KR101818937B1 - Novel Photochromic Naphthopyran Materials with Very Fast Fade Rate - Google Patents

Abstract

The photochromic material according to the present invention is a hydrophilic oligomer group having a hydrophobic substituent. The photochromic naphthopyran compound bonded to the 13-position of the 2,1-f] naphtho [1,2-b] And the hydrophilic oligomer group having the hydrophobic substituent is a cyclic group containing 5 to 30 hydrophilic units (Z) and is a material having a high coloring density, a very rapid coloring and fading rate, and excellent durability.

Description

(Novel Photochromic Naphthopyran Materials with Very Fast Fade Rate)

The present invention relates to photochromic materials. More specifically, the present invention relates to a mixture of photochromic naphthopyran compounds having a hydrophilic substituent on the indeno [2,1-f] naphtho [1,2-b] pyran compound and a hydrophilic oligomer group The present invention relates to a novel photochromic material having a very high fade rate.

Photochromic materials are structurally modified from one form to another in response to light of a particular wavelength, where each form has a specific absorption spectrum for visible light. Particularly, the photochromic material is colored by absorbing light in the visible light region when exposed to sunlight, and the process is reversed while returning to a transparent state in the room. Such a photochromic material can be applied to various applications such as a lens for a spectacle lens, a window glass, a window for an automobile, and the like. Particularly, the discoloration spectacles produced by incorporating a photochromic material also serve as sunglasses for outdoor use, and the color of the lenses becomes transparent in the room, thereby serving as glasses.

When the lens of the discoloration glasses absorbs the ultraviolet rays, sunlight is transmitted to the wearer's eyes through the lens. Therefore, the lens acts as sunglasses. When the lens enters the room, it is converted into a transparent state by heat energy. The wearer ' s field of view may not be optimal during this period. Therefore, photochromic materials are important functions of fade rate. That is, the fading rate is short so that the wearer can wear the glasses in an optimal state without feeling inconveniences. Since the discoloration and discoloration of the photochromic compound is a reversible reaction, there is a need to develop a photochromic compound that can be rapidly discolored by switching from a colored activated-state to an optically transparent base-state as well as a rate of coloring.

Most conventional photochromic materials exhibit relatively rapid color development and discoloration rate in the case of a liquid solution having a low viscosity, but the speed is markedly slowed due to the lack of free space required for the shape change in a rigid lens matrix state. For this reason, in the past, efforts have been made to increase the speed of color development and discoloration by controlling the characteristics of lens metrics. That is, when the lens is made thin, the coloring and fading rate can be increased. However, since the spectacle lens has to maintain a hardness higher than a certain level, the lens maker is in a dilemma between the hardness of the lens and the fading rate.

In an effort to improve the rate of discoloration of a photochromic material, WO1996 / 14596 provides an indeno-fused naphthopyran photochromic compound, which is indeno [2,1-f] And has a specific substituent at 5, 6, 7, 8, 9, 10, 11, 12 or 13 carbon atoms of the naphtho [1,2-b] pyran structure. However, .

WO2004 / 041961 and WO2009 / 146509 disclose a photochromic composition capable of significantly reducing the rate of color change by introducing a flexible oligomer such as polyether or siloxane into the photochromic material. However, these compositions have problems in commercialization due to the acidic decomposability and the complexity of synthesis of the siloxane.

WO2012 / 162725 discloses a photochromic polymer capable of improving the fading rate by introducing various polymers into a photochromic material, but has a problem in industrial production due to the complexity of synthesis.

In addition, U.S. Patent No. 6146554 and WO2013 / 032608 have attempted to improve the fading rate of the photochromic material itself by changing the substituent of indeno [2,1-f] naphtho [1,2-b] , The effect of improving the fading rate is very small, and the synthesis process is complicated, which has problems in industrial production.

In addition, Korean Patent Application No. 2014-0077812 discloses that, in an effort to improve the speed of discoloration of a photochromic material, the Korean Patent Application No. 2014-0077812 discloses a method for producing a photochromic material which is flexible at the 13-position of the indeno [2,1- A photochromic naphthopyran compound incorporating a substituent of sufficient size is still to be provided, but the fading rate still needs to be improved.

Accordingly, the present inventors have provided a novel photochromic material with greatly improved fading rate and residual color, and developed a product such as a photochromic composition containing the same, and a spectacle lens made of this composition.

It is an object of the present invention to provide a novel photochromic material having a high fading rate.

Another object of the present invention is to provide a novel photochromic material having a low residual color.

Another object of the present invention is to provide a photochromic resin composition comprising a photochromic material and a photochromic compound having a fast fading rate and a low residual color.

It is still another object of the present invention to provide a method for producing a product such as a spectacle lens, a film, and a board, which is produced by using a photochromic resin composition comprising a photochromic material and an organic photochromic compound, .

Another object of the present invention is to provide a product such as a spectacle lens, a film, and a board having a fast fading rate and a small residual color, which is manufactured by immersion, coating, impregnation or injection method of a photochromic material in transparent plastic .

These and other objects of the present invention can be achieved by the present invention which is described in detail below.

The photochromic material according to the present invention is a material having a high coloring density, a very fast coloring and fading rate, and excellent durability, wherein the hydrophilic oligomer group having a hydrophobic substituent is indeno [2,1-f] b] pyran compound, and the hydrophilic oligomer group having the hydrophobic substituent is preferably a cyclic group containing 5 to 30 hydrophilic units (Z).

The mixture of photochromic naphthopyran compounds is a mixture of the following formula 1 and formula 2:

In Formula 1 and Formula 2, O is an oxygen atom, Z is _{-OCH 2 -, -OCH 2 CH 2} -, -OCH (CH 3) CH 2 - group, ^{and, q 1, q 2, q} 3, p ¹ , p ² and p ³ are each an integer of 1 to 15, and A is hydrogen, an alkyl group (-R *) or an acyl group (-C (O) R * Y ¹ , Y ² and Y ³ are each hydrogen or a photochromic compound, and ^{one of} Y ¹ , Y ² and Y ³ is necessarily the photochromic compound, The photochromic compound is a group derived from an indeno [2,1-f] naphtho [1,2-b] pyran compound.

In the present invention, the indeno [2,1-f] naphtho [1,2-b] pyran compound is a 3,3-diarylindeno [2,1-f] ] Pyran compound represented by the following formula (3): < EMI ID =

Wherein R ** and W are independently selected from the group consisting of C1-C30 (C1-C30) alkyl, Or a group having one or more alkyl side chains.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, hydroxy, mercapto, nitro, -CN, C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, allyl, Substituted benzyloxy, naphthyl, monosubstituted naphthyl, fluoro, chloro, bromo, C1-C6 alkoxy, C3-C7 cycloalkoxy, phenoxy, monosubstituted phenoxy, benzyloxy, (C 1 -C 6) alkylamino, di-C 7 cycloalkylamino, di C 3 -C 7 cycloalkylamino, C 3 -C 7 cycloamino, di C3-C7 cyclic amino, substituted C3-C7 cycloamino, C3-C7 cyclic amino containing an O, N or S atom, or C3-C7 cyclic amino containing a mono substituted O, N or S atom, N and m are integers of 0 to 3, respectively.

It is preferable that the compound of the formula (1) and the compound of the formula (2) contain the compound of the formula (1) and the compound of the formula (2) in a weight ratio of 8: 2 to 2: 8.

The photochromic resin composition according to the present invention preferably contains 0.0001 to 20 parts by weight of a photochromic material with respect to 100 parts by weight of the host material.

When other organic photochromic compounds other than the photochromic material of the present invention are used in combination, the sum of the combined photochromic materials is preferably 0.001 to 30 parts by weight per 100 parts by weight of the host material.

In the present invention, the host material is preferably a thermosetting resin, a thermoplastic resin, or a mixture thereof.

In the present invention, other organic photochromic compounds include naphthopyran, benzopyran, phenanthropyran, spiro (benzindolin) naphthopyran, spiro (indolin) benzopyran, spiro (indolin) naphthopyran, spiro (Indoline) quinopyrene, spiro (indoline) pyran, spiro (indoline) naphthoxy, spiro (indoline) pyridobenzene, spiro (benzindolin) Naphthoc photo, spiro (indoline) benz photo, or mixtures thereof.

Further, the photochromic product molded from the photochromic resin composition according to the present invention can be produced.

Hereinafter, the present invention will be described in detail.

A photochromic naphthopyran compound bonded to the 13-position of the naphtho [2,1-f] naphtho [1,2-b] pyran compound having hydrophilic substituent The discoloring material has a much faster discoloration rate [tau 1/2 (sec)] than the conventional indeno-condensed naphthopyran photochromic material, and the residual color [4/5 (sec) Therefore, the transparent plastic material is very useful for the spectacle lenses, buildings, and automobile glass industries that require photochromic properties because they are returned to the colorless state very quickly when the ultraviolet rays are removed from the colored state in the presence of ultraviolet rays.

The photochromic material according to the present invention is a hydrophilic oligomer group having a hydrophobic substituent and having a high molecular weight and has a fast coloring and fading rate and excellent durability. A photochromic substance comprising a mixture of photochromic naphthopyran compounds bonded to the 13-position of the compound, wherein the hydrophilic oligomer is preferably a cyclic form containing 5 to 30 hydrophilic units (Z).

Here, the hydrophobic substituent is hydrogen, an alkyl group (-R *), or an acyl group (-C (O) R *), wherein R * is an alkyl group having a straight chain of C1-C30 or one or more alkyl side chains. Preferably, R * is an alkyl group having from 1 to 20 carbon atoms, which is linear or has one or more alkyl side chains. Representative examples of R * include 2-ethylhexyl, decyl, lauryl, isotridecyl, cetyl, oleyl, stearyl, But are not limited thereto.

Also, where a hydrophilic monomer (Z) is _{-OCH 2 -, -OCH 2 CH 2} -, or -OCH (CH ₃₎ CH ₂ - group, and the preferred hydrophilic monomer (Z) is -OCH ₂ CH ₂ - or -OCH (CH ₃ ) CH ₂ - group.

In the present invention, the mixture of photochromic naphthopyran compounds is a mixture of a compound of the following formula (1) and a compound of the following formula (2). The mixture of photochromic naphthopyran compounds is not necessarily limited to the following formulas (1) and (2), and may be a mixture of polyoxyethylene sorbitan monoacylate or polyoxypropylene sorbitan monoacylate Polyoxypropylene sorbitan monoakylate) and the following Y ¹ , Y ² and Y ³ condensation products.

In Formula 1 and Formula 2, O is an oxygen atom, Z is -OCH ₂ -, -OCH ₂ CH ₂ -, or -OCH (CH ₃ ) CH ₂ - group, q ¹ , q ² , q ³ , p ¹ , p ² and p ³ are integers of 1 to 15, respectively. Preferred Z is -OCH ₂ CH ₂ -, or -OCH (CH ₃₎ CH ₂ - group is.

q ^1, q ^2, q ^3, p ^1, p ² and p ³ is yet an integer from 1 to 10, the sum of q ¹ + q ² + q ³ is preferably of 5 to 30 integer, and p ¹ + The sum of p ² + p ³ is preferably an integer of 5 to 30.

The hydrophobic substituent A is hydrogen, an alkyl group (-R *), or an acyl group (-C (O) R *), wherein R * is an alkyl group having a straight chain of C1-C30 or one or more alkyl side chains. Preferably, R * is an alkyl group having from 1 to 20 carbon atoms, which is linear or has one or more alkyl side chains. Representative examples of R * include 2-ethylhexyl, decyl, lauryl, isotridecyl, cetyl, oleyl, stearyl, ), But the present invention is not limited thereto.

Y ¹ , Y ² and Y ³ are each hydrogen or a photochromic compound, and one of Y ¹ , Y ² and Y ³ must be a photochromic compound. The photochromic compound is a group derived from an indeno [2,1-f] naphtho [1,2-b] pyran compound (a1), and more specifically, a group derived from 3,3-diarylindeno [ , 1-f] naphtho [1,2-b] pyran compounds represented by the following formula (3).

In formula (3), O is an oxygen atom and R is hydrogen, hydroxy, an alkyl group (-R **), an aryl group, an alkoxy group (-OR **) And W are each a straight chain or a group having at least one alkyl side chain of C1-C30. Preferred R ** and W are each independently selected from C1-C20 alkyl, C3-C7 cycloalkyl, phenyl, monosubstituted phenyl, disubstituted phenyl, benzyl, monosubstituted benzyl, disubstituted benzyl, naphthyl, monosubstituted naphthyl, (C1-C6) alkylamino (e.g., dimethylamino, methylpropylamino, etc.), arylamino (e.g., phenylamino) : Phenylamino, benzylamino, etc.), monosubstituted arylamino or diacylarylamino group.

(R < 1 > and R < ₂ > are each independently selected from the group consisting of hydroxy, CN, NO2, chloro, bromo, fluoro, amino, C1-C6 alkyl, or C1-C6 alkoxy.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, hydroxy, mercapto, nitro, -CN, C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, allyl, Phenyl, benzyl, monosubstituted benzyl, naphthyl, monosubstituted naphthyl, fluoro, chloro, bromo, C1-C6 alkoxy, C3-C7 cycloalkoxy, phenoxy, monosubstituted phenoxy, benzyloxy, Mono (C1-C6) alkylamino or di (C1-C6) alkylamino such as dimethylamino, diethylamino or dipropylamino, C3 C7 cycloalkoxy (methylpiperidino), O, N, or S atom (e.g., methyl, ethyl, propyl, isopropyl, (Imidazole, morpholino, piperazino, thiomorpholino), or a monosubstituted O, N, or S atom C7 cyclic amino (methylimidazolo, methylpiperazino) which may be substituted by one or more of the above.

Wherein R ³ is located at a carbon atom of a, b, c, d and R ⁴ is located at an e, f, g, h carbon atom and preferred examples of R ³ and R ⁴ include C 1 -C 3 alkyl, C3 alkoxy, piperazino, morpholino, trifluoromethyl, or fluoro. x and y are each an integer of 0 to 3;

R ⁵ is located at positions 5, 6, 7 and 8, and R ⁶ is located at carbons 9, 10, 11, and 12, and the number of substituents n and m is an integer of 0 to 3, respectively. Most preferably, R ⁵ and R ⁶ are each C 1 -C 3 alkyl, C 1 -C 3 alkoxy, piperazino, morpholino, or fluoro.

In the present invention, it is preferable that the mixture of photochromic naphthopyran compounds includes the compound of Formula 1 and the compound of Formula 2 in a weight ratio of 8: 2 to 2: 8.

Which comprises a mixture of a photochromic naphthopyran compound having a hydrophilic substituent at the 13-position of the indeno [2,1-f] naphtho [1,2-b] The photochromic material of the present invention exhibits a faster fading rate [tau 1/2 (sec)] as compared to the conventional indeno-fused naphthopyran photochromic material with a hydrophobic substituent of up to 20 carbon atoms incorporated therein. The discoloration rate [? 1/2 (sec)] is the half value of {? (120) -? (0)} at the maximum absorption wavelength of each specimen after irradiation with ultraviolet light for 120 seconds, . The shorter the time is, the faster the fading rate is.

The photochromic material of the present invention also has low residual color characteristics. The residual color is represented by the fading rate [? 4/5 (sec)]. When the absorbance at the maximum absorption wavelength of each specimen is {? (120) -? (0 )}, And the shorter the time, the smaller the residual color of the photochromic compound upon fading.

Since the photochromic material of the present invention has a rapid fading rate and a very small amount of residual color during fading, the lens wearer moves from the outdoors to the inside of the room, thereby securing a transparent field of view within a few minutes to maintain optimal conditions.

The mixture of the formulas (4) and (5) for preparing the mixture of the formulas (1) and (2) is obtained from the sobit obtained by the dehydration reaction of the sorbitol. At this time, sorbitan is a mixture of 1,4-anhydrosorbitol and 1,5-anhydrosorbitol as main components, and is obtained from the esterification reaction and the addition reaction of ethylene oxide or propylene oxide as a mixture of formulas (4) and (5).

In the formulas (4) and (5), Z is an ethylene oxide group or a propylene oxide group, n is a repeating unit of an ethylene oxide group or a propylene oxide group, and A is an RC (O) - group.

The polyoxyalkylene sorbitan monoalkylate is represented by the formula (4) or the formula (5) sold by the difference in the content of the formula (4) or the formula (5) according to the manufacturer. The polyoxyalkylene sorbitan monoalkylate may be polyoxyethylene sorbitan monoalkylate or polyoxypropylene And includes all structures that can be referred to as polyoxypropylene sorbitan monoalkylate. Specific product names include Polysorbate 20, 40, 60, 80 and Tween 20, 40, 60, 80 and SFT 25, 81, 85, 65

The terminal alcohol group of the mixture of Formula 4 and Formula 5 and the indeno [2,1-f] naphtho [1,2-b] pyran compound of Formula 3 may be prepared by the following reaction scheme.

The synthesis method of binding an alcohol compound to the 13-position OH group of the indeno [2,1-f] naphtho [1,2-b] pyran compound is dehydration in the presence of an acid such as pyridinium para- toluenesulfonic acid, .

The photochromic materials of the present invention may be used alone or in combination with one or more other suitable organic photochromic compounds (complementary photochromic materials) having at least one maximum active absorbance in the range of about 400 to 780 nm, substrate. The photochromic material according to the present invention is dissolved or dispersed in the host material. The composition comprising the photochromic material and the host material according to the present invention is used for producing photochromic articles such as spectacle lenses, films and sheets.

In the present invention, the photochromic material and the organic photochromic compound incorporated into the host material can be suitably adjusted according to the desired color of the final product. For example, when activated with unfiltered sunlight, a photochromic material and an organic photochromic compound are used in a substantial neutral color, i. E., At a rate that represents a color as close to neutral as possible, given the hue of the activated photochromic material . These ratios can be easily implemented by a person having ordinary skill in the art to which the present invention belongs.

The medium gray represents a spectrum having a relatively identical absorbance in the visible region of 400 to 780 nm. The medium brown exhibits a spectrum whose absorbance in the 400 to 550 nm region is somewhat larger than the absorbance in the 550 to 700 nm region.

The content of the photochromic material of the present invention incorporated in the host material is preferably 0.0001 to 20 parts by weight based on 100 parts by weight of the host material.

When the organic photochromic compound is used in combination with the photochromic compound in addition to the photochromic compound of the present invention, the sum of the photochromic substance of the present invention and the other organic photochromic compound is preferably 0.001 to 30 parts by weight per 100 parts by weight of the host material Do. The 'organic photochromic compound' used in the present invention may be used alone or as a mixture of two or more thereof as conventionally known photochromic naphthopyran compounds.

Examples of the organic photochromic compound (supplementary photochromic substance) that can be used in the present invention include other naphthopyran, benzopyran, phenanthropyran, spiro (benzindoline) naphthopyran, spiro (indoline) (Indoline) naphthopyran, spiro (indoline) quinopyrene, spiro (indoline) pyran, spiro (indoline) naphthoxy, spiro (indoline) pyridobenzene, spiro Spiro (benzindoline) naphthoc photo, spiro (indoline) benz photo, or mixtures thereof.

The photochromic material of the present invention can be combined with the host material in the conventional manner described in the following description.

(1) dissolving or dispersing a photochromic material in a monomeric host material, such as by adding a photochromic material to a monomeric host material prior to polymerization and then heating the monomeric host material to heat or ultraviolet Lt; / RTI >

(2) a method of dissolving a photochromic material in an organic solvent, followed by dipping or heat-transferring the host material at a high temperature to absorb a photochromic material in the host material, or a method of dissolving a photochromic material and a host material together in an organic solvent , And the photochromic material is absorbed into the host material by volatilizing the organic solvent.

(3) a method of absorbing a photochromic material in an insulating layer between adjacent layers of a host material, for example, a method of supplying a photochromic material as a polymer film or a method of coating a portion of the host material A method of using a photochromic substrate.

The term "absorbing" or "absorbing" in the above method means permeation of the photochromic material into the host material, solvent transfer of the photochromic material into the porous polymer, vapor phase transfer and other transfer mechanisms.

In the present invention, the (organic) host material is a thermosetting resin, a thermoplastic resin or a mixture thereof.

Preferred examples of thermosetting organic host materials include alkylene diol dimethacrylates (alkylene repeat units 2 to 10); Alkylene diol diacrylates (alkylene repeat units 2 to 10); Neopentyl glycol dimethacrylate; Neopentyl glycol diacrylate; 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (ethoxy repeat units 2 to 10); 2,2-bis [4-acryloxy (polyethoxy) phenyl] propane (ethoxy repeat units 2 to 10); 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (ethoxy repeat units 2 to 10); 2,2-bis [4-methacryloxy (polypropyleneoxy) phenyl] propane (propyleneoxy repeat units 2 to 10); 2,2-bis [4-acryloxy (polypropyleneoxy) phenyl] propane (propyleneoxy repeat units 2 to 10); Polyethylene glycol dimethacrylate (ethyleneoxy repeat units 2 to 23); Polyethylene glycol diacrylate (ethyleneoxy repeat units 2 to 23); Polypropylene glycol dimethacrylate (propyleneoxy repeat units 2 to 14); Polypropylene glycol diacrylate (propyleneoxy repeat units 2 to 14); Trimethylolpropane trimethacrylate; Trimethylolpropane triacrylate; Tetramethylolmethane trimethacrylate; Tetramethylolmethane triacrylate; Tetramethylolmethane tetramethacrylate; Tetramethylolmethane tetraacrylate; Trimethylolpropane triethylene glycol triacrylate; Trimethylolpropane triethylene glycol triacrylate; Ditrimethylolpropane tetramethacrylate; Ditrimethylolpropane tetraacrylate; Methoxypolyethylene glycol methacrylate (ethyleneoxy repeat units 0 to 9); Isostearyl methacrylate; Isobornyl methacrylate; Phenoxypolyethylene glycol acrylate (ethyleneoxy repeat units 1 to 6); Naphthoxyethylene glycol acrylate; Isostearyl acrylate; Isobornyl acrylate; Glycidyl methacrylate; Methacryloyloxypropyltrimethoxysilane; Methacryloyloxypropyltriethoxysilane; Methacryloyloxypropylmethyldimethoxysilane; Acryloyloxypropyltrimethoxysilane; Acryloyloxypropyltriethoxysilane; Acryloyloxypropylmethyldimethoxysilane and the like and a mixture of two or more thereof and a polymer thereof

Another thermoset organic host material is urethane (meth) acrylate, and specific examples thereof include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis 4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate or methylcyclohexane diisocyanate, polyalkylene glycols having repeating units 1 to 4 of ethylene oxide or propylene oxide, or polycaprolactone diol, Low molecular weight polyfunctional polyols such as polyester diol, polycarbonate diol and polybutadiene diol, and polyfunctional polyols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Octanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4- Hydroxyethyl (meth) acrylate, which has been prepared from a urethane prepolymer by reacting a polyol such as hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane or pentaerythritol, Urethane (meth) acrylate, or a polymer thereof. These may be used alone or in combination of two or more.

Another thermoset organic host material is a mixture of isocyanates and thiols or isocyanates and thiols. The isocyanate and the thiol compound are polymers each used by mixing two or more kinds or two or more kinds of them.

Examples of specific isocyanates include ethylene diisocyanate; Trimethylenediisocyanate; Tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; Octamethylene diisocyanate; Nonamethylene diisocyanate; 2,2-dimethylpentane diisocyanate; 2,2,4-trimethylhexane diisocyanate; Decamethylene diisocyanate; Butenediisocyanate; 1,3-butadiene-1,4-diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; 1,6,11-undecane triisocyanate; 1,3,6-hexamethylene triisocyanate; 1,8-diisocyanato-4-isocyanatomethyloctane; 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane; Bis (isocyanatoethyl) carbonate; Bis (isocyanatoethyl) ether; 1,4-butylene glycol dipropyl ether-1,2-diisocyanate; 1,4-butylene glycol dipropyl ether-1,3-diisocyanate; 1,4-butylene glycol dipropyl ether-1,4-diisocyanate; 1,4-butylene glycol dipropyl ether-2,3-diisocyanate; 1,4-butylene glycol dipropyl ether-2,4-diisocyanate; Methyl lysine diisocyanate; Lysine triisocyanate; 2-isocyanatoethyl-2,6-diisocyanatohexanoate; 2-isocyanatopropyl-2,6-diisocyanatohexanoate; Mesitylene diisocyanate; 2,6-di (isocyanatomethyl) furan; 3,8- bis (isocyanato-methyl) tricyclo [5,2,1,0 ^2, 6] decane; 3,9-bis (isocyanato-methyl) tricyclo [5,2,1,0 ^2, 6] decane; 4,8-bis (isocyanato-methyl) tricyclo [5,2,1,0 ^2, 6] decane; 4,9- bis (isocyanato-methyl) tricyclo [5,2,1,0 ^2, 6] decane; 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane; 2,6-bis (isocyanatomethyl) bicyclo [2,2,1] heptane; Bis (isocyanatomethyl) cyclohexane; Dicyclohexylmethane diisocyanate; Cyclohexane diisocyanate; Methylcyclohexane diisocyanate; Dicyclohexyldimethylmethane diisocyanate; 2,2'-dimethyldicyclohexylmethane diisocyanate; Bis (4-isocyanato-n-butylidene) pentaerythritol; Dimer acid diisocyanate; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethylbicyclo [2,2,1] -heptane; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane; 1,3,5-tris (isocyanatomethyl) -cyclohexane; Thiophene-2,5-diisocyanate; Methylthiophene-2,5-diisocyanate; 1,4-dithiane-2,5-diisocyanate; Methyl 1,4-dithiane-2,5-diisocyanate; 1,3-dithiolane-4,5-diisocyanate; Methyl 1,3-dithiolane-4,5-diisocyanate; Methyl 1,3-dithiolane-2-methyl-4,5-diisocyanate; Ethyl 1,3-dithiolane-2,2-diisocyanate; Tetrahydrothiophene-2,5-diisocyanate; Methyltetrahydrothiophene-2,5-diisocyanate; Ethyl tetrahydrothiophene-2,5-diisocyanate; Methyltetrahydrothiophene-3,4-diisocyanate; 1,2-diisothiocyanatoethane; 1,3-diisothiocyanatopropane; 1,4-diisothiocyanatobutane; 1,6-diisothiocyanatohexane; p-phenylenediisopropylidenedisothiocyanate; Cyclohexane diisothiocyanate; 4-isocyanato-4'-isothiocyanatodiphenylsulfide;2-isocyanato-2'-isothiocyanatoethyl ethyl disulfide; Thiodiethyl diisocyanate; Thiodipropyl diisocyanate; Thiodicyldiisocyanate; Dimethyl sulfone diisocyanate; Ditodimethyl diisocyanate; Dithiodiethyl diisocyanate; Dithiodipropyl diisocyanate; Dicyclohexylsulfone-4,4'-diisocyanate; Or 1-isocyanatomethyl thia-2,3-bis (2-isocyanatoethylthia) propane.

Specific examples of thiol compounds include 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane; 1,2-bis (2- (2-mercaptoethylthio) -3-mercaptopropylthio) -ethane; Bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide; 3- (3-mercapto-2- (2-mercaptoethylthio) -propylthio] propylthio} -propane-1-thiol ; 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester; Ethylthio) propane-1-thiol (2-mercaptoethylthio) -3- (2- {2- [ ; Trimethylolpropane tris (mercaptopropionate); Trimethylolethane tris (mercaptopropionate); Glycerol tris (mercaptopropionate); Trimethylolchlorotris (mercaptopropionate); Trimethylolpropane tris (mercaptoacetate); Trimethylol ethane tris (mercaptoacetate); Pentaerythritol tetrakis (mercaptopropionate) (PETMP); Pentaerythritol tetrakis (mercaptoacetate) (PETMA); Bispentaerythritol-ether-hexakis (mercaptopropionate) (BPEHMP); Bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA); Bispentaerythritol hexa (2-mercaptoacetate) (BPEMA); Bistrimethylolpropane tetrakis (3-mercaptopropionate) (BTMPMP); Or bistrimethylolpropane tetrakis (2-mercaptoacetate) (BTMPMA).

Preferable examples of the thermoplastic organic host material include a polyethylene resin, a polypropylene resin, a polyacetal resin, a polyethylene (or propylene) phthalate resin, a polyethylene (or propylene) terephthalate resin, a polyethylene (or propylene) isophthalate resin, Polyvinyl acetate resin, polyvinyl acetate resin, polycarbonate resin, polyacrylic resin, polystyrene resin, polyurethane resin, acrylonitrile styrene resin, acrylonitrile butadiene (ABS) resin, polymethylmethacrylate resin, cellulose acetate, cellulose propionate, cellulose Butyrate, and cellulose acetate butyrate resin.

Examples of the host material containing the photochromic material of the present invention include optically transparent or translucent materials such as planar lenses and ophthalmic lenses, automobile glasses such as windshield glass, aircraft glass, plastic plates, polymer films, etc. can do.

The present invention can be better understood by the following examples, and the following examples are for illustrative purposes only and are not intended to limit the scope of protection of the claims.

Example

Y ¹ , Y ² and Y ³ are each independently hydrogen or 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-indeno [2,1-f] -b] pyran and one of Y ¹ , Y ² and Y ³ is a 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-indeno [ 2,1-f] naphtho [1,2-b] pyran.

16.0 g (0.03 mole) of 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-13-hydroxy-indeno [2,1- ), 18.3 g of polyoxyethylene sorbitan monolaurate (0.015 mole Mn: 1,220, product name: SFT 25) and pyridinium para-toluenesulfonic acid (0.1 g) were dissolved in acetonitrile, Time. After completion of the reaction, the solvent was vacuum distilled to obtain 34 g of a distillation residue. 0.5 g of the distillation residue was fractionated and each component was separated and purified by column chromatography. After separation and purification of each component, NMR peak was confirmed and the results were confirmed. As a result, it was confirmed that 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-indeno [2 , 1-f] naphtho [1,2-b] pyran were substituted by one molecule, 70%, 25% and 5%, respectively.

Comparative Example  One

16.2 g (0.03 mole) of 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-13-hydroxy-indeno [2,1- ), 6.9 g of sorbitan monolaurate (0.015 mole Mw: 346, product name: SF 20) and pyridinium para-toluenesulfonic acid (0.1 g) were dissolved in acetonitrile and maintained in an ultrasonic reactor for 24 hours. After completion of the reaction, the solvent was vacuum distilled to obtain 23 g of a distillation residue. 0.5 g of the distillation residue was fractionated and each component was separated and purified by column chromatography. After separation and purification, NMR spectroscopic analysis of ethylenenic peaks showed that 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-indeno [2,1- f] naphtho [1,2-b] pyran.

Comparative Example  2

16.2 g (0.03 mole) of 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-13-hydroxy-indeno [2,1- ), 6.1 g (0.033 mole Mw: 186.3) of dodecanol and 0.1 g of pyridinium para-toluenesulfonic acid were dissolved in acetonitrile, and the mixture was maintained in an ultrasonic reactor for 10 hours. After completion of the reaction, the solvent was vacuum distilled to obtain 2 g of a distillation residue. 0.5 g of the distillation residue was fractionated and purified by column chromatography. The separated and purified product was analyzed by NMR to find that 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-13-dodecaneoxy-indeno [2,1-f] -b] pyran structure.

Comparative Example  3

16.0 g (0.03 mole) of 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-13-hydroxy-indeno [2,1- ), 19.8 g of polyoxyethylene monomethyl ether (0.033 mole Mw: 600, manufactured by Hara Chemical Co., Ltd., MPEG 600) and 0.1 g of pyridinium para-toluenesulfonic acid were dissolved in acetonitrile and maintained in an ultrasonic reactor for 10 hours Respectively. After completion of the reaction, the solvent was vacuum distilled to obtain 35 g of a distillation residue. 0.5 g of the distillation residue was fractionated and purified by column chromatography. The separated and purified product was analyzed by NMR to find that 3,3-di (4-methoxyphenyl) -6,11,13-trimethyl-13-hydroxy-indeno [2,1- b] pyran structure and an ether bond compound of polyoxyethylene monomethyl ether.

Preparation and evaluation of discoloration lenses

Preparation of discoloring lens specimen : The photochromic material obtained in Example 1 and Comparative Example 1-3 was mixed with a polymerization initiator and a polymerizable monomer, and then injected into a circular polymerization mold and thermally polymerized. Then, the mold was separated to obtain a thickness 2.0 mm transparent photochromic plastic specimen.

0.2 part by weight of azobisisobutyronitrile as a polymerization initiator and 0.03 part by weight of the photochromic material obtained in each of Example 1 and Comparative Example 1-3 were added to 100 parts by weight of the polymerizable monomer at a heat curing temperature of 60 Lt; 0 > C for 2 hours, and further polymerized at 100 < 0 > C for 2 hours to complete the polymerization.

The polymerizable monomer was a mixture of 50 parts by weight of 2,2-bis (4-acryloyloxydiethoxyphenyl) propane (Miramer 240, Miwon Specialties Korea) / polyethylene glycol diacrylate (Miramer 282, ) Was used.

Evaluation of photochromic properties : The photochromic plastic specimens obtained in the present invention were evaluated for the following photochromic properties.

[1] Maximum Absorption Wavelength (? Max): It is the maximum absorption wavelength after color development as determined by a spectrophotometer (instantaneous multi-channel photodetector, UVS-3100) manufactured by Shin-Koh Corporation. The maximum absorption wavelength relates to the hue at the time of color development.

[2] Color Density (A0): Difference between the absorbance {ε (120)} and {ε (0)} of the maximum absorption wavelength before and after light irradiation for 120 seconds. The higher the value, the better the photochromic characteristics.

(3) Fading speed (τ1 / 2 (sec)): The absorbance at each of the maximum wavelengths of each specimen is {ε (120) -ε (0)} when irradiated with ultraviolet light for 120 seconds, Of the time required to decline. The shorter this time, the faster the fading rate.

(4) The discoloration rate (τ4 / 5 (sec)): The absorbance at the maximum absorption wavelength of each specimen was {ε (120) -ε (0)} when irradiated with ultraviolet light for 120 seconds, Of the time required to decline to 4/5 of the time. The shorter this time, the less the residual color of the photochromic dye at fading.

[5] initial coloring {ε (0)}: absorbance at the maximum absorption wavelength in the unexposed state. For example, in an optical material such as a spectacle lens, the lower the value, the better the photochromic property.

[6] Remaining ratio (A200 / A0 x 100): The following acceleration test was carried out in order to evaluate the durability of color development by light irradiation and heat. The obtained specimens were accelerated by accelerated conditions (0.51 W / m ² at 340 nm, temperature 65 ° C., relative humidity 50%, 200 hours) on a Cu line Xenon tester Xe-3-HS. Thereafter, the above-mentioned coloring density was evaluated before and after the test, and the color development density (A0) before the test and the color development density (A200) after the test were measured. The ratio (A200 / A0) As an indicator. The higher the residual ratio, the higher the durability of color development.

The test results are shown in Table 1 below.

division lambda max. Color density Fade rate Initial staining Remaining rate nm A0 1/2 (sec.) 4/5 (sec.)          ε (0) A2 A200 / A0 x 100 Example 1 570 0.71 24 120 0.17 87 Comparative Example 1 570 0.74 55 280 0.2 80 Comparative Example 2 570 0.75 62 325 0.2 84 Comparative Example 3 560 0.72 58 297 0.2 85

From the result of the test, the photochromic material of the present invention has a hydrophobic substituent having a hydrophobic substituent at the 13-position, and thus the rate of discoloration becomes significantly faster than that of Comparative Example 1-3 in which the substituent is only introduced with a hydrophilic or hydrophobic group Able to know.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

The -OCH2-, -OCH2CH2-, or -OCH (CH3) CH2- group at the 13-position of 3,3-diaryl-indeno [2,1-f] 1 to 15, wherein the photochromic material is a mixture of the following formula (1) and (2):

In the above formulas (1) and (2)
O is an oxygen atom, Z is _{-OCH 2 -, -OCH 2 CH 2} - , or -OCH (CH ₃₎ CH ₂ - group, ^{and, q 1, q 2, q} 3, p 1, p 2 and p ³ are Each of which is an integer of 1 to 15,
A is hydrogen, an alkyl group (-R ^* ) or an acyl group (-C (O) R ^* ), wherein R ^* is an alkyl group having a straight chain of C1-C30 or having at least one alkyl side chain,
Y ¹ , Y ² and Y ³ are each hydrogen or a photochromic compound, and ^{one of} Y ¹ , Y ² and Y ³ is a photochromic 3,3-diaryl-indeno [2,1-f] Yl [1,2-b] pyran compound.
delete The photochromic material according to claim 1, wherein the 3,3-diaryl-indeno [2,1-f] naphtho [1,2-b]

In Formula 3,
R is hydrogen, hydroxy, alkyl (-R **), aryl, alkoxy (-OR **) or -OC (O) W group, wherein R ** and W are each straight chain, A group having at least one alkyl side chain,
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, hydroxy, mercapto, nitro, -CN, C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, allyl, phenyl, benzyl, (C1-C6) alkoxy, C3-C7 cycloalkoxy, phenoxy, benzyloxy, naphthoxy, amino, mono C3-C7 cycloalkylamino, di-C3-C7 cycloalkylamino, C3-C7 cycloamino, C3-C7 cyclic amino containing O, N or S atoms,
x and y are each an integer of 0 to 3, and
n and m each represent an integer of 0 to 3;
The photochromic material of claim 1, wherein the mixture comprises the compound of Formula 1 and the compound of Formula 2 in a weight ratio of 8: 2 to 2: 8.
100 parts by weight of host material; And
0.0001 to 20 parts by weight of the photochromic material according to any one of claims 1 to 3;
And a photochromic resin.
The photochromic resin composition according to claim 5, wherein the host material is a thermosetting resin, a thermoplastic resin, or a mixture thereof.
6. The photochromic resin composition according to claim 5, wherein the photochromic material further comprises another organic photochromic compound.
8. The composition of claim 7, wherein the other organic photochromic compound is selected from the group consisting of naphthopyran, benzopyran, phenanthropyran, spiro (benzindolin) naphthopyran, spiro (indolin) benzopyran, spiro (indolin) (Indoline) Pyridobenzane, Spiro (Indoline) Pyridobenzane, Spiro (Indoline) Pyridobenzene, Spiro (Indoline) Pyridobenzene, Spiro Indolin) naphthot photo, spiro (indoline) benz photo, or a mixture thereof.
A photochromic article molded from the photochromic resin composition according to claim 6.