KR20070096329A - Photochromic coating composition of uv curable type, and photocromic polyuretane coating membrane using the same, and photochromic optical article comprising the same - Google Patents

Abstract

A dual curing photochromic coating composition, a photochromic polyurethane coating film using the composition, and an optical industrial product containing the photochromic polyurethane coating film are provided to improve the adhesive strength to a substrate and to allow a photochromic film to be formed easily without the coating processes of two steps. A dual curing photochromic coating composition comprises a photochromic dye; a binder; a photoinitiator; and a solvent, wherein the binder comprises a polyurethane prepolymer and a multifunctional acrylate compound in a ratio of 90:10 to 60:40 by weight. Preferably the polyurethane prepolymer comprises a polyester-based polyurethane oligomer, polyol and polyisocyanate; and the multifunctional acrylate compound comprises a C1-C20 alkyl acrylate, a hydroxyalkyl acrylate of a C1-C20 alkyl group, and an alkylene glycol acrylate of a C1-C20 alkyl group.

Description

Dual curing type photochromic coating composition, photochromic polyurethane coating film using the same, and photochromic optical product including the same. SAME}

The present invention relates to a dual-curable photochromic coating composition, a photochromic polyurethane coating film using the same, and a photochromic optical product including the same, and more particularly, to be manufactured through UV and thermal curing to have excellent abrasion resistance and a substrate. The present invention relates to a dual-curable photochromic coating composition capable of easily forming a photochromic film having excellent adhesion to a film, a photochromic polyurethane coating film using the same, and a photochromic optical product including the same.

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

The photochromic coating film is prepared in a thin film form by coating and curing the surface of the product to form a coating composition to form a coating film. As such a coating composition, a photochromic dye is dispersed in an acrylic resin and a solvent, followed by mixing an initiator capable of polymerization or crosslinking to irradiate heat or light to perform a curing reaction.

However, in the case of the photochromic coating film using the acrylic resin, it exhibits excellent transparency and has a high surface hardness but a low difference in optical density, and the durability of the dye is very short. Thus, the photochromic product manufactured using the same has problems in practical use. Thus, in the case of using a separate flexible polyurethane resin, but excellent in photochromic properties, the surface hardness is lowered requires a separate hard coating layer.

The present invention is to solve the problems of the prior art as described above, an object of the present invention by using a polyacryl-polyurethane oligomer has a sufficient wear resistance surface of the coating film provides a free space required for photochromic dye activation in the coating film It is to provide a dual curing photochromic coating composition to increase the optical density and excellent coloring / decolorization rate.

Another object of the present invention is to provide a photochromic polyurethane coating film prepared from the double curable photochromic coating composition.

Still another object of the present invention is to provide a photochromic optical industrial product comprising the photochromic polyurethane coating film.

In order to achieve the above object, the present invention comprises a photochromic dye, a binder, a photoinitiator and a solvent, wherein the binder is a dual curing type comprising a polyurethane prepolymer and a polyfunctional acrylate compound in a weight ratio of 90:10 to 60:40 It provides a photochromic coating composition.

The polyurethane prepolymer preferably comprises polyurethane oligomers, polyols and polyisocyanates. In addition, the multifunctional acrylate compound includes an alkyl acrylate having an alkyl group having 1 to 20 carbon atoms, a hydroxy alkyl acrylate having an alkyl group having 1 to 20 carbon atoms, and an alkylene glycol acrylate having an alkyl group having 1 to 20 carbon atoms. It is desirable to.

The present invention also provides a photochromic polyurethane coating film obtained by ultraviolet curing and thermosetting of the dual curing photochromic coating composition and having a thickness of 5 to 40 μm.

In addition, the present invention provides an optical substrate comprising: a) an optical substrate; And b) the photochromic polyurethane coating film of claim 16 on one or both surfaces of the optical substrate.

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

The dual-curable photochromic coating composition of the present invention comprises a polyurethane prepolymer and a polyfunctional acrylate compound as a binder in a ratio, and performs UV curing and thermal curing sequentially, without using a large amount of photoinitiator, wear resistance In addition, there is a feature that can provide a photochromic coating film with improved optical density and coloration / discoloration speed.

Such bicurable photochromic coating compositions of the present invention comprise photochromic dyes, binders, photoinitiators and solvents.

In particular, the binder is preferably used by mixing the polyurethane prepolymer and the polyfunctional acrylate compound in a weight ratio of 90:10 to 60:40, more preferably 80:20 to 60:40. If the content of the polyurethane prepolymer is excessive, the surface hardening degree of the coating film is weak, causing the film to melt during hard coating. On the contrary, if the content of the polyfunctional acrylate compound is excessive, the coloring degree is weak and the decolorization rate is slow. Since there exists a concern, it uses suitably within the said range.

In this case, the polyurethane prepolymer preferably contains 25 to 35% by weight of polyester-based polyurethane oligomer, 15 to 25% by weight of polyol and 50 to 60% by weight of polyisocyanate.

The polyester-based polyurethane oligomer has a number average molecular weight of 30,000 to 50,000, the viscosity is 100 to 3000 cps (viscosity of a solution dissolved in 15% concentration in cyclohexane), Tg is -30 to 40 ℃ It is preferable to use one with . These polyurethanes can be used directly by polymerization or commercially available. For example, Noveon's ESTANE® 5701 TPU, ESTANE® 5703 TPU, ESTANE® 5707 TPU, ESTANE® 5708 TPU, ESTANE® 5713 TPU, ESTANE® 5714 TPU, ESTANE® 5715 TPU, ESTANE® 5719 TPU, and ESTANE® 5778 TPU Etc.

The polyol may be a conventional compound used for preparing a polyurethane prepolymer, and is not particularly limited. Preferably, the polyol may use one or more selected from the group consisting of polyester polyols, polyether polyols, polyacryl polyols, and polycarbonate polyol diols. Examples of the polyols include 1,4-butanediol, diethylene glycol, dipropylene glycol, polyalkylene glycols having alkyl groups having 1 to 5 carbon atoms, and polyalkylene ether polyols. The polyalkylene ether polyols include polytetramethylene ether glycol, poly (oxytetramethylene) ether glycol, poly (oxytetramethylene) ether glycol, poly (oxy-1,2-propylene) ether glycol and poly (oxy-1, 2-butylene) ether glycol may be used at least one selected from the group consisting of. The polyisocyanate may be a conventional compound used for preparing a polyurethane prepolymer, and is not particularly limited. Preferably, aliphatic and aromatic isocyanates and the like can be used. For example, the aliphatic diisocyanate includes 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate and α, α-xylylene diisocyanate. The aromatic polyisocyanate may be selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, and toluene diisocyanate.

In addition, the multifunctional acrylate compound included in the dual curing photochromic coating composition of the present invention is not only crosslinked with the polyester-based polyurethane prepolymer, but also crosslinked between acrylate-based compounds (monomers, oligomers). A coating film having a dimensional network structure is prepared. In this case, the term "multifunctional" as used herein means that crosslinking may be performed by including at least two or more, preferably 2 to 10, double bonds in the molecular structure. Therefore, the polyfunctional acrylate compound used in the present invention is di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate, hepta ( Meta) acrylate, octa (meth) acrylate, nona (meth) acrylate, and deta (meth) acrylate.

Preferably, the multifunctional acrylate compound is an alkyl acrylate having an alkyl group having 1 to 20 carbon atoms, a hydroxy alkyl acrylate having an alkyl group having 1 to 20 carbon atoms, and an alkylene glycol having an alkyl group having 1 to 20 carbon atoms. It is preferred to include acrylates, and each component is included in 10 to 80% by weight, 5 to 10% by weight, and 5 to 10% by weight.

The alkyl acrylate having an alkyl group having 1 to 20 carbon atoms is an alkyl acrylate containing 2 to 10 acrylate functional groups, typically methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, tri (meth ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol At least one selected from the group consisting of penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate can be used.

The hydroxy alkyl acrylate having an alkyl group having 1 to 20 carbon atoms is hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxy-poly (alkyleneoxy Alkyl (meth) acrylate, pentaerythritol hydroxy tri (meth) acrylate, pentaerythritol hydroxy tetra (meth) acrylate, dipentaerythritol dihydroxy hexa (meth) acrylate, dipentaerythritol At least one selected from the group consisting of dihydroxy penta (meth) acrylate, pentaerythritol tetra hydroxy tetra (meth) acrylate, and ditrimethylolpropane tetrahydroxy tetra (meth) acrylate can be used.

The alkylene glycol diacrylate having an alkyl group having 1 to 20 carbon atoms is ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and hexamethylene di (meth) acrylate. , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol Di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glyceryl ethoxylate di (meth) acrylate, and glyceryl propoxylate di (meth) acrylic One or more types selected from the group consisting of rates can be used.

As long as the photochromic dye used for the coating composition of this invention can be used as long as it is a compound which shows normal photochromic property, it does not specifically limit in this invention. Representatively, naphthopyrans, benzopyrans, phenanthropyrans, indenonaphthopyrans, spiro (benz indoline) naphthopyrans, spiro (indoline) benzopyrans, spiro (indolin) naphthopyrans, spiro (indoline) ) Quinopyran, Spiro (Indolin) Pyran, Spiro (Indolin) Naphthog, Spiro (Indoline) Pyridobenzoxazine, Spiro (Benz Indoline) Pyridobenzoxazine, Spiro (Benz Indoline) Nap Toxazine, spiro (indoline) benzoxazine, chromen, pulgide (fulgide), pulgimide (fulgimide) and the like can be prepared and used directly or purchased commercially available. The photochromic dye is used in an amount of 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the binder. If the content of the compound is less than the above range, it is difficult for the prepared coating film to have proper photochromic properties, and if it is outside the above range, there is a possibility that the dye may not be sufficiently dissolved in the coating solution and may be precipitated and economically undesirable.

In addition, the initiator is activated by UV to proceed the cross-linking reaction of the multifunctional acrylate compound cross-linking agent and / or binder. The kind of the photoinitiator is not particularly limited, and any one commonly used in the art may be used. Preferably, the initiator may use an ultraviolet decomposition initiator, and typically 1-hydroxy cyclohexylphenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin iso Propyl ether, benzoin butyl ether and the like. In particular, the photoinitiator is used in a very small amount in the entire coating composition, as compared to the conventional double curable coating composition used 7% by weight or more, the coating composition of the present invention performs a dual curing process, such as UV / thermal curing, Preferably it is used 1 to 5 parts by weight, more preferably 1 to 3 parts by weight based on 100 parts by weight of the binder resin.

In addition, the solvent is used to dissolve or disperse the components of the coating composition of the present invention, and serves to dilute to a viscosity suitable for coating. In addition, the solvent may be used for dissolving or dispersing each component even in preparing a polyurethane prepolymer. The solvent is benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol, propyl alcohol, propylene carbonate, N-methyl pyrrolidinone, N-vinyl pyrrolidinone, N-acetyl pi Rollidinone, N-hydroxymethyl pyrrolidinone, N-butyl pyrrolidinone, N-ethyl pyrrolidinone, N- (N-octyl) pyrrolidinone, N- (N-dodecyl) pyrrolidinone, 2 -Methoxyethyl ether, xylene, cyclohexane, 3-methyl cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, methanol, amyl propionate, methyl propionate, propylene glycol methyl ether, diethylene glycol Monobutyl ether, dimethyl sulfoxide, dimethyl formamide, ethylene glycol, mono- and di-alkyl ethers of ethylene glycol and derivatives thereof (commercially available as CELLOSOLVE industrial solvent), and mixtures of these solvents It may be used in selected from the group consisting of, but is not limited to these. Preferably, the mixed solvent is most preferable when cyclohexanone, ethyl acetate, dimethylformamide, diacetylacetone, ethyl cellosolve, and isopropyl alcohol are mixed in a predetermined ratio. The solvent is preferably used in an amount of 80 to 150 parts by weight, more preferably 90 to 120 parts by weight based on 100 parts by weight of the binder. If the content is less than the above range, each composition is difficult to disperse sufficiently, coating is not easy to the substrate, not easy to work, it is difficult to obtain a uniform coating film, and if it exceeds the above range, several coating processes must be performed. This makes the process complicated.

In addition, the double curable photochromic coating composition and the polyurethane prepolymer composition according to the present invention may further include additives used in conventional photochromic coating compositions as necessary. The content of the additive is also used within the content range of conventional additives. As the additive, UV stabilizers, plasticizers, fillers, tackifiers, viscosity modifiers, impact modifiers, antioxidants, etc. may be used, and may be appropriately selected and used by those skilled in the art. do. For example, in preparing the polyurethane prepolymer, a catalyst may be used to promote the condensation reaction of the polyol and the polyisocyanate, specifically, dibutyltindilaurate (DBTDL, dibutyltindilaurate), zinc octoate, iron acetyl aceto One or more selected from the group consisting of iron acetyl acetonate, N, N-dimethyl ethanolamine and triethylene diamine can be used.

On the other hand, the production method of the UV-curable photochromic coating composition of the present invention is not particularly limited, and can be prepared according to a conventional production method. Preferred examples include the addition of polyurethane oligomers, polyols and polyisocyanates to prepare polyurethane prepolymers, photochromic dyes, photoinitiators, solvents and alkylene glycol diacrylates, and hydroxyalkyl acrylics in the polyurethane prepolymers. It can be prepared by a method comprising the step of adding a multifunctional acrylate compound comprising a rate.

In addition, the present invention can provide an optical product and a photochromic polyurethane coating film that can be used therein using the dual curing photochromic coating composition. The composition of the present invention can be used for various purposes in addition to the optical product, and when used in the optical product, it is preferable to be prepared in the form of a coating film having a certain transmittance, photochromic polyurethane having a thickness of 5 to 40 ㎛ More preferably, it is prepared in the form of a coating film.

The manufacturing method of the photochromic polyurethane coating film is not particularly limited and may be prepared by coating the coating composition on one or both surfaces of the optical substrate and curing the coating composition. For example, after performing the wet coating process of the dual curable coating composition on the surface of the substrate of the industrial product to be coated, it is dried at 60 to 90 ℃ to form a film, UV irradiation to perform UV curing, 120 to The photochromic coating film may be prepared by performing a thermosetting at 140 ° C.

The present invention can greatly increase the wear resistance of the surface of the photochromic coating film by performing UV curing as described above, it can impart excellent adhesion to the substrate. However, uniform curing may not be performed until the inside of the coating film, so that the entire photochromic coating film may have the same physical properties by performing UV curing followed by thermal curing. Therefore, the photochromic coating film prepared through the dual curing of the present invention can provide a free space required for the activation of the photochromic dye dispersed in the crosslinked resin can increase the optical density and the coloration / decolorization rate.

At this time, the light curing by UV irradiation may be used a variety of lamp wavelength 200 ~ 400nm that can irradiate UV, and irradiated with an intensity of about 100 to about 3000 mJ / cm ² UV-A range. The time for exposing the curable coating to the light source depends on the wavelength and intensity of the light source, the photoinitiator and the thickness of the coating. In general, the exposure time is an amount of time sufficient to produce a coating that is sufficiently cured to substantially cure or physically handle the coating and then postcure by heat.

The wet coating method is not particularly limited in the present invention, and conventional wet coating methods such as spray coating, spin coating, dip coating, and doctor blading coating are used.

In addition, the photochromic coating film prepared in the present invention may be included on one or both sides of the optical substrate may be applied to various optical industrial products. For example, optical products include optical and planar lenses, face shields, goggles, camera lenses, windows, automotive transparencies, inks (eg liquid or paste containing photochromic dyes used for writing and printing). , Ornaments (eg, plastic films and sheets, textiles) and coating compositions (eg, paint and protective documents such as passports, driver's licenses and check marks on banknotes) and the like.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the examples are only for illustrating the present invention and are not limited thereto.

Example

Preparation Example 1 Preparation of Polyurethane Prepolymer A

120 g of methyl ethyl ketone and 180 g of cyclohexanone were added to a jacket reactor, and 70 g of polyurethane Estane 5701 ^® (Noveon, Inc., polyurethane including Brønsted's salt, number average molecular weight 40,000) was added. Stir at 80 ° C for hours.

Here, polytetramethyleneetherglycol (Terathane 1000 ^® , Mw = 1000, Sigma Aldrich) 14 g, 1,4-butanediol 1.5 g, polyester polyol resin (dispersed in n-butyl acetate, Desmophen 670BA ^® , Bayer G) After adding 17 g, the mixture was stirred at room temperature for 30 minutes. Subsequently, 124 g of alicyclic polyisocyanate (blocked with MEKO, Vestant B 1358A ^® , manufactured by Degus), 0.3 g of dibutyltindilaurate (DBTDL), and 1.2 g of Tego 410 ^® additive from Tego as a flow improver 1.2 g of Tego 450 ^® was added and stirred until uniform to prepare a polyurethane prepolymer.

Preparation Example 2; Preparation of Polyurethane Prepolymer B

A polyurethane prepolymer was prepared in the same manner as in Preparation Example 1, except for replacing the polyurethane Estane 5701 ^® with Estane 5778 ^® (number average molecular weight 375,00) in the A composition.

Preparation Example 3 Preparation of Polyurethane Composition C

A polyurethane prepolymer was prepared in the same manner as in Preparation Example 1, except that 10 g of a liquid epoxy resin (LER 840 ^® , viscosity 9000-1000 cps, LG Chem) was further added to the A composition. .

Preparation Example 4 Preparation of Multifunctional Acrylate Dispersion A

In a jacket reactor, 27 g of dipentaerythritol hydroxypenta acrylate (DPHA) and 5 to 3 pentaerythritol triacrylate (PETA) of UCB-SK 91 g, bifunctional 9-ethylene glycol diacrylate (9-EGDA, 9-ethyleneglycol diacrylate) 6 g of acrylate was added, followed by 76 g of ethyl cellosolve, 38 g of isopropyl alcohol, and 130 g of methanol. Diluted in mixed solvent. 10 g of Darocur 1173 ^® , Irgacure 184 ^® , and Irgacure 907 ^® of Ciba Inc. were added as photoinitiators, and 1 g of Tego 453 ^® Tego additive was added thereto, followed by mixing for 30 minutes to prepare a polyacryl A composition.

Preparation Example 5 Preparation of Multifunctional Acrylate Dispersion B

A polyacryl composition B was prepared in the same manner as in Preparation Example 4, except that 45 g of hydroxyethyl methacrylate (HEMA, Hydroxyethyl methacrylate) was further added to the polyacrylic A composition.

The photochromic coating composition was prepared by mixing the photochromic dye with the polyurethane prepolymer and the acrylate dispersion prepared through the preparation example.

Example 1 Preparation of Photochromic Coating Composition 1

In 60 g of the polyurethane prepolymer prepared in Preparation Example 1, 2.0 g of photochromic dyes (naphthopyran, James Robinson's Reversacol Flame, which exhibits orange color when exposed to ultraviolet rays), and tinuvin's tinubin as a UV stabilizer Polyurethane prepolymer was prepared by adding 1.4 g of Tinuvin) 144 ^® .

20 g of the acrylate dispersion A prepared in Preparation Example 4 was added thereto, followed by stirring to prepare a photochromic coating composition.

Example 2: Preparation of Photochromic Coating Composition 2

A photochromic coating composition was prepared in the same manner as in Example 1, except that dispersion B prepared in Preparation Example 5 was used as the acrylate dispersion.

Example 3: Preparation of Photochromic Coating Composition 3

A photochromic coating composition was prepared in the same manner as in Example 1, except that the prepolymer B prepared in Preparation Example 2 was used as the polyurethane prepolymer.

Example 4 Preparation of Photochromic Coating Composition 4

A photochromic coating composition was prepared in the same manner as in Example 1, except that the prepolymer C prepared in Preparation Example 3 was used as the polyurethane prepolymer.

Comparative Example 1: Preparation of Photochromic Coating Composition 5

In 100 g of the polyurethane prepolymer prepared in Preparation Example 1, 2.0 g of photochromic dyes (naphthopyran, James Robinson's Reversacol Flame, which is orange when exposed to ultraviolet rays), and Tinuvin (Shibagaigi's) as UV stabilizers Photochromic coating composition was prepared by adding 1.4 g of Tinuvin) 144 ^® .

Comparative Example 2: Preparation of Photochromic Coating Composition 6

To 100 g of the acrylate dispersion B prepared in Preparation Example 4, 2.0 g of photochromic dyes (naptopyran, James Robinson's Reversacol Flame, which appeared orange when exposed to ultraviolet light), and Tinuvin (Shibagaigi's) as UV stabilizers Photochromic coating composition was prepared by adding 1.4 g of Tinuvin) 144 ^® .

Example 5-8 and Comparative Example 3-4: Preparation of Photochromic Coating Film

Each coating composition prepared above was coated on the lens surface to form a photochromic coating film.

Specifically, the medium refractive lens for eyeglasses (BS manufactured by Handoksa Co., Ltd., refractive index: 1.553) was etched in NaOH at 60 ° C. for 4 minutes, and then coated on the coating composition prepared above, followed by preliminary drying in an oven at 80 ° C. to volatilize the solvent. . Thereafter, UV curing was performed at a UV irradiation amount of 2000 mJ / cm 2, followed by thermosetting in an oven at 130 ° C. for 1 hour to prepare a polyurethane photochromic coating film which had undergone double curing.

Experimental Example 1: Measurement of Physical Properties

In order to find out the physical properties of the coating film prepared above was carried out as follows and the results obtained are shown in Table 1 below.

(1) optical density (OD)

The cured coating film was irradiated with UV rays of 365 nm (1.35 mW / cm ² ) for 2 minutes and immediately placed on a UV-vis detector to measure output light in decolorized and colored states, respectively. Calculated based on.

(2) λ _max

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

(3) t _1/2

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 for the light source to be restored to half of the complete decolorization state.

(4) scratch resistance

The scratch resistance of the double cured photochromic lens was measured using the Fischer microhardness measuring method.

(5) adhesion

A cross cut cellotape peel test was performed on the crosslinked cured film. Specifically, by making 11 horizontal and vertical scales of 1 mm ² each to the substrate at 1 mm intervals on the coating film, make 100 eyes of 1 mm ² , attach the cellophane tape on it, and then abruptly remove it three times in one place. The results were measured.

○: cross-linking curing even if repeated three times

(Triangle | delta): When the number of peeling eyes is 1-50 by repeating 3 times

X: 3 times repeated peeling eyes 51-100

(6) 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).

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 ΔOD _max 0.75 0.83 0.85 0.80 0.94 0.24 λ _max 480 nm 482 nm 480 nm 480 nm 490 nm 483 nm t _1/2 75 sec 83 sec 72 sec 64 sec 68 sec > 500 sec Scratch resistance 165 N / mm ² 155 N / mm ² 135 N / mm ² 150 N / mm ² 10.18 N / mm ² 135 N / mm ² Adhesion ○ ○ ○ ○ ○ ○ Photochromic layer film thickness 15 μm 16 μm 18 μm 15 μm 16 μm 13 μm

As can be seen from Table 1, in the case of Examples 1 to 4, it can be seen that even in the case of the same film thickness compared to Comparative Example 2, excellent photochromic properties. This is because as the resin of the polyurethane enters the coating liquid, the photochromic dye is provided with a lot of free space, thereby increasing the efficiency of the dye. In addition, by adding a UV curable resin, the surface hardness is significantly improved wear resistance compared to the case using only polyurethane.

The double-curable photochromic coating composition of the present invention can provide a photochromic coating film in an easy manner by coating on a substrate and undergoing UV curing and thermal curing without undergoing a two-step coating process as in the prior art. In addition, the photochromic coating film not only has excellent abrasion resistance, but also has excellent optical density and high coloration / discoloration speed, various lenses, sun protection lenses, filters, camera optical systems, decorations, windows, optical recording media, optical switches, and photosensitive drums. It can be applied to various industrial products such as recording devices, fibers and optical devices.

Claims (16)

A photocurable dye comprising a photochromic dye, a binder, a photoinitiator and a solvent, wherein the binder comprises a polyurethane prepolymer and a polyfunctional acrylate compound in a weight ratio of 90:10 to 60:40. The dual curable photochromic coating composition of claim 1, wherein the polyurethane prepolymer comprises a polyester-based polyurethane oligomer, a polyol, and a polyisocyanate. The double curable photochromic of claim 2 wherein the polyurethane polymer comprises 25 to 35 weight percent polyester-based polyurethane oligomer, 15 to 25 weight percent polyol, and 50 to 60 weight percent polyisocyanate. Coating composition. The method of claim 2, wherein the polyester-based polyurethane oligomer has a number average molecular weight of 30,000 to 50,000, a viscosity of 100 to 3000 cps (viscosity of a solution dissolved in cyclohexanone at a concentration of 15%), Tg is -30 Dual curing type photochromic coating composition is from 40 ℃. The double curable photochromic coating composition according to claim 2, wherein the polyol is at least one selected from the group consisting of polyester polyols, polyether polyols, polyacrylic polyols, and polycarbonate polyol diols. 3. The polyisocyanate of claim 2, wherein the polyisocyanate is 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate and α, α-xylylene di And at least one member selected from the group consisting of isocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, and toluene diisocyanate. The method of claim 1, wherein the multifunctional acrylate compound is an alkyl acrylate having an alkyl group having 1 to 20 carbon atoms, a hydroxy alkyl acrylate having an alkyl group having 1 to 20 carbon atoms, and an alkylene having an alkyl group having 1 to 20 carbon atoms. A dual curable photochromic coating composition comprising glycol acrylate. The method of claim 7, wherein the alkyl acrylate having an alkyl group having 1 to 20 carbon atoms is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, tri (meth) acrylate, ditrimethylol propane tetra (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra ( It is at least one member selected from the group consisting of meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate double curable photochromic coating composition. The hydroxy alkyl acrylate having an alkyl group having 1 to 20 carbon atoms is hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxy. Poly (alkyleneoxy) alkyl (meth) acrylate, pentaerythritol hydroxy tri (meth) acrylate, pentaerythritol hydroxy tetra (meth) acrylate, dipentaerythritol dihydroxy hexa (meth) acrylic 1 type selected from the group consisting of latex, dipentaerythritol dihydroxy penta (meth) acrylate, pentaerythritol tetrahydroxy tetra (meth) acrylate, and ditrimethylolpropane tetrahydroxy tetra (meth) acrylate It is more than double curable photochromic coating composition. The method of claim 7, wherein the alkylene glycol acrylate having an alkyl group having 1 to 20 carbon atoms is ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, hexamethylene di (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, dipropylene glycol di (meth) acrylic Latex, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glyceryl ethoxylate di (meth) acrylate, and glyceryl propoxyl At least one member selected from the group consisting of late di (meth) acrylates; Water. The method of claim 1, wherein the photochromic dye comprises 0.5 to 10 parts by weight based on 100 parts by weight of the binder, the photoinitiator comprises 1 to 5 parts by weight based on 100 parts by weight of the binder, and the solvent is based on 100 parts by weight of the binder Dual curable photochromic coating composition comprising from 80 to 150 parts by weight. The photochromic dye according to claim 1, wherein the photochromic dye is naphthopyran, benzopyran, phenanthropyran, indenonaphthopyran, spiro (benzindolin) naphthopyran, spiro (indolin) benzopyran, spiro (indolin) Naphthopyran, Spiro (Indoline) Quinopyran, Spiro (Indoline) Pyran, Spiro (Indoline) Naphthoxazine, Spiro (Indoline) pyridobenzoxazine, Spiro (benz indoline) At least one member selected from the group consisting of spiro (benzindolin) naphthoxazine, spiro (indolin) benzoxazine, chromen, organo-metal dithizonate, pulgide, and pulgimide Dual curable photochromic coating composition. The method of claim 1, wherein the photoinitiator is 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), Diisopropyl peroxydicarbonate (IPP), tertiary butylhydroperoxide (TBPO), 1-hydroxyhexylphenylketone, benzophenone, 2-hydroxy-1- [4- (hydroxyethoxy) phenyl] Double curable photochromic coatings selected from the group consisting of 2-methyl-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-bis (hydroxymethyl) Composition. The method of claim 1, wherein the solvent is benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol, propyl alcohol, propylene carbonate, N-methyl pyrrolidinone, N-vinyl pyrroli Dinone, N-acetyl pyrrolidinone, N-hydroxymethyl pyrrolidinone, N-butyl pyrrolidinone, N-ethyl pyrrolidinone, N- (N-octyl) pyrrolidinone, N- (N-dodecyl Pyrrolidinone, 2-methoxyethyl ether, xylene, cyclohexane, 3-methyl cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, methanol, amyl propionate, methyl propionate, propylene glycol Methyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethyl formamide, ethylene glycol, mono- and di-alkyl ethers of ethylene glycol and derivatives thereof (hexafluoroanti as a CELLOSOLVE industrial solvent) Dual curable photochromic coating composition of two or more member selected from the group consisting of carbonate. A photochromic polyurethane coating film obtained by ultraviolet curing and thermosetting of the dual curing photochromic coating composition according to any one of claims 1 to 14, and having a thickness of 5 to 40 µm. a) optical substrate; And b) the photochromic polyurethane coating film of claim 16 on one or both surfaces of the optical substrate. Photochromic optical industrial product comprising a.