KR100855215B1 - Responsive naphthopyran compound, photochromic polyurethane coating liquid composition comprising the same, photochromic polyurethane and photochromic optical article comprising the same - Google Patents

Abstract

The present invention relates to a reactive naphthopyran compound, a photochromic polyurethane coating liquid composition comprising the same, a photochromic polyurethane, and a photochromic optical article including the same, and more particularly, to Formula 1 or It relates to a reactive naphthopyran compound represented by 2, a photochromic polyurethane coating liquid composition comprising the same, a photochromic polyurethane grafted with a reactive naphthopyran, and a photochromic optical article comprising the same.

Since the photochromic polyurethane coating solution composition of the present invention includes a naphthopyran compound which can be grafted directly to a polyurethane molecule, phase separation does not occur even in the coating solution, and the photochromic coating film prepared therefrom may be used. There is no blooming phenomenon due to, there is an advantage that the photochromic properties can be maintained for a long time.

[Formula 1] [Formula 2]

In Chemical Formulas 1 and 2, X ¹ to X ⁴ Has the same structure as in the detailed description of the invention.

Responsive, Photochromic, Naphthopyran, Polyurethane, Graft, Coating Film

Description

REACTIVE NAPHTHOPYRAN COMPOUND, A PHOTOCROMIC POLYURETHANE COATING COMPOSITION CONTAINING THE NAPHTHOPYRAN COMPOUND, A PHOTOCROMIC POLYURETHANE GRAFTED WITH THE NAPHTHOPYRAN GRAFT, AND A PHOTOCHROMIC OPTICAL ARTICLE COMPRISING THE SAME}

[Industrial use]

The present invention relates to a reactive naphthopyran compound, a photochromic polyurethane coating liquid composition comprising the same, a photochromic polyurethane and a photochromic optical product comprising the same, and more particularly, without phase separation in the coating liquid. , Reactive naphthopyran compound with no blooming phenomenon over time when manufactured with a coating film, photochromic polyurethane coating liquid composition comprising the same, photochromic polyurethane and photochromic optical products comprising the same It is about.

[Private Technology]

Eyewear products such as sunglasses, fashion lenses, over-the-counter and prescription lenses, sports masks, face shields and goggles require transparent plastics that can provide good image quality while reducing incident light to the eye.

In response to this need, considerable attention has been paid to photochromic plastic products used for optical applications. In particular, ophthalmic photochromic plastic lenses have been of interest because of the weight advantages they offer over glass lenses.

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 a color change occurs visually. In general, photochromic materials exhibit a color change (coloring) when exposed to ultraviolet light, and return to their original color or colorless state when the ultraviolet light is blocked.

Eye products where photochromic material (s) are applied to or incorporated into the product exhibit this reversible color change and consequently a reversible light transfer change.

The literature describes that such mechanisms govern the reversible color change, ie the change in the absorption spectrum in the electromagnetic spectrum of visible light (400-700 nm), which is characteristic of different types of organic photochromic compounds. It is.

See, eg, John C. Crano, "Chromogenic Materials (Photochromic)", Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition, 1993, pp. 321-332 describe mechanisms that govern the reversible color change of organic photochromic compounds (eg, indolino spiropyran and indolino spiroxazine) include an electron cyclic mechanism. That is, when exposed to activating ultraviolet light, these organic photochromic compounds are transformed from colorless ring-opening form to colored ring-opening form.

In contrast, the electron cyclization mechanism that governs the reversible color change of photochromic fulgide compounds is believed to involve a transformation from colorless ring-opening forms to colored ring closure forms.

U.S. Pat.Nos. 5,130,353 and 5,185,390 produced photochromic plastic articles by incorporating photochromic materials into plastic substrates by surface absorption techniques. For example, one or more photochromic dyes / compounds may first be applied to the surface of a plastic article as neat photochromic dyes / compounds or in dissolved form in a polymer or other organic solvent carrier, and then the coated surface is heated to By diffusing the photochromic dye / compound (s) into the subsurface area of the lens (commonly referred to as "absorption"), the photochromic dye is incorporated into the subsurface area of a plastic product such as a lens.

U. S. Patent No. 6,187, 444 describes forming an organic photochromic coating on the surface of these plastic substrates in order to enable the use of thermoset polymers, thermoplastic polycarbonates and highly crosslinked optical polymer materials as plastic substrates in photochromic products. Suggested.

The polymer forming the photochromic coating layer as described above changes color or cracks as time passes, and degradation (degradation) occurs that loses its original properties little by little by heat or light. To avoid this problem, most polymer products essentially contain 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, but may deteriorate the coating properties when used excessively, a blooming (blooming) phenomenon that the photochromic dye leaks after a long time appears.

Recently, a method of using naphthopyran compounds in photochromic layers has been proposed. However, naphthopy itself does not have a reactive functional group that can be combined with the polyurethane polymer, and simply exists in a mixed state in the coating film, so phase separation may occur over time, and blooming may still occur. There is a problem.

The present invention is to solve the problems of the prior art as described above, it is an object of the present invention to provide a reactive naphthopyran compound that can be grafted directly to the polyurethane polymer.

Another object of the present invention is to provide a photochromic polyurethane coating solution composition comprising the reactive naphthopyran compound.

Still another object of the present invention is to provide a photochromic polyurethane grafted with the reactive naphthopyran compound.

Still another object of the present invention is to provide a photochromic optical product including a coating film prepared from the photochromic polyurethane coating liquid composition.

The present invention to achieve the above object,

It provides a reactive naphthopyran compound represented by the formula (1) or formula (2):

In Chemical Formulas 1 and 2,

X ¹ to X ⁴ 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, an alkyl amine group, a halogen group and a -LP group,

At least one of X ¹ to X ⁴ is a -LP group,

The L is a linker connecting the naphthopyran core and the P, -OOC-, -OOC-R _1- , -OOC-R ₁ -COO-, -R ₂ -OOC-R ₁ -COO-R _3- , and -OOC-NH-R ₄ -NH-COO-, wherein R ₁ To R ₃ are each independently a branched or straight chain alkyl group having 1 to 20 carbon atoms, R ₄ is a branched or straight chain alkyl group having 1 to 40 carbon atoms and an aromatic group having 6 to 40 carbon atoms,

P is -R ₅ -Z, R ₅ is a branched or straight chain alkyl group having 1 to 10 carbon atoms, Z is a reactive terminal selected from -OH, -COOH, or -COOR ₆ , the R ₆ Is an alkyl group having 1 to 20 carbon atoms.

In addition, the present invention is diisocyanate; Polyols; A reactive naphthopyran compound represented by Formula 1 or Formula 2; And it provides a photochromic polyurethane coating solution composition comprising a catalyst.

The present invention also provides a photochromic polyurethane grafted with the reactive naphthopyran compound.

The present invention also provides a photochromic optical article comprising a coating film prepared from the photochromic polyurethane coating liquid composition.

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

The naphthopyran compound is represented by the following Chemical Formula a, and is known as a photochromic dye that changes color depending on light irradiation.

 [Formula a]

Although the naphthopyran compound is mixed with the polyurethane resin precursor or the diisocyanate and polyol in the monomer state to form a coating film, the naphthopyran compound is present only in the mixed state with the polyurethane polymer, and cannot form a bond with the polyurethane polymer.

However, the 'reactive naphthopyran compound' according to the present invention may be grafted directly to the polyurethane polymer because it contains at least one hydroxyl group (-OH), which is a reactive functional group to be grafted to the polyurethane polymer.

The reactive naphthopyran compound of the present invention is represented by the formula (1) or (2), and preferred examples thereof include compounds represented by the following formulas (3) to (6).

On the other hand, the photochromic polyurethane coating liquid composition of the present invention is diisocyanate; Polyols; A reactive naphthopyran compound represented by Formula 1 or Formula 2; And catalysts.

In general, polyurethane resins are prepared by polymerization of diisocyanates and polyols, and the reactive naphthopyran compounds of the present invention react with diisocyanates with polyols to impart photochromic properties to polyurethane resins.

In the present invention, the diisocyanate is generally used in the preparation of the polyurethane resin, so the kind is not particularly limited, but aliphatic diisocyanate, alicyclic diisocyanate, blocked aliphatic diisocyanate, and blocked alicyclic ring It is preferable that it is at least 1 type selected from the group which consists of group diisocyanate. More preferably, the diisocyanate is hexamethylene diisocyanate, 1,3,3-trimethyl hexamethylene diisocyanate, isophorone diisocyanate, toluene-2,6-diisocyanate and 4,4'-dicyclohexylmethane diisocyanate One or more selected from the group consisting of can be used.

In addition, the polyol is not particularly limited as it may also be used in the production of general polyurethane resin, but is not particularly limited, high molecular weight polyol including polyester polyol, polyether polyol, polyacrylic polyol, and polycarbonate polyol; And one or more selected from the group consisting of low molecular weight polyols having a molecular weight of 50 to 500 g / mol. The high molecular weight polyols form soft segments of polyurethane, and the low molecular weight polyols form hard segments of polyurethane.

At this time, the polyol is preferably included in 50 to 300 parts by weight, more preferably 75 to 200 parts by weight based on 100 parts by weight of the diisocyanate. That is, the content of the polyol is preferably 50 parts by weight or more so that the coating film is sufficiently cured, and the content of the polyol is preferably 300 parts by weight or less in order to prevent appearance defects and performance degradation of the coating film according to the unreacted material.

The reactive naphthopyran compound may be used to select the compound represented by the formula (1) or 2, the content is preferably included 1 to 20 parts by weight based on 100 parts by weight of the diisocyanate. That is, it is preferable to include 1 part by weight or more in order to exhibit the minimum photochromic properties, and preferably 20 parts by weight or less in order to prevent the dark initial color and to secure the mechanical properties of the coating layer. .

The catalyst may be added to those commonly used in the production of polyurethane resins. In this case, the content of the catalyst is preferably included in 0.01 to 10 parts by weight based on 100 parts by weight of the diisocyanate in consideration of the reaction efficiency.

In addition, the coating liquid composition of the present invention may further include an organic solvent, if necessary. The organic solvent is not particularly limited because it can be selected and used within the usual range, but is not particularly limited, benzene, toluene, methyl ethyl ketone, acetone, ethanol, methanol, propanol, isopropanol, tetrahydrofuran, dioxane, ethyl acetate, ethylene One or more selected from the group consisting of glycol, xylene, cyclohexane and N-methyl pyrrolidinone may be used, and the content thereof may be 10 to 100 parts by weight of the diisocyanate in consideration of reaction efficiency and thickness of the coating film. It is preferably included to 70 parts by weight.

On the other hand, the photochromic polyurethane of the present invention is characterized in that it is grafted with the reactive naphthopyran compound.

In order for the photochromic polyurethane to exhibit excellent photochromic properties, the reactive naphthopyran compound is preferably grafted at a ratio of 1.0% by weight or more with respect to the diisocyanate and the polyol as a whole. In order to secure mechanical properties, it is preferable to be grafted at a ratio of 20% by weight or less. However, the content is just described a preferred example, the scope of the present invention is not limited thereto, and the content of the naphthopyran compound can be arbitrarily adjusted according to the degree of the desired color.

On the other hand, the present invention provides a photochromic optical product comprising a coating film prepared from the photochromic polyurethane coating liquid composition.

The coating liquid composition is coated by coating on one or both surfaces of the optical substrate and the optical substrate using conventional wet coating methods such as spray coating, spin coating, dip coating, and doctor blading coating, and coating the coating film by ultraviolet or thermal curing. Can be formed.

At this time, the coating film is preferably formed to have a certain degree of transparency in order to be applied to the optical product, it is more preferably manufactured in the form of a photochromic polyurethane coating film having a thickness of 5 to 40 ㎛.

In addition, the coating and curing process of the polyurethane coating film is not significantly different from the curing process of the conventional polyurethane coating film, and since the optimum conditions can be determined within the usual range, it is not particularly limited in the present invention. However, in order to obtain better characteristics of the coating film, when an unblocked type of diisocyanate is used, the reaction is preferably performed at 25 to 80 ° C., and a diisocyanate of a blocked type is used. When using, it is preferable to harden at 100-150 degreeC.

Industrial products to which such coatings can be applied include those in which photochromic materials are typically used, such as optical lenses, flat lenses, face shields, goggles, camera lenses, windows, automotive transparents, inks, decorations, It can be used for films, sheets, coatings, paints and protective documents (such as passports, driver's licenses and check marks on banknotes).

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[Response type Naphthopyran  Preparation of Compound

Example  One

According to Scheme 1 below, a reactive naphthopyran compound represented by Chemical Formula 3 was prepared.

Scheme 1

(Preparation of Compound of Formula 8)

10.0 g (62.0 mmol) of 2,7-dihroxynaphthalene represented by Formula 7, 0.65 g (2.6 mmol) of pyridinium-p-toulenesulfonate, and pyridinium-p-toulenesulfonate A solution of 11.0 g (104 mmol) of trimethyl orthoformate dissolved in 30 mL of ethylene chloride; and 1,1-diphenyl-2-propyn-1-ol (1,1-diphenyl -2-propyn-1-ol) 6.0 g (29.0 mmol) dissolved in 20 mL of ethylene chloride (ethylene chloride) was mixed to prepare a reaction mixture.

After the reaction mixture was reacted by refluxing for 2 hours while boiling, the reaction mixture was cooled to room temperature (about 25 ° C.), and the solvent was evaporated in vacuo. The organic layer obtained from this was dried over anhydrous sodium sulfate and condensed under reduced pressure.

The reaction product obtained in the above process was passed through a silica gel chromatography ( n- hexane: ethyl acetate = 1: 2 volume ratio) apparatus to obtain a purple solid represented by Chemical Formula 1 in Scheme 1 (4.0 g, yield 40%). ; ¹ H NMR (500 MHz, CDCl ₃ ): δ = 6.24 (d, 1H), 6.92 (d, 1H), 7.07.17 (d, 1H), 7.26 (m, 2H), 7.27 (s, 1H), 7.33 (m, 4 H), 7.49 (d, 4 H), 7.6 (q, 2 H).

(Compound Preparation of Formula 9)

900 mg (2.57 mmol) of the compound of Formula 8, 32 g (0.26 mmol) of dimethylaminopyridine (DMAP) were dissolved in 10 mL of dichloromethane (CH ₂ Cl ₂ ), and then glutaric anhydride 290 mg (2.57 mmol) was added. The reaction mixture was then reacted by refluxing for 4 hours with boiling. The organic layer obtained from this was dried over anhydrous sodium sulfate and condensed under reduced pressure.

The reaction product obtained in the above process was passed through a silica gel chromatography ( n- hexane: ethyl acetate = 1: 1 volume ratio) apparatus to obtain a compound represented by Chemical Formula 9 in Scheme 1 (620 mg, yield 53%); ¹ H NMR (500 MHz, CDCl ₃ ): δ = 2.11 (q, 2H), 2.55 (t, 2H), 2.71 (t, 2H), 6.25 (d, 1H), 7.03 (dd, 1H), 7.18 ( t, 2H), 7.24 (m, 2H), 7.29 (m, 4H), 7.45 (m, 4H), 7.63 (m, 2H), 7.71 (d, 1H).

(Compound Preparation)

Compound 310 mg (0.67 mmol) of the above formula 9, N - (3- dimethylaminopropyl) - N '- ethylcarbodiimide 288 mg (1.01 mmol) and DMAP 9 mg (0.07 mmol) in dichloromethane (CH ₂ Cl ₂ ) After dissolving in 10 mL, 0.13 mL (1.01 mmol) of 1,3-propanediol was added. The reaction mixture was then reacted by refluxing for 4 hours with boiling. The organic layer obtained from this was dried over anhydrous sodium sulfate and condensed under reduced pressure.

The reaction product obtained in the above process was passed through a silica gel chromatography ( n- hexane: ethyl acetate = 1: 1 volume ratio) apparatus to obtain a compound represented by Chemical Formula 3 in Scheme 2 (235 mg, yield 67%); ¹ H NMR (500 MHz, CDCl ₃ ): δ = 2.07 (m, 2H), 2.47 (m, 2H), 2.66 (m, 2H), 3.62 (m, 2H), 3.71 (m, 2H), 4.29 ( m, 2H), 6.25 (dd, 1H), 7.03 (d, 1H), 7.18 (t, 2H), 7.24 (m, 2H), 7.29 (m, 4H), 7.45 (m, 4H), 7.63 (m , 2H), 7.71 (d, 1H).

Example  2

According to Scheme 1, a reactive naphthopyran compound represented by Chemical Formula 4 was prepared.

(Preparation of Compound of Formula 4)

1.02 g (2.2 mmol) of the compound of formula 9 prepared in Example 1, 0.98 g (6.6 mmol) of triethyleneglycol, 0.50 g (2.6 mmol) of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide ) And 13.3 mg (0.11 mmol) of DMAP were dissolved in 30 mL of dichloromethane (CH ₂ Cl ₂ ) to prepare a reaction mixture. The reaction mixture was then reacted by refluxing for 4 hours with boiling.

After the reaction, the reaction mixture was cooled to room temperature (about 25 ° C.) and washed with brine (100 mL × 3). The organic layer obtained therefrom was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated in vacuo to obtain the compound of formula 4 in the form of a transparent oil.

Example  3

According to Scheme 2 below, a reactive naphthopyran compound represented by Chemical Formula 5 was prepared.

Scheme 2

(Preparation of Compound of Formula 11)

3.0 g (5.9 mmol) of the compound represented by Formula 10 and 0.9 g (11.8 mmol) of glutaric anhydride were dissolved in 100 mL of dichloromethane (CH ₂ Cl ₂ ) to give a reaction mixture. After the preparation, the reaction mixture was reacted under reflux with boiling for 8 hours in the presence of dimethylaminopyridine (DMAP) corresponding to about 1% by weight of the catalyst.

After the reaction, the reaction mixture was cooled to room temperature (about 25 ° C.) and washed with brine (100 mL × 3). The organic layer obtained from this was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated in vacuo.

The reaction product remaining in the above process was passed through a silica gel chromatography ( n- hexane: ethyl alcohol = 1: 1 volume ratio) apparatus to obtain a dark green solid represented by Chemical Formula 11 (2.1 g, yield 60%); ¹ H NMR (500 MHz, CDCl ₃ ): δ == 1.95 (quintet, 2H), 2.05 (m, 4H), 2.40 (q, 4H), 2.90 (s, 6H), 3.41 (m, 4H), 3.75 (s, 3H), 5.23 (s, 2H), 6.15 (d, 1H), 6.66 (d, 1H), 6.80 (t, 3H), 6.93 (d, 1H), 7.13 (s, 1H), 7.19 ( s, 1H), 7.34 (d, 2H), 7.43 (d, 2H), 7.54 (d, 1H).

(Compound Preparation of Formula 5)

415 mg (0.67 mmol) of the compound of Formula 11, 288 mg (1.01 mmol) of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide, and 9 mg (0.07 mmol) of DMAP were diluted with dichloromethane (CH ₂ Cl ₂ ) After dissolving in 10 mL, 0.13 mL (1.01 mmol) of 1,3-propanediol was added. The reaction mixture was then reacted by refluxing for 4 hours with boiling.

The organic layer obtained therefrom was dried over anhydrous sodium sulfate, and condensed under reduced pressure to obtain a compound represented by Chemical Formula 5.

Example  4

According to Scheme 2, a reactive naphthopyran compound represented by the following Chemical Formula 6 was prepared.

(Preparation of Compound of Formula 8)

1.36 g (2.2 mmol) of a compound of Formula 11 prepared in Example 3, 0.98 g (6.6 mmol) of triethylene glycol, 0.50 g (2.6 mmol) of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide And 13.3 mg (0.11 mmol) of DMAP were dissolved in 30 mL of dichloromethane (CH ₂ Cl ₂ ) to prepare a reaction mixture. The reaction mixture was then reacted at reflux for 4 hours while boiling.

After the reaction, the reaction mixture was cooled to room temperature (about 25 ° C.) and washed with brine (100 mL × 3). The organic layer obtained therefrom was dried over anhydrous MgSO 4, filtered, and the solvent was evaporated in vacuo to obtain a compound represented by Chemical Formula 6.

[Responsive Polyurethane Of coating film  Produce]

Production Example  One

38 g of a coating liquid (LG Chemical Co., Ltd., AT21PC: polyurethane monomer coating liquid containing polyol, diol, and diisocyanate) was added to the reactor, 0.76 g of a reactive naphthopyran compound represented by Chemical Formula 3 was injected therein, and then thiuvin- 0.38 g of 144 (Tinuvin ^™ , manufactured by Ciba-Geigy Co., Ltd.) was added thereto, and stirred at room temperature for 3 hours to prepare a coating composition.

The prepared coating composition was applied on a 3 mm thick glass plate, spin coated at 1000 rpm for 20 seconds, and cured at 130 ° C. for 1 hour to prepare a photochromic polyurethane coating film.

Production Example  2

A photochromic polyurethane coating film was prepared in the same manner as in Preparation Example 1, except that 0.76 g of a reactive naphthopyran compound of Formula 4 was used.

Production Example  3

A photochromic polyurethane coating film was prepared in the same manner as in Preparation Example 1, except that 0.76 g of a reactive naphthopyran compound of Formula 5 was used.

Production Example  4

A photochromic polyurethane coating film was prepared in the same manner as in Preparation Example 1, except that 0.76 g of a reactive naphthopyran compound of Formula 6 was used.

Comparative example  One

A photochromic polyurethane coating film was prepared in the same manner as in Preparation Example 1, except that 0.76 g of a general naphthopyran compound represented by the following Formula 12 was used.

[Formula 12]

Comparative example  2

A photochromic polyurethane coating film was prepared in the same manner as in Preparation Example 1, except that 0.76 g of the naphthopyran compound represented by the following Formula 13 was used.

[Formula 13]

Comparative example  3

A photochromic polyurethane coating film was prepared in the same manner as in Preparation Example 1, except that 0.76 g of the naphthopyran compound represented by the following Formula 14 was used.

[Formula 14]

[ Photochromic  Polyurethane Of coating film  Property measurement]

In order to determine the physical properties of the photochromic polyurethane coating film prepared according to Preparation Examples 1 to 4, and Comparative Examples 1 to 3, the following experiment was performed, and the results are shown in Table 1 below.

(1) optical density (OD)

The cured coating film was irradiated with ultraviolet light (1.35 mW / cm ² ) of 365 nm wavelength for 5 minutes, and then immediately measured by using a UV-Vis detector, the output light in the decolorized and colored state, respectively. At this time, ΔOD was calculated according to the following formula (1).

[Calculation 1]

(2) Desorption speed  ( t _{One /2} )

The transmittance at the λ _max wavelength of the sample exposed to ultraviolet light under the same conditions as the optical density (OD) measurement was measured by the time taken to recover to half of the complete decolorization state after the light source was removed.

(3) weather resistance ( T _{One /2} )

Each sample was irradiated for 8 hours at a wavelength of 340 nm, a light quantity of 0.77 W / m ² , and 60 ° C. using a UVA fluorescent lamp in ATLAS UV 2000, an accelerated weathering tester, and condensation was performed at 50 ° C. for 4 hours. After repeating the process (ASTM G 154-99), the optical density was measured and measured by the time taken for the absorption intensity at the initial λ _max wavelength to decrease by half.

(4) film thickness

The film thickness was measured by observing the cross section using a micrometer.

division Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 ΔOD _max 0.52 0.54 0.72 0.67 0.45 0.35 0.58 λ _{max (nm)} 430 430 490 490 425 432 490 t _1/2 (sec) 26 30 354 294 150 15 > 3000 T _1/2 (hr) 150 135 120 115 115 85 107 Film thickness (㎛) 15 14 16 15 14 15 16

As shown in Table 1, the polyurethane coating film grafted with the reactive naphthopyran compound according to the present invention has a high optical density, a short discoloration time, excellent discoloration, and excellent durability.

Since the photochromic polyurethane coating solution composition of the present invention includes a naphthopyran compound which can be grafted directly to a polyurethane molecule, phase separation does not occur even in the coating solution, and the photochromic coating film prepared therefrom may be used. There is no blooming phenomenon, and there is an advantage that the photochromic property can be maintained for a long time.

Claims (9)

Reaction type naphthopyran compound represented by the following general formula (1) or (2): [Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2, X ¹ to X ⁴ 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, an alkyl amine group, a halogen group and a -LP group, At least one of X ¹ to X ⁴ is a -LP group, The L is a linker connecting the naphthopyran core and the P, -OOC-, -OOC-R _1- , -OOC-R ₁ -COO-, -R ₂ -OOC-R ₁ -COO-R _3- , and -OOC-NH-R ₄ -NH-COO- is selected from the group consisting of, R ₁ to R ₃ are each independently a branched or straight alkyl group having 1 to 20 carbon atoms R ₄ is a branched or straight chain alkyl group having 1 to 40 carbon atoms, or an aromatic group having 6 to 40 carbon atoms, P is -R ₅ -Z, R ₅ is a branched or straight chain alkyl group having 1 to 10 carbon atoms, Z is a reactive terminal selected from -OH, -COOH, or -COOR ₆ , the R ₆ Is an alkyl group having 1 to 20 carbon atoms. Diisocyanate; Polyols; Reaction type naphthopyran compound represented by Formula 1 or Formula 2 of claim 1; And Catalyst for polymerization reaction of the diisocyanate and polyol Photochromic polyurethane coating solution composition comprising a. The method of claim 2, Per 100 parts by weight of the diisocyanate, 50 to 300 parts by weight of the polyol; 1 to 20 parts by weight of the reactive naphthopyran compound; And 0.01 to 10 parts by weight of the catalyst Photochromic polyurethane coating solution composition comprising a. The method of claim 2, The diisocyanate is at least one member selected from the group consisting of aliphatic diisocyanate, alicyclic diisocyanate, blocked aliphatic diisocyanate, and blocked alicyclic diisocyanate. The method of claim 2, The polyol is at least one high molecular weight polyol selected from the group consisting of polyester polyols, polyether polyols, polyacryl polyols, and polycarbonate polyols; And at least one low molecular weight polyol having a molecular weight of 50 to 500 g / mol. The method of claim 2, The reactive naphthopyran compound is a photochromic polyurethane coating solution composition is selected from the group consisting of compounds represented by the following formula (3). [Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

A photochromic polyurethane grafted with a reactive naphthopyran compound represented by Formula 1 or Formula 2 of claim 1. The method of claim 7, wherein The polyurethane is a photochromic polyurethane in which the reactive naphthopyran compound is grafted at a ratio of 1.0 to 20% by weight relative to the total weight of diisosinate and polyol. A photochromic polyurethane coating film prepared from the photochromic polyurethane coating liquid composition according to any one of claims 2 to 6 and having a thickness of 5 to 40 µm. Photochromic optics comprising a.