KR20070098182A - A reactive spironaphthoxazine compound, a photocromic poly(meth)acrylic polymer coating composition containing the spironaphthoxazine compound, a photocromic poly(meth)acrylic polymer grafted with the spironaphthoxazine, and a photochromic optical article comprising the same - Google Patents

Abstract

A reactive spironaphthoxazine compound is provided to inhibit phase separation over time and blooming phenomena of the spironaphthoxazine compound by serving reactive groups capable of directly grafting with polyacrylic polymer molecules. A reactive spironaphthoxazine compound represented by the formula(1) is provided, wherein X^1 to X^3 are each independently hydrogen, C1-C10 alkyl group, hydroxy group, C1-C10 alkoxy group, C1-C10 hydroxy alkyl group, 5- or 6-membered heterocyclic group substituted by N, O or S, amine group substituted by C1-C4 alkyl group or -L-P group; L is a linker for connecting spironaphthoxazine core portion to P, and is selected from -OOC-, -OOC-R1-, -R2-OOC-R1-COO-, -OOC-R1-COO-, -NH-CO-R3-COO- and -OOC-HN-R3-NH-COO-; R1 and R2 are each independently C1-C10 branched or linear alkyl group; R3 is C1-C10 branched or linear alkyl group or C6-C40 aromatic group; and P is acrylate or methacrylate containing vinyl group.

Description

Reactive spironaphthoxazine compound, photochromic polyacrylic coating liquid composition comprising the same, photochromic polyacrylic and photochromic optical products comprising the same THE SPIRONAPHTHOXAZINE COMPOUND, A PHOTOCROMIC POLY (METH) ACRYLIC POLYMER GRAFTED WITH THE SPIRONAPHTHOXAZINE, AND A PHOTOCHROMIC OPTICAL ARTICLE COMPRISING THE SAME}

[Industrial use]

The present invention relates to a reactive spironaphthoxazine compound, a photochromic polyacrylic coating liquid composition comprising the same, a photochromic polyacrylic and a photochromic optical product comprising the same, and more particularly, a phase separation phenomenon occurs in the coating liquid. Reaction type spironaphthoxazine compound which does not have a blooming phenomenon over time when manufactured with a coating film, a photochromic polyacrylic coating liquid composition comprising the same, a photochromic polyacryl, and a photochromic including the same It relates to an optical product.

 [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.

Spirooxazine compounds are mainly used as the photochromic compounds used in the photochromic layer of general photochromic products. Korean Unexamined Patent Publication No. 2004-0071228 describes an example in which a photochromic organic polymer coating layer including one or more organic photochromic materials is formed on a surface of an organic polymer substrate.

In addition, JP 2005-215640 A describes a photochromic lens including a thermosetting polyacrylic resin layer containing a photochromic compound.

In this case, however, the photochromic material is a general spiroxazine compound, which itself does not have a reactive functional group that can be combined with a polyacrylic polymer, and simply exists in a mixed state in the coating film over time. Accordingly, there may be a phase separation phenomenon, and a blooming phenomenon in which the photochromic dye leaks out may occur.

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

Another object of the present invention is to provide a photochromic polyacrylic coating liquid composition comprising the reactive spironaphthoxazine compound.

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

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

The present invention to achieve the above object,

It provides a reactive spironaphthoxazine compound represented by the formula (1):

In Chemical Formula 1,

X ¹ to X ³ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a hydroxy alkyl group having 1 to 10 carbon atoms, at least one substituted with N, O, or S It is selected from the group consisting of a 5- or 6- heterocyclic group, an amine group substituted with an alkyl group having 1 to 4 carbon atoms, and -LP group,

At least one of X ¹ to X ³ is a -LP group,

The L is a linker connecting the spironaphthoxone core and the P, -OOC-, -OOC-R _1- , -R ₂ -OOC-R ₁ -COO-, -OOC- R ₁ -COO-, -NH-CO-R ₃ -COO- and -OOC-HN-R ₃ -NH-COO- is selected from the group, wherein R ₁ and R ₂ are each independently 1 to 10 carbon atoms Phosphorus branched or straight chain alkyl, R ₃ is branched or straight chain alkyl having 1 to 10 carbon atoms and aromatic group having 6 to 40 carbon atoms,

P is an acrylate or methacrylate group containing a vinyl group, preferably P is represented by the following formula (2):

In Formula 2, R ₄ is hydrogen or a methyl group, R ₅ is a branched or straight alkyl group having 1 to 5 carbon atoms, a is 0 or 1.

Moreover, this invention is bisphenol-A di (meth) acrylate; Polyethylene glycol di (meth) acrylates; Reactive spironaphthoxazine compound represented by Formula 1; And it provides a photochromic polyacrylic coating liquid composition comprising an ultraviolet initiator or a thermal initiator.

The present invention also provides a photochromic polyacryl grafted with the reactive spironaphthoxazine compound.

In addition, the present invention provides a photochromic optical article comprising a coating film of 5 to 40 ㎛ thickness prepared from the photochromic polyacrylic coating liquid composition.

In the present invention, the 'di (meth) acrylate' means a diacrylate or dimethacrylate.

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

The spironaphthoxazine compound is represented by the following formula (3) and is known as a photochromic dye whose color changes depending on whether light is irradiated.

The spironaphthoxazine compound is mixed with a polyacrylic resin precursor or a bisphenol A-based di (meth) acrylate and a polyethylene glycol-based di (meth) acrylate in a monomer state to form a coating film. It is present only and cannot form a bond with the polyacrylic resin.

However, the 'reactive spironaphthoxazine compound' according to the present invention may be grafted directly to the polyacrylic resin because it contains at least one (meth) acryl group, which is a reactive functional group to be grafted to the polyacrylic resin.

The reactive spironaphthoxazine compound of the present invention is represented by the formula (1), and examples thereof include compounds represented by the following formulas (4) to (7).

On the other hand, the photochromic polyacrylic coating liquid composition of the present invention is bisphenol A-based di (meth) acrylate; Polyethylene glycol di (meth) acrylates; Reactive spironaphthoxazine compound represented by Formula 1; And ultraviolet initiators or thermal initiators.

Generally, polyacrylic resins are prepared by polymerization of bisphenol A-based di (meth) acrylate and polyethylene glycol-based di (meth) acrylate, and the reactive spironaphthoxazine compound of the present invention is graft-bonded to the polyacrylic resin. To give photochromic properties.

In the present invention, the bisphenol A-based di (meth) acrylate is generally used in the manufacture of a polyacrylic resin, so its kind is not particularly limited, but bisphenol A-based ethylene oxide dimethacrylate, bisphenol A At least one selected from the group consisting of a propylene oxide dimethacrylate, a bisphenol A ethylene oxide diacrylate, and a bisphenol A propylene oxide diacrylate is preferable.

In addition, the polyethylene glycol-based di (meth) acrylate may also be used in the production of a general polyacrylic resin can be used, but the type thereof is not particularly limited, triethylene glycol di (meth) acrylate, PEG 600 di (meth) It is preferable that at least 1 sort (s) is chosen from the group which consists of a) acrylate, PEG 400 di (meth) acrylate, and PEG 200 di (meth) acrylate.

In this case, the polyethylene glycol di (meth) acrylate is preferably contained in 25 to 150 parts by weight based on 100 parts by weight of the bisphenol A-based di (meth) acrylate. That is, it is preferable to include at least 25 parts by weight in consideration of flexibility, and preferably at most 150 parts by weight in consideration of the structural properties of the coating layer.

As the reactive spironaphthoxazine compound, a compound represented by Chemical Formula 1 may be selected and used, and the content may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the bisphenol A-based di (meth) acrylate. desirable. That is, it is preferable to include at least 1 part by weight in order to exhibit at least a photochromic property, and to include at least 20 parts by weight in order to prevent excessive initial color and to secure the mechanical properties of the coating layer. .

The initiator may be added to those commonly used in the production of polyacrylic resins. In this case, the initiator may be used by selecting an ultraviolet (UV) initiator or a thermal initiator according to the curing method of the coating film, the content is 0.1 to 100 parts by weight of the bisphenol A-based di (meth) acrylate in consideration of the reaction efficiency It is preferably included in 10 parts by weight.

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 may 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 is in consideration of the reaction efficiency and the thickness of the coating film. It is preferably included in 10 to 70 parts by weight based on 100 parts by weight of the rate.

On the other hand, the photochromic polyacrylamide of the present invention polymerized from the coating solution composition is characterized in that the reactive spironaphthoxazine compound is graft bonded.

In order for the photochromic polyacryl to exhibit excellent photochromic properties, the reactive spironaphthoxazine compound is based on the total weight of the bisphenol A-based di (meth) acrylate and polyethylene glycol-based di (meth) acrylate. It is preferable to be grafted at a ratio of 1.0 wt% or more, and to be grafted at a ratio of 20.0 wt% or less in order to secure excessive discoloration and mechanical properties of the coating layer. However, the content is just described a preferred example, the scope of the present invention is not limited thereto, and the content of the spironaphthoxazine 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 polyacrylic 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 polyacrylic coating film having a thickness of 5 to 40 ㎛.

In addition, the coating and curing process of the polyacrylic coating film is not significantly different from the curing process of the conventional polyacrylic coating film, and since the optimum conditions can be determined within a conventional range, the present invention is not particularly limited. However, in order to obtain better characteristics of the coating film, the coated coating liquid may be dried at 60 to 90 ° C. to form a film, and the photochromic coating film may be manufactured through UV irradiation and curing. At this time, the light curing by UV irradiation may be used a variety of lamps that can be irradiated with UV, irradiated with an intensity of about 100 to about 3000 mJ / cm ² UV-A range.

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 Spironaphtok Photo  Preparation of Compound

Example  One

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

Scheme 1

(Compound Preparation of Formula 9)

3.0 g (8.7 mmol) and 1.99 g (17.4 mmol) of glutaric anhydride represented by Chemical Formula 8 of Scheme 1 were dissolved in 100 mL of dichloromethane (CH ₂ Cl ₂ ) to prepare a reaction mixture. The reaction mixture was reacted at reflux with boiling for 4 hours in the presence of dimethylaminopyridine (DMAP) corresponding to about 1% by weight of the catalytic amount.

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 acetate = 1: 1 volume ratio) apparatus to obtain a brown solid represented by Chemical Formula 9 in Scheme 1 (2.33 g, yield 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).

(Preparation of Compound of Formula 4)

Compound 1.0 g (2.18 mmol) of the above formula 9, N - (3- dimethylaminopropyl) - N '- ethylcarbodiimide 630 mg (3.27 mmol) and DMAP 27 mg (0.22 mmol) in dichloromethane (CH ₂ Cl ₂ ) After dissolving in 10 mL, 0.46 mL (3.27 mmol) of hydropropyl methacrylate was added. 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 (30 mL × 3). The organic layer thus obtained was dried over anhydrous sodium sulfate, filtered and then condensed under reduced pressure.

The reaction product remaining in the above process was passed through a silica gel chromatography ( n- hexane: ethyl acetate = 1: 1 volume ratio) apparatus to convert the photochromic spironaphthoxazine compound represented by Chemical Formula 4 of Scheme 1 into a transparent oil form. Obtained (660 mg, yield 52%); ¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.20 (m, 3H), 1.29 (m, 3H), 1.33 (s, 3H), 1.94 (m, 2H), 2.10 (m, 2H), 2.51 ( m, 2H), 2.70 (m, 2H), 2.77 (s, 3H), 5.24 (m, 2H), 5.56 (m, 2H), 6.12 (m, 2H), 6.54 (d, 1H), 6.86 (m , 2H), 7.12 (m, 3H), 7.60 (d, 1H), 7.71 (m, 2H), 8.23 (s, 1H).

Example  2

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

Scheme 2

(Preparation of Compound of Formula 11)

1.0 g (2.9 mmol) of the compound represented by Chemical Formula 10 of Formula 2 and 0.29 g (2.9 mmol) of phthalic anhydride were dissolved in 100 mL of dichloromethane (CH ₂ Cl ₂ ) to prepare a reaction mixture. Thereafter, the reaction mixture was reacted under reflux with boiling for 4 hours in the presence of dimethylaminopyridine (DMAP) corresponding to about 1% by weight of the catalytic amount.

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 process was passed through a silica gel chromatography ( n- hexane: ethyl acetate = 1: 1 volume ratio) apparatus to obtain a blue solid represented by Chemical Formula 11 in Scheme 2 (0.13 g, yield 10%). ); ¹ H NMR (500 MHz, CDCl ₃ ): δ = 1.35 (s, 3H), 1.36 (s, 3H), 2.76 (s, 3H), 2.86 (t, 2H), 2.99 (t, 2H), 6.58 ( d, 1H), 6.92 (t, 1H), 7.00 (d, 1H), 7.10 (d, 1H), 7.16 (dd, 1H), 7.23 (t, 1H), 7.66 (d, 1H), 7.73 (s , 1H), 7.76 (d, 1H), 8.24 (ds, 1H).

(Compound Preparation of Formula 5)

Compound 0.97 g (2.18 mmol) of Formula 11, N - (3- dimethylaminopropyl) - N '- ethylcarbodiimide 630 mg (3.27 mmol) and DMAP 27 mg (0.22 mmol) in dichloromethane (CH ₂ Cl ₂ ) After dissolving in 10 mL, 0.46 mL (3.27 mmol) of hydropropyl methacrylate was added. 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 (30 mL × 3). The organic layer thus obtained was dried over anhydrous sodium sulfate, filtered and then condensed under reduced pressure.

The reaction product remaining in the above process is passed through a silica gel chromatography ( n- hexane: ethyl acetate = 1: 1 volume ratio) apparatus to convert the reactive spironaphthoxazine compound represented by Chemical Formula 5 of Scheme 2 in the form of a transparent oil. Got it.

Example  3

According to Scheme 3, a reactive spironaphthoxazine compound represented by Chemical Formula 6 was prepared.

Scheme 3

(Preparation of Compound of Formula 12)

30 mL of dichloromethane was injected into the reactor, and 2- (3,3-dimethyl-2-methyleneindolin-1-yl) ethanol (2- (3,3-dimethyl-2-methyleneindolin-1-yl) ethanol) 2.0 g (7.03 mmol), 85 mg (0.7 mmol) of dimethylamino pyridine (DMAP) were added and mixed uniformly, followed by addition of 802 mg (7.03 mmol) of glutaric anhydride. The resulting mixture was refluxed for 16 hours, then distilled under reduced pressure to remove the solvent and unreacted material, and then the crude product obtained was used for the next step.

Inject 30 mL of ethanol into the reactor and reflux for 16 hours by adding 1.78 g (5.62 mmol) of the compound prepared above and 973 mg (5.62 mmol) of 1-nitroso-2-naphthol. I was. After the completion of the reaction, the obtained purple reaction solution was depressurized, and the obtained residue was subjected to silica gel chromatography ( n- hexane: ethyl acetate = 4: 1, 1: 2) to obtain a brown oil product corresponding to Chemical Formula 12 of Scheme 3. Obtained (1.20 g, 45%); 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).

(Compound Preparation of Chemical Formula 6)

Compound 1.03 g (2.18 mmol) of Formula 12, N - (3- dimethylaminopropyl) - N '- ethylcarbodiimide 630 mg (3.27 mmol) and DMAP 27 mg (0.22 mmol) in dichloromethane (CH ₂ Cl ₂ ) After dissolving in 10 mL, 0.46 mL (3.27 mmol) of hydropropyl methacrylate was added. The reaction mixture was then reacted at reflux with boiling for 4 hours.

After the reaction, the reaction mixture was cooled to room temperature (about 25 ° C.) and washed with brine (30 mL × 3). The organic layer thus obtained was dried over anhydrous sodium sulfate, filtered and then condensed under reduced pressure.

The reaction product remaining in the above process is passed through a silica gel chromatography ( n- hexane: ethyl acetate = 1: 1 volume ratio) device to convert the reactive spironaphthoxazine compound represented by Chemical Formula 6 of Scheme 2 in the form of a transparent oil. Got it.

Example  4

According to Scheme 4, a reactive spironaphthoxazine compound represented by Formula 7 was prepared.

Scheme 4

(Compound Preparation)

50 mL of dimethylformamide (DMF) was injected into the reactor, followed by 2.21 1,3,3-trimethyl-2-methyleneindolin-5-amine (1,3,3-trimethyl-2-methyleneindolin-5-amine). g (11.7 mmol) and 142 mg (1.17 mmol) of dimethylaminopyridine were added. To this was added 1.6 g (14.0 mmol) of glutic anhydride and refluxed for 16 h. After completion of the reaction, the crude product (crude product) obtained by concentrating the final reaction product under reduced pressure was used in the next step.

Then, 50 mL of ethanol was injected into the reactor, and 2.12 g (7.01 mmol) of 4- (1,3,3-trimethyl-2-methyleneindoline-5-ylcarbamoyl) butanoic acid, which was a crude product, prepared above. And 1.21 g (7.01 mmol) of 1-nitroso-2-naphthol were refluxed for 16 hours. The crude product (Formula 13) obtained by concentrating the final reaction under reduced pressure was used in the next step.

(Preparation of Compound of Formula 7)

Compound 1.00 g (2.18 mmol) of Formula 13, N - (3- dimethylaminopropyl) - N '- ethylcarbodiimide 630 mg (3.27 mmol) and DMAP 27 mg (0.22 mmol) in dichloromethane (CH ₂ Cl ₂ ) After dissolving in 10 mL, 0.46 mL (3.27 mmol) of hydropropyl methacrylate was added. The reaction mixture was then reacted at reflux with boiling for 4 hours.

After the reaction, the reaction mixture was cooled to room temperature (about 25 ° C.) and washed with brine (30 mL × 3). The organic layer thus obtained was dried over anhydrous sodium sulfate, filtered, and then condensed under reduced pressure to obtain a reactive spironaphthoxazine compound corresponding to Chemical Formula 7 of Scheme 4 in the form of a transparent oil.

[Response type Polyacrylic Of coating film  Produce]

Production Example  One

50 g of a UV-curable photochromic coating solution (manufactured by LG Chemical, AU21PC: a reactive polyacrylic coating solution containing a diacrylate mixture, vinyl, and polyacryl) was added thereto, and a reactive spironaphthoxazine compound of Formula 4 was 1.78. After injecting g, 0.38 g of Irgacure 184 and Irgacure 819, which are photo initiators, were added as initiators, respectively, and stirred at room temperature for 1 hour to prepare a coating composition.

The coating composition was roll-coated with meyer bar # 30 on the surface of the polycarbonate film (0.8 mm thick I-component), followed by preliminary drying in an oven at 80 ° C. for 5 minutes to volatilize the solvent. Subsequently, the obtained film was irradiated with 2000 mJ / cm 2 by an ultraviolet curing machine to prepare a coating film.

Production Example  2

A photochromic polyacrylic coating film was prepared in the same manner as in Preparation Example 1, except that 1.78 g of a reactive spironaphthoxazine compound of Formula 5 was used.

Production Example  3

A photochromic polyacrylic coating film was prepared in the same manner as in Preparation Example 1, except that 1.78 g of a reactive spironaphthoxazine compound of Formula 6 was used.

Production Example  4

A photochromic polyacrylic coating film was prepared in the same manner as in Preparation Example 1, except that 1.78 g of a reactive spironaphthoxazine compound of Formula 7 was used.

Comparative example  One

A photochromic polyacrylic coating film was prepared in the same manner as in Preparation Example 1, except that 1.78 g of a general spironaphthoxazine compound represented by Chemical Formula a was used.

[Formula a]

[ Photochromic Polyacrylic Of coating film  Property measurement]

In order to determine the physical properties of the photochromic polyacrylic coating film prepared according to Preparation Examples 1 to 4 and Comparative Example 1, 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 rays (1.35 mW / cm ² ) having a wavelength of 365 nm for 5 minutes, and then immediately measured by using a UV-Vis detector to measure output light in decolorized and colored states, 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 ΔOD _max 0.45 0.48 0.48 0.42 0.42 λ _{max (nm)} 605 610 600 605 601 t _1/2 (sec) 13 15 12 15 8 T _1/2 (hr) 180 156 175 150 85 Film thickness (㎛) 25 22 22 23 22

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

Since the photochromic polyacrylic coating liquid composition of the present invention contains a spirotaphtoxazine compound which can be grafted directly to a polyacryl molecule, a phase separation phenomenon does not occur even in the coating liquid, and the photochromic coating film prepared therefrom is There is no blooming phenomenon over time and there is an advantage that the photochromic property can be maintained for a long time.

Claims (9)

Reaction type spironaphthoxazine compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, X ¹ to X ³ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, a hydroxy alkyl group having 1 to 10 carbon atoms, at least one substituted with N, O, or S It is selected from the group consisting of a 5- or 6- heterocyclic group, an amine group substituted with an alkyl group having 1 to 4 carbon atoms, and -LP group, At least one of X ¹ to X ³ is a -LP group, The L is a linker connecting the spironaphthoxone core and the P, -OOC-, -OOC-R _1- , -R ₂ -OOC-R ₁ -COO-, -OOC- R ₁ -COO-, -NH-CO-R ₃ -COO- and -OOC-HN-R ₃ -NH-COO- is selected from the group, wherein R ₁ and R ₂ are each independently 1 to 10 carbon atoms Phosphorus branched or straight chain alkyl, R ₃ is branched or straight chain alkyl having 1 to 10 carbon atoms and aromatic group having 6 to 40 carbon atoms, P is an acrylate or methacrylate group containing a vinyl group. Bisphenol A type di (meth) acrylate; Polyethylene glycol di (meth) acrylates; Reactive spironaphthoxazine compound represented by Formula 1 of claim 1; And UV initiator or thermal initiator Photochromic polyacrylic coating liquid composition comprising a. The method of claim 2, To 100 parts by weight of the bisphenol A-based di (meth) acrylate, 25 to 150 parts by weight of the polyethylene glycol di (meth) acrylate; 1 to 20 parts by weight of the reactive spironaphthoxazine compound; And 0.1 to 10 parts by weight of the initiator Photochromic polyacrylic coating liquid composition comprising a. The method of claim 2, The bisphenol A-based di (meth) acrylate is bisphenol A-based ethylene oxide dimethacrylate, bisphenol A-based propylene oxide dimethacrylate, bisphenol A-based ethylene oxide diacrylate, and bisphenol A-based propylene oxide diacrylate Photochromic polyacrylic coating liquid composition which is selected from the group consisting of one or more. The method of claim 2, The polyethylene glycol di (meth) acrylate is composed of triethylene glycol di (meth) acrylate, PEG 600 di (meth) acrylate, PEG 400 di (meth) acrylate, and PEG 200 di (meth) acrylate. Photochromic polyacrylic coating liquid composition which is selected from one or more of the group. The method of claim 2, The reactive spironaphthoxazine compound is a photochromic polyacrylic coating liquid composition selected from the group consisting of compounds represented by the following formula (4) to (7). [Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

Photochromic polyacryl grafted with the reactive spironaphthoxazine compound represented by the general formula (1). The method of claim 7, wherein The polyacryl is grafted at a ratio of 1.0 to 20.0% by weight based on the total weight of the bisphenol A-based di (meth) acrylate and polyethylene glycol-based di (meth) acrylate. Photochromic polyacrylic will be. A photochromic polyacrylic coating film prepared from the photochromic polyacrylic 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.