blockers, and radical inhibitors.

The additive has the advantage of increasing the life of the photochromic layer by preventing the decomposition of the polymer, the coating property is reduced when used excessively, the blooming phenomenon appears after a long time. Recently, a method for further improving the durability of the photochromic dye has been proposed by changing the structure of the spirooxazine itself, such as introducing a new functional group to the spirooxazine.

Accordingly, an object of the present invention is to provide a novel compound for photochromic dyes, a method for preparing the same, and a photochromic dye including the same, which have improved weather resistance and lifespan, and have a fast coloration / discoloration rate without using an additive.

In order to achieve the above object, the present invention provides a spirooxazine derivative represented by the following formula (1):

In Chemical Formula 1,

R ₁ and R ₂ are each independently hydrogen, a hydroxy group, an alkyl group having 1 to 5 carbon atoms; An alkoxy group having 1 to 5 carbon atoms, a hydroxy alkyl group having 1 to 5 carbon atoms, a pyrrolidinyl, an imidazolynidyl, an oxazolidinyl, a furanyl group, and a dioxola Nil group (dioxolanyl), thiophenyl group, piperidinyl group, piperidinyl group, piperazinyl group, pyrimidinyl group, pyrimidyl group, pyranyl group, pyranyl group, dioxanyl group, dioxanyl group, thiopyranyl group ( thiopyranyl), dimethyl amine group, diethyl amine group, methyl ethyl amine group, methyl propyl amine group, ethyl propyl amine group, halogen group, and -LP,

At least one of R ₃ to R ₅ is -LP,

P is an ultraviolet stabilizer,

L is a linker linking the spiroxazine core and P,

M and n are integers from 1 to 4.

In another aspect, the present invention provides a method for preparing a spirooxazine derivative of Formula 1 comprising the step of binding the electrophilic terminal of the linker compound between the nucleophilic terminal of the spirooxazine compound, and the nucleophilic terminal of the ultraviolet light stabilizer, respectively to provide.

In another aspect, the present invention provides a photochromic dye comprising a spiroxazine derivative represented by the formula (1).

Hereinafter, the present invention will be described in more detail.

The spirooxazine derivatives of the present invention are novel compounds in which a spirooxazine core having photochromic properties is bridged with a linker of various compounds used as UV stabilizers. Therefore, the spirooxazine derivatives of the present invention do not need a separate UV stabilizer, which increases the lifespan of the dye, and has the feature of improving the coloration / discoloration rate of photochromic.

Spirooxazine derivatives according to the present invention is represented by the formula (1), wherein at least one of the R ₁ to R ₄ is characterized in that the -LP group combined with a linker and UV stabilizer.

At this time, the L may be any chemical structure that can connect the spiroxazine core and the UV stabilizer, but -OOC-, -OOC-R _5- , -OOC-R ₅ -COO-, -OOC-R ₅ -, -OOCNH-R ₆ -NHCOO-, R ₅ is branched or straight alkyl having 1 to 10 carbon atoms, R ₆ is branched or straight alkyl having 1 to 10 carbon atoms, And aliphatic or aromatic groups having 6 to 40 carbon atoms.

In addition, each P is independently from UV stabilizers such as UV absorbers, hindered amine light stabilizers (HALS), hindered phenol light stabilizers, antioxidants and the like. It is preferred to include derived substituents.

,

,

,

, 및

로 이루어진 군에서 선택되는 것이 더 바람직하다.The UV stabilizer P is a benzotriazole stabilizer, a benzophenone stabilizer, a triadine stabilizer, an aryl ester stabilizer, a piperidinyl stabilizer, an oxanilide stabilizer, a hindered amine stabilizer, It is preferable to select from the group which consists of a dud phenol type | system | group stabilizer, a semi-hindered phenol type | system | group stabilizer, and a phenylene diamine type | system | group stabilizer, Among these, 2-hydroxy phenyl benzotriazolyl group and 2-hydroxy benzophene Non-group, 2-hydroxyphenyl triazonyl group, 2-hydroxy-4- alkoxy benzophenone group, tetramethyl piperidinyl, 4-hydroxy- tetramethyl piperidinyl, 1, 3- benzol dicarboxamide- N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) [Nylostab ^® , S-EED ^® ], 2,2,4,4-tetramethyl-7-oxa-3 , 20-diazaspiro [5.1.11.2] henicoic acid-21-one [Hostavin ^® N 20], poly-[[6-[(1,1,3,3-tetramethylbutyl ) Amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl -[(2,2,6,6-tetramethyl-4-piperidinyl) imino]], 2,2,4,4-tetramethyl-7-oxa-3,20-diazaspiro [5.1 .11.2] reaction product of heneic acid-21-one with epichlorohydrin [Hostavin ^® N 30],

,

,

,

, And

More preferably, it is selected from the group consisting of.

Most preferred examples of the spirooxazine derivatives of the present invention are selected from the group consisting of compounds represented by the following general formulas (1a) to (1g).

[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

[Formula 1g]

The spirooxazine derivatives according to the present invention are usually colorless, and when activated by a light source such as sunlight, mercury, xenon, or UV radiation, they are instantly colored in a compound-specific color (for example, blue). Is switched. In particular, the photochromic properties of the spiroxazine derivatives are further improved by bridging the ultraviolet stabilizer 'P' capable of inhibiting oxidation by the linker 'L'.

In addition, the spirooxazine derivatives of the present invention vary the UV stabilization mechanism according to the type of UV stabilizer 'P'. Representatively, when P is a benzotriazole group, a benzophenol group, or a triamine group, an ultraviolet absorbing mechanism may be followed to reduce photosensitization by sending heat energy obtained by absorbing ultraviolet rays to a spirooxazine core through a linker. In addition, when P is a hindered amine group, the photocatalytic properties of the spirooxazine core are increased by a radical trapping mechanism that captures radicals generated by light and reduces photosensitivity without absorbing ultraviolet rays. Improve.

Hereinafter will be described a method for preparing a spirooxazine derivative according to the present invention.

The spirooxazine derivatives of the present invention can be prepared according to a process comprising the step of binding the electrophilic ends of the linker compounds, respectively, between the nucleophilic ends of the spirooxazine compounds and the nucleophilic ends of the ultraviolet stabilizer. .

Preferably, the manufacturing method of the spiroxazine derivative

(a) reacting the linker compound with the ultraviolet stabilizer, and then reacting the spirooxazine compound with the compound to which the linker-ultraviolet stabilizer is bound,

(b) reacting the spirooxazine compound with the linker compound, and then reacting the spirooxazine-linker bound compound with the ultraviolet stabilizer, or

(c) after reacting the indole compound, which is a precursor of the spirooxazine compound, to the linker compound, and then reacting the nitroso compound to prepare a spirooxazine compound having a linker, and reacting it with an ultraviolet stabilizer. .

In the method for preparing the spirooxazine derivative, the coupling reaction between the nucleophilic end of the spirooxazine compound or the UV stabilizer and the electrophilic end of the linker compound may be performed according to conventional condensation reaction conditions, and specific reaction conditions may be used. Although it depends on a substance, it turns out easily from the content described in the Example of this invention.

The kind of the nucleophilic terminal and the electrophilic terminal is not particularly limited, but preferred examples of the nucleophilic terminal of the spirooxazine compound or the ultraviolet stabilizer include a hydroxyl group, an amine group, and a thiol group. In addition, preferable examples of the electrophilic terminal of the linker compound include an isocyanate group, an hydride group, an ester group, an ether group, a carbonate group, and a urethane group.

In addition, the spirooxazine compound is preferably selected from the compounds represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₅ are each independently hydrogen, a hydroxy group, an alkyl group having 1 to 5 carbon atoms; An alkoxy group having 1 to 5 carbon atoms, a hydroxy alkyl group having 1 to 5 carbon atoms, a pyrrolidinyl, an imidazolynidyl, an oxazolidinyl, a furanyl group, and a dioxola Nil group (dioxolanyl), thiophenyl group, piperidinyl group, piperidinyl group, piperazinyl group, pyrimidinyl group, pyrimidyl group, pyranyl group, pyranyl group, dioxanyl group, dioxanyl group, thiopyranyl group ( thiopyranyl), a dimethyl amine group, a diethyl amine group, a methyl ethyl amine group, a methyl propyl amine group, an ethyl propyl amine group, and a halogen group, and m and n are integers of 1 to 4.

The linker compound has an electrophilic terminal selected from the group consisting of an isocyanate group, an anhydride group, an ester group, an ether group, a carbonate group, and a urethane group, and is -OOC-, -OOC-R ₅ -by a condensation reaction. It is preferably a compound containing a substituent capable of forming a linker unit selected from the group consisting of -OOC-R ₅ -COO-, -OOC-R _5- , and -OOCNH-R ₆ -NHCOO-.

The UV stabilizer is a benzotriazole compound, a benzophenone compound, a triadine compound, an aryl ester compound, a piperidinyl compound, an oxanilide compound, a hindered amine compound, a hindered phenol compound, a semi-hin It is preferable to select from the group which consists of a dod phenol type compound, and a phenylene diamine type compound.

The ultraviolet stabilizer may be manufactured directly or a commercially available ultraviolet stabilizer may be used.

The spirooxazine derivatives of the present invention prepared according to the above method have photochromic properties that change color when activated by a light source such as solar radiation, mercury, xenon or UV radiation, and thus are used as photochromic dyes on the surface of various industrial products. Used as a coating film to be coated.

In this case, the coating film is prepared by preparing a composition comprising the spirooxazine derivative, the polymer resin and the solvent of the present invention, and then coating the surface of the industrial product to be coated, followed by drying and curing.

The polymer resin used in the coating film may use a conventional coating polymer without particular limitation, and preferably any one selected from the group consisting of polyolefin, polyester, polycarbonate, polyacrylate, polyurethane, and epoxy resin. The above polymer resin can be used.

The solvent suitable for the production of the coating film can also be selected within the usual range, there is no particular limitation, benzene, toluene, methyl ethyl ketone, acetone, ethanol, methanol, propanol, isopropanol, tetrahydrofuran, dioxane, ethyl Preference is given to using one or more selected from the group consisting of acetate, ethylene glycol, xylene, cyclohexane and N-methyl pyrrolidinone.

The coating method of the coating film may be a conventional wet coating method such as spray coating, spin coating, dip coating, and doctor blading coating, and is not particularly limited.

Industrial products to which such coatings can be applied include applications in which photochromic materials are typically used, such as optical and planar lenses, face shields, goggles, camera lenses, windows, automotive transparents, inks, for example Liquid or paste-containing photochromic dyes used in writing and printing, decorations, such as plastic films and sheets, textiles and coating compositions, eg paints and protective documents, eg passports, driver's licenses And check marks of banknotes and the like.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Production Example  1: Preparation of Linker Compound

(2-butyl- Malonic Acid Diethyl  Ester (2-butyl- malonic  acid diethyl ester)

A linker compound represented by Chemical Formula 5 was prepared according to Scheme 1 below.

Scheme 1

500 mL of ethanol (abs.) Was injected into the reactor, and 2.85 g of sodium was added thereto to prepare sodium ethoxide. After the temperature of the reactor was maintained at 50 ° C., 20 g of diethyl malonate ( 3 ) was added thereto, and then 13.5 mL of n-butyl bromide ( 4 ) was slowly added to 100 mL of ethanol, and 4 The reaction was carried out for time.

After completion of the reaction, the obtained reaction was distilled under reduced pressure to remove the solvent, and the residue was extracted using a mixed solvent of water / dichloromethane (1: 1, v / v) (300 mL × 3). Subsequently, the organic layer was separated, the solvent was removed under reduced pressure, and the obtained residue was subjected to fractional distillation under vacuum to separate 2-butyl-malonic acid diethyl ester of colorless transparent liquid separated at 130-140 ° C. ester, 5 ) was recovered.

¹ H NMR (500 MHz, CDCl ₃ ): δ = 0.88-0.89 (t, 4H), 1.23-0.29 (m, 10H), 1.8-1.9 (q, 2H), 3.2-3.4 (t, 1H), 4.1 -4.2 (q, 4H)

Production Example  2: (Preparation of UV Stabilizer)

(3,5-di-t-butyl-4- Hydroxy -benzyl) Trimethyl  Production of ammonium)

According to Scheme 2, an ultraviolet stabilizer represented by Chemical Formula 7 was prepared.

Scheme 2

After 300 mL of dichloromethane was injected into the reactor, 7.90 g of 2,6-di-t-butyl-4- (dimethylamino) methyl phenol ( 6 ) was added and dissolved. Subsequently, 8.52 g of iodomethane was added, followed by stirring at room temperature for 2 hours.

After the completion of the reaction, the reaction product was depressurized to remove the solvent and the unreacted substance, and then the obtained residue was washed with dichloromethane (300 mL ⅹ 3), and then filtered to 7.74 g of (3,5-di-t-butyl-4-). Hydroxy-benzyl) trimethyl ammonium ( 7 ) was recovered.

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.554 (s, 18H), 3.170 (s, 9H), 4.55 (s, 2H), 5.59 (s, 1H), 7.415 (s, 2H)

Production Example  3: Spirook Photo  Manufacture of core

According to Scheme 3, a compound represented by Chemical Formula 2 was prepared:

Scheme 3

After injecting 100 ml of distilled water and 350 ml of acetic acid into the reactor, naphthalene-2,7-diol (100 g, 8 ) was added thereto and stirred at a temperature of 5 ° C. for 30 hours. . Sodium nitride (NaN, 43.2 g) was added thereto, followed by stirring for 1 hour. The obtained reaction solution was filtered, the filtrate was washed with distilled water (500 mlX3), residual acetic acid was removed, and the residue obtained by distillation under reduced pressure was vacuum dried overnight in an oven at 90 ° C. to obtain 1-nitrosonaphthalene-2,7-diol. (1-nitroso-naphthalene-2,7-diol, 9 ) was prepared.

¹ H NMR (500 MHz, CDCl ₃ ): δ = 6.75-6.95 (m, 2H), 7.40-7.80 (m, 3H)

The prepared 1-nitroso naphthalene-2,7-diol (40 g, 9 ) was injected into the reactor, 400 ml of ethanol was added, and then 1,3,3-trimethyl- diluted in 200 ml of ethanol. 2-methylene indoline (1,3,3-trimethyl-2-methyleneindoline, 36.8 g, 10 ) was slowly added dropwise for 30 minutes. After refluxing for 4 hours, the reaction was terminated by cooling to room temperature. The red precipitate precipitated at the bottom of the reactor during cooling is filtered off using methanol. The precipitate obtained was dried in vacuo at 90 ° C. overnight to give a compound of formula 2 (57 g).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.367 (s, 6H), 2.768 (s, 3H), 6.50 (d, 1H), 6.708 (t, 1H), 6.809 (t, 1H), 6.878 ( d, 1H), 7.016 (d, 1H), 7.129 (d, 1H), 7.53 (d, 1H), 7.55 (d, 1H), 7.62 (s, 1H), 7.984 (s, 1H).

Production Example  4: Spirook Photo  Linkers in the precursor Combined  Preparation of the compound

(2- (3,3-dimethyl-2- Methylene indoline -1-yl) ethanol production)

According to Scheme 4 below, a title compound having a linker bonded to an indole compound which is a precursor of spiroxazine was prepared.

Scheme 4

Inject 50 ml of chloroform into the reactor, and then add 2,3,3-trimethylindolinine (2, 3, 3-trimethylindolenine, 3.2 mL, 20 mmol, 11 ). After adding bromoethanol (2-bromoethanol, 1.7 mL, 24 mmol, 4-1 ) to reflux for 16 hours, the reaction was terminated by lowering the temperature of the reactor to room temperature. The reaction solution was concentrated under reduced pressure to remove the solvent and the unreacted substance, and the obtained precipitate was washed with ethyl acetate to obtain a pink solid compound. The pink solid compound was washed with NaOH (10%, 300 ml) and then extracted with dichloromethane (100 ml). The organic layer was separated, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure to yield 2- (3,3-dimethyl-2-methyleneindolin-1-yl) ethanol as a yellow oil (yield: 85%, 3.46 g) , 12 ).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.26 (s, 3H), 1.45 (s, 3H), 1.52 (s, 3H), 3.43 (m, 2H), 3.71 (m, 2H), 6.80 ( m, 1H), 6.95 (m, 1H), 7.18 (m, 1H), 7.22 (m, 1H)

Production Example  5: Spirook Photo  Linkers in the precursor Combined  Preparation of the compound

(1,3,3- Trimethyl -2-methylene-5- Indolin Amine  Produce)

According to Scheme 5, a title compound having a linker bonded to an indole compound which is a precursor of spirooxazine was prepared.

Scheme 5

Injecting (14. 17.7 mL, 100 mmol , 11) turned in 1,3,3- trimethyl-2-methylene in the reactor is maintained at 5 ℃ and stirred was slowly added dropwise to sulfuric acid (45 ml). Nitric acid (7.5 mL, 110 mmol) was slowly added dropwise thereto over 1 hour, followed by stirring, followed by stirring at .7 ° C for 3 hours. The resulting reaction was allowed to stand overnight in a refrigerator to give an orange-brown solution. The solution was poured onto crushed ice and neutralized by addition of aqueous NaOH solution (pH 4-5) to obtain an orange-red precipitate. The precipitate was filtered and washed sequentially with distilled water and ether, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was recrystallized from dichloromethane to give a yellow-brown solid 1,3,3-trimethyl-2-methylene-5-nitroindolin (52%, 1.13 g, 13 ).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.35 (s, 6H), 3.13 (s, 3H), 4.12 (d, 1H), 6.50 (d, 1H), 7.93 (s, 1H), 8.14 ( d, 1H)

Subsequently, hydrochloric acid (115 ml) and SnCl ₂ (stannous chloride, 30.4 g, 160 mmol) were sequentially injected into the reactor, and the 1,3,3-trimethyl-2-methylene-5-nit roindolin was prepared above. (5.0 g, 22.9 mol, 13 ) was added and refluxed for 16 h. After the reaction was completed by lowering the temperature to room temperature, the reaction solution was poured into crushed ice, and concentrated NaOH solution was added thereto to make the reaction solution basic, followed by extraction using ethyl acetate (200 mlX3). The organic layer was separated, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to prepare 1,3,3-trimethyl-2-methylene-5-indoline amine (95%, 4.03 g, 14 ).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.31 (s, 6H), 2.99 (s, 3H), 3.70 (d, 2H), 6.35 (m, 1H), 6.50 (m, 1H), 6.60 ( m, 1H)

Example  1: Preparation of the compound represented by Formula 1a

(1) Linker and UV Stabilizer

According to Scheme 6, a compound in which a UV stabilizer was linked to a linker was prepared.

Scheme 6

After injection of 200 mL of ethanol into the reactor at room temperature, 0.29 g of Na was added to prepare sodium ethoxide, followed by (3,5-di-t-butyl-4-hydroxy-benzyl) trimethyl ammonium ( 7 2.7 g were added and stirred.

6.08 g of 2-butyl malonic acid diethyl ester ( 5 ) was injected thereto, and the temperature of the reactor was raised to 80 ° C., and the reaction was performed under reflux for 3 hours.

After the completion of the reaction, the reaction product was depressurized to remove the solvent, and the obtained residue was extracted with a mixed solvent of water / dichloromethane (1: 1, v / v, 300 mL).

Select the organic layer after extraction to remove the solvent under reduced pressure to prepare 5.21 g 2-butyl-2- (3,5-di-t-butyl-4-hydroxy-benzyl) malonic acid diethyl ester) ( 15 ) It was.

¹ H NMR (500 MHz, CDCl ₃ ): δ = 0.885 (t, 3H), 1.1-1.4 (m, 26H), 1.746 (t, 2H), 3.14 (s, 2H), 4.1-4.2 (q, 4H ), 5.03 (s, 1 H), 6.83 (s, 2 H).

500 mL of dry was injected into the reactor, followed by addition of 11.2 g of potassium- t -butoxide while maintaining at 0 ° C. To this was added 0.46 mL of water and stirred for 5 minutes, followed by the 2-butyl-2- (3,5-di-tertiary-butyl-4-hydroxy-benzyl) malonic acid diethyl ester ( 15 ) 2.51 g was added, and the temperature of the reactor was increased to 25 ° C. and reacted for 3 hours.

After the completion of the reaction, the reaction product was extracted with water (300 mL), and then the organic layer was selected and extracted again with dichloromethane (300 mL), followed by distillation under reduced pressure, to obtain 2.1 g of 2-butyl-2- (3,5-di-. Tert-butyl-4-hydroxy-benzyl) malonic acid ( 16 ) was prepared.

¹ H NMR (500 MHz, CDCl ₃ ): δ = 0.883 (t, 3H), 1.13-1.49 (m, 22H), 1.95 (t, 2H), 3.19 (s, 2H), 6.92 (s, 2H).

(2) Introduction of the linker-ultraviolet stabilizer to the spirooxazine core

A spirooxazine derivative was prepared according to Scheme 7 below.

Scheme 7

 After dichloromethane (200 ml) and dimethylformamide (200 ml) were injected into the reactor, the compound of formula 16 prepared above (0.46 g), N- (3-dimethylaminopropyl) -N'-ethyl carbodii Mid (N- (3-dimethylaminopropyl) -N'-ethyl-carbodiimide, 0.30 g, HCl form) and dimethylaminopyridine (4.8 mg, catalytic amount) were sequentially injected and then mixed uniformly. To this was injected a compound of formula 2 (0.546 g) obtained in Preparation Example 3 and refluxed for 5 hours. After the reaction was completed, the solvent and unreacted material were removed under reduced pressure. The obtained residue was extracted with water / dichloromethane (300 ml, 1: 1), and the organic layer was separated and purified by column chromatography using silica gel to prepare a spiroxazine derivative of Chemical Formula 1a ( 250 mg).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 0.810 (t, 3H), 1.14-1.50 (m, 30H), 2.674 (s, 3H), 2.80-2.90 (m, 3H) 6.495 (d, 1H) , 6.719 (t, 1H), 6.824 (t, 1H), 6.896 (d, 1H), 6.999 (s, 2H), 7.016 (d, 1H), 7.144 (d, 1H), 7.53 (d, 1H), 7.55 (d, 1 H), 7.62 (s, 1 H), 7.984 (s, 1 H)

Example  2: Preparation of the compound represented by Formula 1b

A linker was connected to the spirooxazine core according to Scheme 8, and then reacted with a UV stabilizer compound to prepare a spirooxazine derivative represented by Chemical Formula 1b.

Scheme 8

 (1) linker linkage reaction

After dichloromethane (100 ml) was injected into the reactor, the compound of formula 2 (3.0 g, 8.7 mmol) obtained in Preparation Example 3 was used as a spiroxazine core, and glutaric anhydride (1.99 g) was added. , 17.4 mmol, 17 ) and dimethylaminopyridine (1% by weight, catalytic amount) were injected and refluxed for 4 hours. The reaction was terminated by lowering the temperature of the reactor to room temperature, and then washed with salt (100 ml x 3).

The organic layer was then separated, dried over anhydrous MgSO ₄ , filtered and the filtrate was concentrated under reduced pressure. The obtained residue was subjected to column chromatography (SiO ₂ : nucleic acid: ethyl acetate = 1: 1) to prepare a compound of formula 18 as a brown colored solid (2.33 g, 60%).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.35 (s, 3H), 1.36 (s, 3H), 2.17 (quintet, 2H), 2.60 (t, 2H), 2.75 (t, 2H), 2.77 ( s, 3H), 6.59 (d, 1H), 6.92 (t, 1H), 7.0 (d, 1H), 7.10 (d, 1H), 7.14 (dd, 1H), 7.23 (t, 1H), 7.66 (d , 1H), 7.73 (s, 1H), 7.76 (d, 1H), 8.24 (ds, 1H).

(2) Connection reaction of UV stabilizer

After dichloromethane (30 ml) was injected into the reactor, Compound 18 (1.0 g, 2.2 mmol), 1,2,2,6,6-pentamethylpiperidin-4-ol (1) prepared in (1) was used. 1,2,2,6,6-pentamethylpiperidin-4-ol, 0.45 g, 2.6 mmol, 19 ), N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide ( N- (3-dimethylaminopropyl) N'- ethylcarbodiimide (hereafter DCC, 0.50 g, 2.6 mmol) and dimethylaminopyridine (DMAP, 13.3 mg, 0.11 mmol) were added and mixed uniformly and then refluxed for 4 hours.

Thereafter, the reaction was terminated by lowering the temperature of the reactor to room temperature, and then the reaction solution was washed with salt (30 ml x 3).

Then, dried over anhydrous MgSO ₄ , filtered and depressurized to remove the solvent, and the obtained residue was subjected to column chromatography (SiO ₂ : nucleic acid: ethyl acetate = 1: 1) to give a green spirooxazine derivative. Was obtained (0.8 g, 60%, 1b ).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.11 (s, 6H), 1.19 (s, 6H), 1.35 (s, 3H), 1.36 (s, 3H), 2.15 (quintet, 2H), 2.50 ( t, 2H), 2.72 (t, 2H), 2.77 (s, 3H), 5.12 (m, 1H), 6.59 (d, 1H), 6.91 (t, 1H), 7.0 (d, 1H), 7.10 (d , 1H), 7.15 (dd, 1H), 7.21 (t, 1H), 7.66 (d, 1H), 7.73 (s, 1H), 7.75 (d, 1H), 8.25 (ds, 1H).

Example  3: Preparation of the compound represented by Formula 1c

In the same manner as in Example 2, the spirooxazine derivative represented by Chemical Formula 1c was prepared by changing the type of UV stabilizer compound.

(1) linker linkage reaction

The compound of Formula 18 was prepared by reacting the spiroxazine compound of Formula 2 with a linker according to the same method as Example 2.

(2) Connection reaction of UV stabilizer

According to Scheme 9, a spiroxazine derivative represented by Chemical Formula 1c was prepared.

Scheme 9

After dichloromethane (30 ml) was injected into the reactor, the compound of formula 18 (1.0 g, 2.2 mmol) and 2,6-di-t-butyl-4-hydroxy-methylphenol (2, 6-di- tert -butyl-4- hydroxy-methylphenol, 0.62 g, 2.6 mmol, 20), EDC (0.50 g, 2.6 mmol) and dimethylaminopyridine (DMAP, 13.3 mg, uniformly mixed was added to 0.11 mmol) It was then refluxed for 2 hours. After the reaction was completed by lowering the reactor to room temperature, the reaction solution was washed with brine (30 ml x 3), and the solvent was removed under reduced pressure, and the obtained residue was subjected to column chromatography (SiO ₂ : nucleic acid: ethyl acetate = 1: 1). ) Was obtained to obtain a compound of formula 1c of a bright green solid (0.75 g, 50%).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.35 (s, 3H), 1.36 (s, 3H), 1.46 (s. 18H), 2.17 (quintet, 2H), 2.56 (t, 2H), 2.74 ( t, 2H), 2.77 (s, 3H), 5.01 (s, 2H), 6.59 (d, 1H), 6.92 (t, 1H), 6.99 (d, 1H), 7.09 (d, 1H), 7.10 (dd , 1H), 7.20 (s, 4H), 7.23 (t, 1H), 7.66 (d, 1H), 7.72 (s, 1H), 7.76 (d, 1H), 8.24 (ds, 1H).

Example  4: Preparation of the compound represented by Formula 1d

After linking a linker to an indole compound which is a spirooxazine derivative according to Scheme 10 below, the resultant was reacted with a nitroso compound to prepare a spirooxazine to which the linker was bound, which was reacted with an ultraviolet light stabilizer compound to represent the compound of Formula 1d. A spirooxazine derivative was prepared.

Scheme 10

(1) Linking reaction of linker

Inject dichloromethane (30 ml) into the reactor, 2- (3,3-dimethyl-2-methyleneindolin-1-yl) ethanol (2- (3,3-dimethyl-2-methyleneindolin-1-yl) ethanol, 2.0 g, 7.03 mmol, 21 ), dimethylamino pyridine (DMAP, 85 mg, 0.7 mmol) were added and mixed uniformly, followed by glutaric unhydride (802 mg, 7.03 mmol, 17 ). . The resulting mixture was refluxed for 16 hours, then distilled under reduced pressure to remove the solvent and unreacted material, and the crude reaction obtained was used in the next step (in situ, 22 ) .

Injecting ethanol (30 ml) into the reactor and the compound prepared above (1.78 g, 5.62 mmol, 22 ) and 1-nitroso-2-naphthol (1-nitroso-2-naphthol, 973 mg, 5.62 mmol, 23 ) It was added to reflux for 16 hours. After the completion of the reaction, the obtained purple reaction solution was depressurized and the obtained residue was subjected to gradient silica gel chromatography ( n- hexane: ethyl acetate = 4: 1, 1: 2) to give a brown oil product (45%, 1.20 g). , 24 ).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.29 (s, 3H), 1.34 (s, 3H), 1.86-1.99 (m, 2H), 2.30-2.45 (m, 4H), 3.42-3.57 (m , 2H), 4.23-4.33 (m, 2H), 6.67 (d, 1H), 6.90 (t, 1H), 6.98 (m, 1H), 7.05 (m, 1H), 7.22 (m, 1H), 7.40 ( m, 1H), 7.58 (m, 1H), 7.69 (m, 1H), 7.81 (s, 1H), 8.51 (m, 1H).

(2) Connection reaction of UV stabilizer

Injecting dimethylformamide (30 ml) to the reactor, the compound prepared above (2.3 g, 5.0 mmol, 24 ), 1,2,2,6,6-pentamethylpiperidin-4-ol as a UV stabilizer (1,2,2,6,6-pentamethylpiperidin-4-ol, 1.28 g, 7.5 mmol, 19 ), DCC (1.55 g, 7.5 mmol) and dimethylaminopyridine (DMAP, 61 mg, 0.5 mmol) were mixed and then reacted at 60 ° C. for 16 hours. The reaction solution was distilled under reduced pressure to remove the solvent and the unreacted product, which was then extracted with a dichloromethane / salt (250 ml / 250 ml) mixed solvent. The aqueous layer was washed three times with dichloromethane, dried over anhydrous sodium sulfate, and then the organic layer was separated and distilled under reduced pressure to obtain a residue obtained by gradient silica gel chromatography (n-hexane: ethyl acetate = 8: 1, 2: 1). Was carried out to give a compound represented by the formula 1d of the yellow color in the oil state (35%, 240 mg).

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.06 (s, 3H), 1.07 (s, 3H), 1.14 (s, 3H), 1.15 (s, 3H), 1.26 (s, 3H), 1.33 ( s, 3H), 1.42-1.50 (m, 2H), 1.79-1.90 (m, 4H), 2.32 (s, 3H), 2.73 (m, 1H), 2.38 (m, 2H), 3.41-3.57 (m, 2H), 4.27 (m, 2H), 5.06 (m, 2H), 6.87 (d, 1H), 6.89 (m, 1H), 6.98 (m, 1H), 7.07 (m, 1H), 7.20 (m, 1H ), 7.39 (m, 1H), 7.56 (m, 1H), 7.67 (m, 1H), 7.74 (m, 2H), 8.54 (m, 1H).

Example  5: Preparation of the compound represented by Formula 1e

In the same manner as in Example 4, a spirooxazine derivative represented by Chemical Formula 1e was prepared by changing the type of UV stabilizer compound.

(1) linker linkage reaction

After linking the linker to the indole compound which is a spirooxazine derivative according to the same method as in Example 4, the resultant was reacted with the nitroso compound to prepare a spirooxazine compound represented by Formula 24.

(2) Connection reaction of UV stabilizer

Thereafter, dimethylformamide (30 ml) was injected into the reactor, and the compound of Chemical Formula 24 (2.3 g, 5.0 mmol) and 2,6-di-t-butyl-4-hydroxy-methylphenol (1.77) were UV stabilizers. g, 7.5 mmol, 20 ), DCC (1.55 g, 7.5 mmol) and dimethylaminopyridine (DMAP, 61 mg, 0.5 mmol) were mixed and then reacted at 60 ° C. for 16 hours. The reaction solution was distilled under reduced pressure to remove the solvent and the unreacted product, which was then extracted with a dichloromethane / brine (250 ml / 250 ml) mixed solvent. The aqueous layer was washed three times with dichloromethane, dried over anhydrous sodium sulfate, and the organic layer was separated and distilled under reduced pressure to obtain a residue obtained by gradient silica gel chromatography (n-hexane: ethyl acetate = 8: 1, 3 :). 1) was carried out to give an oily yellow colored compound of formula 1e (17%, 580 mg)

[Formula 1e]

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.28 (s, 6H), 1.34 (s, 18H), 1.86 (m, 2H), 2.28 (m, 4H), 2.42 (s, 2H), 3.39- 3.55 (m, 2H), 4.07 (m, 2H), 4.25 (m, 2H), 6.67 (d, 1H), 6.86 (m, 1H), 6.90 (m, 1H), 7.04 (m, 1H), 7.17 (m, 2H), 7.20 (m, 1H), 7.36 (m, 1H), 7.52 (m, 1H), 7.61 (m, 1H), 7.70 (m, 1H), 7.52 (s, 1H), 8.55 ( m, 1 H).

Example  6: Preparation of the compound represented by Formula 1f

According to Scheme 11, a spiroxazine derivative represented by Formula 1f was prepared:

Scheme 11

(1) linker linkage reaction

After injecting dimethylformamide (DMF, 50 ml) into the reactor, 1,3,3-trimethyl-2-methyleneindolin-5-amine (1,3,3-trimethyl-2-methyleneindolin-5-amine, 2.21 g, 11.7 mmol, 14 ), dimethylaminopyridine (142 mg, 1.17 mmol) was added. To this was added glutic anhydride (1.6 g, 14.0 mmol, 17 ) and refluxed for 16 hours. After the reaction was completed, the crude product (crude product) obtained by concentrating the final reaction product under reduced pressure was used in the next step ( in situ , 25 ).

Ethanol (50 ml) was injected into the reactor, and 4- (1,3,3-trimethyl-2-methyleneindolin-5-ylcarbamoyl) butanoic acid (2.12 g, 7.01 mmol, 25 ) prepared above was prepared. And 1-nitroso-2-naphthol (1.21 g, 7.01 mmol, 23 ) was added and refluxed for 16 hours. The crude product obtained by concentrating the final reaction under reduced pressure was used in the next step ( in situ , 26 ).

(2) Connection reaction of UV stabilizer

After injecting dimethylformamide (10 ml) into the reactor, the compound prepared above (1.0 g, 2.18 mmol, 26 ), 1,2,2,6,6-pentamethylpiperidin-4-ol, a UV stabilizer (1,2,2,6,6-pentamethylpiperidin-4-ol, 560 mg, 3.27 mmol, 19 ), DCC (675 mg, 3.27 mmol) and dimethylaminopyridine (DMAP, 27 mg, 0.22 mmol) were added After the reaction was carried out at 60 ℃ for 16 hours. The reaction product was distilled under reduced pressure to remove the solvent and the unreacted product, and the mixture was extracted with dichloromethane / brine (50 ml / 50 ml) mixed solvent. The aqueous layer was washed three times with dichloromethane, dried over anhydrous sodium sulfate, and the organic layer was separated and distilled under reduced pressure to obtain a residue obtained by silica gel chromatography (n-hexane: ethyl acetate = 8: 1, 3: 1). ) To give an oily yellow compound of formula 1f (18%, 240 mg):

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.25 (s, 3H), 1.27 (s, 3H), 1.32 (s, 6H), 1.37 (s, 6H), 1.79-1.90 (m, 4H), 2.03-2.10 (m, 2H), 2.47 (t, 2H), 2.52 (t, 2H), 2.75 (s, 3H), 3.43 (t, 1H), 6.45 (d, 1H), 7.04 (d, 1H) , 7.23 (d, 1H), 7.29-7.35 (m, 2H), 7.49 (t, 1H), 7.72 (d, 1H), 7.36 (m, 2H), 8.34 (s, 1H), 8.57 (d, 1H )

Example  7: Preparation of the compound represented by Chemical Formula 1g

In the same manner as in Example 6, the spirooxazine derivative represented by Chemical Formula 1g was prepared by changing the type of UV stabilizer compound.

(1) linker linkage reaction

After linking the linker to the indole compound which is a spirooxazine derivative in the same manner as in Example 6, the resultant was reacted with the nitroso compound to prepare a spirooxazine compound of formula 26 in which the linker was bound.

(2) Connection reaction of UV stabilizer

After injection of dimethylformamide (10 ml) into the reactor, the compound of formula 26 (1.0 g, 2.18 mmol) prepared above, and 2,6-di-t-butyl-4-hydroxy-methylphenol (UV stabilizer) 773 mg, 3.27 mmol, 20 ), DCC (675 mg, 3.27 mmol) and dimethylaminopyridine (DMAP, 27 mg, 0.22 mmol) were added, followed by reaction at 60 ° C. for 16 hours. The resulting reaction was distilled under reduced pressure to remove the solvent, and extracted with dichloromethane / brine (50 ml / 50 ml) mixed solvent. The aqueous layer was separated and dried over anhydrous sodium sulfate, and the residue obtained by distillation under reduced pressure was subjected to silica gel chromatography (n-hexane: ethyl acetate = 10: 1) to obtain an oily yellow compound represented by Chemical Formula 1g. Compound obtained (17%, 250 mg).

[Formula 1g]

¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.23-1.26 (br, 15H), 1.30-1.40 (br, 9H), 2.03 (s, 2H), 2.04-2.10 (m, 2H), 2.42 (t , 2H), 2.52 (t, 2H), 2.70 (s, 3H), 3.61-3.67 (br, 1H), 4.01-4.07 (br, 1H), 6.44 (d, 1H), 6.94 (d, 1H), 7.26 (d, 1H), 7.35-7.44 (m, 4H), 7.54 (t, 1H), 7.62 (d, 1H), 7.71 (s, 1H), 7.72 (s, 1H), 8.51 (s, 1H) , 8.57 (d, 1 H)

Example  8

The coating liquid to the reactor (LG Chemical Co. product, UT11PCF) the input, and then inject the photochromic dye compound prepared in Example 1, TINUVIN -770 (TINUWIN ^TM, Ciba-Geigy Ltd.) at a room temperature was added 3 Stirring for a time to prepare a coating composition.

Each of the coating compositions prepared above was coated on the 3 mm thick glass plate, spin coated at 1000 rpm for 20 seconds, and cured at 130 ° C. for 1 hour to prepare a coating film.

Example  9

36 g of a coating solution (manufactured by LG Chem, UT11PCF) was added to the reactor, and 1.5 g of the photochromic dye compound prepared in Example 2 was injected, followed by 220 mg of Iganox-1010 (IRGANOX ^™ , manufactured by Ciba-Geigy Co., Ltd.). To add a stirred for 3 hours at room temperature to prepare a coating composition.

After the process was performed in the same manner as in Example 8 to prepare a coating film.

Example  10

39.1 g of a coating solution (manufactured by LG Chemical Co., Ltd., UT11PCF) was added to the reactor, and 1.7 g of the photochromic dye compound prepared in Example 3 was injected, followed by addition of 600 mg of thybinin-770, followed by stirring at room temperature for 3 hours. To prepare a coating composition.

After the process was performed in the same manner as in Example 8 to prepare a coating film.

Example  11

47 g of a coating liquid (manufactured by LG Chemical Co., Ltd., UT11PCF) was added thereto, 2.2 g of the photochromic dye compound prepared in Example 4 was added thereto, and then 1.06 g of Iganox-1010 was added thereto, followed by stirring at room temperature for 3 hours. To prepare a coating composition.

After the process was performed in the same manner as in Example 8 to prepare a coating film.

Example  12

47 g of a coating solution (manufactured by LG Chemical Co., Ltd., UT11PCF) was added to the reactor, and 2.25 g of the photochromic dye compound prepared in Example 5 was injected, followed by addition of 1.03 g of Iganox-1010, followed by stirring at room temperature for 3 hours. To prepare a coating composition.

After the process was performed in the same manner as in Example 8 to prepare a coating film.

Example  13

47 g of a coating solution (manufactured by LG Chemical Co., Ltd., UT11PCF) was added thereto, 2.5 g of the photochromic dye compound prepared in Example 6 was added thereto, and 870 mg of tinubin -770 was added thereto, followed by stirring at room temperature for 3 hours. To prepare a coating composition.

After the process was performed in the same manner as in Example 8 to prepare a coating film.

Example  14

38 g of a coating solution (manufactured by LG Chemical Co., Ltd., UT11PCF) was added thereto, 2.0 g of the photochromic dye compound prepared in Example 7 was added thereto, and 686 mg of tinubin-770 was added thereto, followed by stirring at room temperature for 3 hours. To prepare a coating composition.

 After the process was performed in the same manner as in Example 8 to prepare a coating film.

Comparative example  One

48 g of a coating liquid (manufactured by LG Chemical, UT11PCF) was added to the reactor, 1.18 g of a commercial photochromic dye OXFORD BLUE (manufactured by JAMES ROBINSON), and then 1.06 g of IRGANOX-1010 and tinubin- 770 mg of 770 was added thereto, followed by stirring at room temperature for 3 hours to prepare a coating composition.

After the process was performed in the same manner as in Example 8 to prepare a coating film.

Comparative example  2

In Comparative Example 1, after the coating composition was prepared without adding tinuvin-770, a coating film was prepared in the same manner.

Experimental Example  One

In order to determine the physical properties of the coating film prepared in Examples 8 to 14 and Comparative Examples 1 and 2, the results obtained are shown in Table 1 below.

(1) optical density (OD)

The cured coating film was irradiated with 365 nm ultraviolet light (1.35 mW / cm ² ) for 5 minutes and immediately placed on a UV-vis detector to measure output light at each of a decolorized and colored state, wherein ΔOD was calculated according to Equation 1 below. Calculated by:

(2) t _{One /2}

Under the same conditions as the optical density measurement, the transmittance value at the λ _max wavelength of the sample exposed to ultraviolet light was measured as the time taken to recover from the light source to half of the complete decolorization state.

(3) weather resistance

In the ATLAS UV 2000, an accelerated weathering tester, a UVA fluorescent lamp was used to irradiate for 8 hours at a temperature of 0.77 W / m ² at 60 ° C and a condensation at 50 ° C for 4 hours (ASTM G). 154-99) The optical density was measured by exposing the sample to the cycle and the time taken for the absorption intensity at the initial λ _max wavelength to decrease by half (T _1/2 ).

(4) film thickness

The film thickness was determined by observing the cross section of the lens coated with a high magnification scanning electron microscope (Field Emission Scanning Electron Microscope, FE-SEM).

TABLE 1

division Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 ΔOD _max 0.43 0.75 0.43 0.69 0.38 0.57 0.56 0.46 0.48 λ _max 613 nm 610 nm 610 nm 630 nm 604 nm 631 nm 630 nm 601 nm 601 nm t _1/2 13 sec 15 sec 12 sec 13 sec 16 sec 20 sec 13 sec 7 sec 7 sec T _1/2 115 hr 50 hr 75 hr 95 hr 160 hr 100 hr 110 hr 90 hr 30 hr Photochromic layer thickness 5 μm 5 μm 5 μm 5 μm 5 μm 5 μm 5 μm 5 μm 5 μm

In the results of Table 1, in Examples 8 to 14, weather resistance was improved compared to Comparative Example 2 using a dye having the same wavelength (blue). At this time, in the case of Examples 9 and 10, although the weather resistance slightly weakened compared to Comparative Example 1 to which the UV stabilizer was added separately, other physical properties were superior to Comparative Example 1. In addition, in Examples 8, 11, 12, and 13, weather resistance was greatly improved. In addition, the ΔOD was _max will increase was equal to or improved, t _1/2.

Therefore, in the case of the dye containing the spirooxazine derivatives synthesized through chemical bonding with the ultraviolet stabilizer of the present invention, the basic photochromic physical properties show a certain degree of change, depending on the type of stabilizer and the substituent structure. It can be seen that the weather resistance is increased.

As described above, the spirooxazine derivatives substituted with various functional groups were prepared according to the present invention, and it was confirmed that the compound increased the coloration / decolorization rate in photochromic properties. These spirooxazine derivatives are photochromic dyes and are widely used in industrial products such as lenses, sun protection lenses, filters, camera optical systems, decorations, windows, optical recording media, optical switches, photosensitive drums, recording devices, fibers, and optical devices. Is applied.

Claims (9)

 Spirooxazine derivatives represented by Formula 1 below: [Formula 1]

In Chemical Formula 1, R ₁ and R ₂ are each independently hydrogen, a hydroxy group, an alkyl group having 1 to 5 carbon atoms; An alkoxy group having 1 to 5 carbon atoms, a hydroxy alkyl group having 1 to 5 carbon atoms, a pyrrolidinyl, an imidazolynidyl, an oxazolidinyl, a furanyl group, and a dioxola Nil group (dioxolanyl), thiophenyl group, piperidinyl group, piperidinyl group, piperazinyl group, pyrimidinyl group, pyrimidyl group, pyranyl group, pyranyl group, dioxanyl group, dioxanyl group, thiopyranyl group ( thiopyranyl), dimethyl amine group, diethyl amine group, methyl ethyl amine group, methyl propyl amine group, ethyl propyl amine group, halogen group, and -LP, At least one of R ₃ to R ₅ is -LP, P is an ultraviolet stabilizer, L is a linker linking the spiroxazine core and P, M and n are integers from 1 to 4. 2. The method of claim 1, wherein L is -OOC-, -OOC-R ₅ - selected from the group consisting of, and _{-OOCNH-R 6 -NHCOO- -, -OOC} -R 5 -COO-, -OOC-R 5 Become, R ₅ is branched or straight chain alkyl having 1 to 10 carbon atoms, R ₆ is a spirooxazine derivative having 1 to 10 carbon atoms or branched alkyl, and aliphatic or aromatic group having 6 to 40 carbon atoms. According to claim 1, wherein P is independently a benzotriazole stabilizer, a benzophenone stabilizer, a triadene stabilizer, an aryl ester stabilizer, a piperidinyl stabilizer, an oxanilide stabilizer, a hindered A spiroxazine derivative selected from the group consisting of an amine stabilizer, a hindered phenol stabilizer, a semi-hindered phenol stabilizer, and a phenylene diamine stabilizer. The method of claim 1, wherein P is a 2-hydroxy phenyl benzotriazolyl group, 2-hydroxy benzophenone group, 2-hydroxyphenyl triazonyl group, 2-hydroxy-4-alkoxybenzophenone group, tetra Methyl piperidinyl, 4-hydroxy-tetramethylpiperidinyl, 1,3-benzoldicarboxamide-N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) , 2,2,4,4-tetramethyl-7-oxa-3,20-diazaspiro [5.1.11.2] henicoic acid-21-one, poly-[[6-[(1,1,3 , 3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino]- 1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl) imino]], 2,2,4,4-tetramethyl-7-oxa-3,20 Diazadispiro [5.1.11.2] henicoic acid-21-one, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadiespiro [5.1.11.2] henicoic acid- Reaction product of 21-one with epichlorohydrin,

,

,

,

, And

Spirooxazine derivatives selected from the group consisting of. The spiroxazine derivative of claim 1, wherein the spiroxazine derivative is selected from the group consisting of compounds represented by the following Chemical Formulas 1a to 1g. [Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

[Formula 1g]

A method for preparing a spirooxazine derivative of Formula 1 comprising the step of binding the electrophilic end of the linker compound, respectively, between the nucleophilic end of the spirooxazine compound, and the nucleophilic end of the ultraviolet stabilizer. The method of claim 6, wherein the spiroxazine derivative is prepared by (a) reacting the linker compound with the ultraviolet stabilizer, and then reacting the spirooxazine compound with the compound to which the linker-ultraviolet stabilizer is bound, (b) reacting the spirooxazine compound with the linker compound, and then reacting the spirooxazine-linker bound compound with the ultraviolet stabilizer, or (c) reacting the indole compound which is a precursor of the spirooxazine compound and the linker compound, and then reacting the nitroso compound to prepare a spirooxazine compound having a linker, and reacting it with an ultraviolet light stabilizer. Method for producing a spirooxazine derivative comprising a. The method of claim 6, The spirooxazine compound is a compound represented by the following Chemical Formula 2 as a compound before the linker-ultraviolet stabilizer is bonded in Chemical Formula 1, The linker compound has an electrophilic terminal selected from the group consisting of an isocyanate group, an anhydride group, an ester group, an ether group, a carbonate group, and a urethane group, and is -OOC-, -OOC-R ₅ -by a condensation reaction. A compound capable of forming a linker unit selected from the group consisting of -OOC-R ₅ -COO-, -OOC-R _5- , and -OOCNH-R ₆ -NHCOO-, The UV stabilizer is a benzotriazole compound, a benzophenone compound, a triadine compound, an aryl ester compound, a piperidinyl compound, an oxanilide compound, a hindered amine compound, a hindered phenol compound, a semi-hin Method for preparing a spirooxazine derivative selected from the group consisting of a phenolic compound, and a phenylene diamine compound: [Formula 2]

In Chemical Formula 2, R ₁ to R ₅ are each independently hydrogen, a hydroxy group, an alkyl group having 1 to 5 carbon atoms; An alkoxy group having 1 to 5 carbon atoms, a hydroxy alkyl group having 1 to 5 carbon atoms, a pyrrolidinyl, an imidazolynidyl, an oxazolidinyl, a furanyl group, and a dioxola Nil group (dioxolanyl), thiophenyl group, piperidinyl group, piperidinyl group, piperazinyl group, pyrimidinyl group, pyrimidyl group, pyranyl group, pyranyl group, dioxanyl group, dioxanyl group, thiopyranyl group ( thiopyranyl), a dimethyl amine group, a diethyl amine group, a methyl ethyl amine group, a methyl propyl amine group, an ethyl propyl amine group, and a halogen group, and m and n are integers of 1 to 4.  A photochromic dye comprising a spiroxazine derivative according to any one of claims 1 to 5.