JP4424981B2 - Chromene compounds - Google Patents

Description

  The present invention relates to a novel chromene compound useful as a photochromic compound for photochromic eyeglass lenses.

Photochromism is a reversible action that quickly changes color when a compound is exposed to light containing ultraviolet light, such as sunlight or mercury lamp light, and returns to its original color when the light is turned off and left in the dark. . A compound having this property is called a photochromic compound and is used as a material for a photochromic plastic lens.
In photochromic compounds used for such applications, (1) the degree of coloring in the visible light region (hereinafter referred to as initial coloring) before irradiation with ultraviolet rays is low, (2) coloring when irradiated with ultraviolet rays Degree (hereinafter referred to as the color density) is high, (3) the speed from the start of UV irradiation until the color density reaches saturation (hereinafter also referred to as high color sensitivity), (4) The speed from the end of irradiation to the return to the original state (hereinafter referred to as the fading speed) is fast, (5) the repetitive durability of this reversible action is good, and (6) the dispersibility in the host material used is high. In order to increase the viscosity, there is a demand for the property of being dissolved at a high concentration in the monomer composition that becomes the host material after curing.
As a photochromic compound that can satisfy such requirements, a chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton is known (see Patent Documents 1 and 2). ).

On the other hand, in photochromic plastic lenses, it is preferred to develop colors such as gray or brown, and such intermediate colors are developed at several types of photochromic compounds having different color tones, specifically 430 to 530 nm. It is obtained by mixing a yellow to red compound having a maximum absorption at the time and a purple to blue compound having a maximum absorption at the time of color development at 550 to 650 nm.
However, when the color tone is adjusted by such a method, various problems occur due to the difference in the photochromic properties of the mixed compounds. For example, when the durability of a compound that develops yellow color is lower than that of a compound that develops blue color, the color tone will gradually change to a strong blue tone when used over a long period of time. In addition, when the color development sensitivity and fading speed of the yellow compound are lower than that of the blue compound, the color tone in the middle of color development is strong blue, and the color tone in the middle of color fading becomes a color tone with strong yellowness, etc. Will occur.

It is considered that such a problem can be solved by using a compound that has two or more absorption maximums at the time of color development and develops a neutral color with a single compound. So far, compounds as shown in the following formulas (I) to (III) are known as photochromic compounds having an absorption maximum of 2 or more at the time of color development, but they are colored in a neutral color and shown in the above (1) to (5) There is no known photochromic compound that satisfies such requirements.
That is, the following formula (I)

The chromene compound represented by (see Patent Document 3) has a lower absorption at 430 to 530 nm than that at 550 to 650 nm, and does not show an intermediate color as the color tone.

  In addition, the following formula (II)

The chromene compound represented by (see Patent Document 4) has a problem of high initial coloration and low repetition durability.

  In addition, the following formula (III)

Although the chromene compound represented by (see Patent Document 5) develops an intermediate color, it has a problem that the fading speed is slow and the repetition durability is still low.

International Publication No. 99/15518 International Publication No. 2001/60811 Pamphlet International Publication No. 96/14596 Pamphlet International Publication No. 2000/35902 Pamphlet International Publication No. 2001/19813 Pamphlet

  Therefore, the present invention shows an intermediate color as the color tone, further improves the photochromic characteristics as compared with the above-mentioned compounds, has less initial coloring, high color development sensitivity, high color fading speed, and little coloration at the time of deterioration. It is an object of the present invention to provide a chromene compound that has a low decrease in color density when used, that is, a chromene compound having excellent photochromic durability, and that can be dissolved in a monomer composition as a base material to be used at a high concentration. And

  The present inventors have intensively studied to solve the above problems. As a result, in a chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton, which is known to give excellent photochromic properties, indeno (2,1-f) A compound having a specific substituent introduced at the 12-position of the naphtho (1,2-b) pyran structure develops a neutral color without impairing its excellent photochromic properties, and the compound has little initial coloration and a fading rate. The present invention was completed by obtaining the knowledge that it is fast.

That is, the first present invention is a chromene compound represented by the following formula (1).

{Where R is ¹ And R ² Are bonded to each other to form a spiro bond at position 13 of the indeno (2,1-f) naphtho (1,2) pyran structure,

(Wherein the carbon atom represented by 13 refers to the 13th carbon atom of the indeno (2,1-f) naphtho (1,2-b) pyran structure),
R ³ And R ⁴ Each independently represents an unsubstituted aryl group, an aryl group having an alkoxy group, an aryl group having a morpholino group, or a 2,6-dimethylpiperidino group or 2,2,6,6-tetramethylpiperidi An aryl group having
R ⁵ Is a hydrogen atom or an alkoxy group,
R ⁷ Is an alkyl group, a cycloalkyl group, an alkoxy group, an unsubstituted aryl group, an acyl group, a halogen atom, -O (C) OCH ₃ Or a trifluoromethyl group,
R ¹⁴ Is an alkoxy group, a morpholino group, an aryl group having a morpholino group, or a 2,6-dimethylpiperidino group;
R ¹⁵ Is a hydrogen atom, an unsubstituted aryl group, an aryl group having an alkyl group, an aryl group having an alkoxy group, a 2,6-dimethylpiperidino group, or a morpholino group. }

  Moreover, 2nd this invention is a photochromic composition containing the chromene compound of the said invention. Furthermore, the third aspect of the present invention is a photochromic optical article having, as a constituent member, a polymer molded body in which the chromene compound of the present invention is dispersed, and the fourth aspect of the present invention includes all or one of at least one surface. An optical article having, as a constituent member, an optical substrate coated with a polymer film in which a chromene compound of the present invention is dispersed.

  The chromene compound of the present invention exhibits an intermediate color tone, low initial coloration, high color development sensitivity, high color density, and fast discoloration rate even when dispersed in a solution or a polymer solid matrix. In addition to exhibiting excellent photochromic properties, it also exhibits excellent durability. Therefore, for example, when a photochromic lens is made using the chromene compound of the present invention, it quickly darkens when it goes outdoors, and it becomes dark and neutral, and when it returns from the outdoors to the room, it fades quickly to the original color tone. By returning, a highly durable photochromic lens that can be used for a long time can be obtained. Further, the photochromic lens has a feature that no color shift occurs even when the color is emitted or faded or after long-term use.

The chromene compound of the present invention has the following formula:

(In the formula, the numerical values represent the positions of carbon atoms and hydrogen atoms.)
A 12-position of the indeno (2,1-f) naphtho (1,2-b) pyran structure, having an indeno (2,1-f) naphtho (1,2-b) pyran structure represented by It has a specific organic group ( corresponding to the group R ⁷ ) on the carbon atom. A chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton is known to exhibit excellent photochromic properties, but has a specific substituent at the 12-position. By having it, while maintaining its excellent photochromic characteristics, it is possible to develop a dark intermediate color with a single compound, reduce initial coloration, and increase the fading speed.

The chromene compound of the present invention has an intermediate color tone, a high color development sensitivity, a low initial coloration, a fast fading speed, and a good photochromic durability, from the following formula (1). It is the chromene compound shown . Chromene compound represented by the following formula (1) is not easy photochromic properties are colored to good intermediate color.

{Where R is ¹ And R ² Are bonded to each other to form a spiro bond at position 13 of the indeno (2,1-f) naphtho (1,2) pyran structure,

(Wherein the carbon atom represented by 13 refers to the 13th carbon atom of the indeno (2,1-f) naphtho (1,2-b) pyran structure),
R ³ And R ⁴ Each independently represents an unsubstituted aryl group, an aryl group having an alkoxy group, an aryl group having a morpholino group, or a 2,6-dimethylpiperidino group or 2,2,6,6-tetramethylpiperidi An aryl group having
R ⁵ Is a hydrogen atom or an alkoxy group,
R ⁷ Is an alkyl group, a cycloalkyl group, an alkoxy group, an unsubstituted aryl group, an acyl group, a halogen atom, -O (C) OCH ₃ Or a trifluoromethyl group,
R ¹⁴ Is an alkoxy group, a morpholino group, an aryl group having a morpholino group, or a 2,6-dimethylpiperidino group;
R ¹⁵ Is a hydrogen atom, an unsubstituted aryl group, an aryl group having an alkyl group, an aryl group having an alkoxy group, a 2,6-dimethylpiperidino group, or a morpholino group. }

In the chromene compound of the present invention, the substituent R ⁷ bonded to the carbon atom at the 12-position of the indeno (2,1-f) naphtho (1,2-b) pyran structure is an alkyl group, a cycloalkyl group, a haloalkyl group, An alkoxy group, an unsubstituted aryl group, an acyl group, a halogen atom, —O (C) OCH ₃ , or a trifluoromethyl group.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.

Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the unsubstituted aryl group include a phenyl group and a naphthyl group.

Examples of the acyl group include an acetyl group and an ethylcarbonyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ¹ and R ² in the above formula (1) are a ring in which R ¹ and R ² are bonded to each other and spiro-bonded to the 13th position of the indeno (2,1-f) naphtho (1,2-b) pyran structure. And, it is a group forming any one kind of ring represented by the following formula.

In the formula, the carbon atom represented by 13 refers to the carbon atom at the 13th position of the indeno (2,1-f) naphtho (1,2-b) pyran structure.

Chromene compound of the present invention, by having these aliphatic rings, fading rate is Ri a particularly fast, can be reduced initial coloring.

R ³ and R ⁴ in the formula (1) are each independently an unsubstituted aryl group, an aryl group having an alkoxy group, an aryl group having a morpholino group, or a 2,6-dimethylpiperidino group. Alternatively, it is an aryl group having a 2,2,6,6-tetramethylpiperidino group.

Examples of the unsubstituted aryl group include unsubstituted aryl groups having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.

The aryl group having an alkoxy group is preferably a group in which 1 to 7, particularly 1 to 4 of hydrogen atoms of an unsubstituted aryl group having 6 to 10 carbon atoms are substituted with an alkoxy group. As an alkoxy group, a C1-C5 alkoxy group is preferable. Specific examples of suitable alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group and the like. Suitable aryl groups having an alkoxy group include a methoxyphenyl group, an ethoxyphenyl group, a dimethoxyphenyl group, a trimethoxyphenyl group, and a methoxybiphenyl group, and specifically a 4-methoxyphenyl group.

The aryl group having the morpholino group is preferably a group in which 1 to 7, particularly 1 to 4 of the unsubstituted aryl group having 6 to 10 carbon atoms is substituted with a morpholino group. Suitable aryl groups having a morpholino group include morpholinophenyl groups. The substitution position of the morpholino group is not particularly limited, and the total number thereof is not particularly limited, but the substitution position is preferably substituted at the 3-position or 4-position when the aryl group is a phenyl group, and the number is 1. Preferably there is. Specifically, 4-morpholinophenyl group is mentioned.

The aryl group having the 2,6-dimethylpiperidino group or the 2,2,6,6-tetramethylpiperidino group is an unsubstituted aryl group having 6 to 10 carbon atoms and 1 to 7 hydrogen atoms. In particular, a group in which 1 to 4 are substituted with a 2,6-dimethylpiperidino group or a 2,2,6,6-tetramethylpiperidino group is preferable. The substitution position of the 2,6-dimethylpiperidino group or the 2,2,6,6-tetramethylpiperidino group is not particularly limited, and the total number thereof is not particularly limited. Is preferably substituted at the 3- or 4-position, and the number is preferably 1. Specific examples include 4- (2,6-dimethylpiperidino) phenyl group and 4- (2,2,6,6-tetramethylpiperidino) phenyl group.

It is particularly preferable that at least one of R ³ and R ⁴ is any group shown in the following (a) to (b) .

(a) an aryl group having a 2,6-dimethylpiperidino group or a 2,2,6,6-tetramethylpiperidino group
(b) An aryl group having a morpholino group.

In the substituted aryl group in the above (a) to (b) , the substitution position of the substituent is not particularly limited, and the total number thereof is not particularly limited, but the substitution position is 3 when the aryl group is a phenyl group. It is preferably substituted at the 4- or 4-position, and the number is preferably 1. Specific examples of suitable substituted aryl groups include 4-morpholinophenyl group and 4- (2,6-dimethylpiperidino) phenyl group.

In the present invention, a more preferred chromene compound of the present invention is R ⁴ Is a chromene compound in which (a) an aryl group having a 2,6-dimethylpiperidino group or 2,2,6,6-tetramethylpiperidino group and (b) an aryl group having a morpholino group.

R ^{5 in the} formula (1) is a hydrogen atom or an alkoxy group. Among them, as an alkoxy group, a Hammett number of −0.49 to −0.20 is medium, specifically, a methoxy group (σ = −0.28), an ethoxy group (σ = −0.21), propoxy Group (σ = −0.26) and the like.

R ^{14 in the} formula (1) is an alkoxy group, a morpholino group, an aryl group having a morpholino group, or a 2,6-dimethylpiperidino group.

Examples of the alkoxy group include a moderate electron donating group having a Hammett number of −0.49 to −0.20. Specifically, a methoxy group (σ = −0.28), an ethoxy group ( and alkoxy groups such as σ = −0.21) and propoxy groups (σ = −0.26).

Examples of the aryl group having a morpholino group include a p-morpholinophenyl group (σ = −0.16) which is a weak electron-donating group having a Hammett number of −0.19 to −0.01.

  Specific examples of the particularly preferred chromene compound in the present invention include the following compounds.

  The chromene compound of the present invention generally exists as a colorless, pale yellow, pale green solid or viscous liquid at ordinary temperature and pressure, and can be confirmed by the following means (a) to (c).

(B) By measuring a proton nuclear magnetic resonance spectrum ( ¹ H-NMR), a peak based on an aromatic proton and an alkene proton in the vicinity of δ 5.0 to 9.0 ppm, and in the vicinity of δ 1.0 to 4.0 ppm. Peaks based on protons of alkyl groups and alkylene groups appear. Moreover, the number of protons of each linking group can be known by relatively comparing the respective spectrum intensities.

  (B) The composition of the corresponding product can be determined by elemental analysis.

(C) By measuring a ¹³ C-nuclear magnetic resonance spectrum (13 C-NMR), a peak based on carbon of an aromatic hydrocarbon group in the vicinity of δ110 to 160 ppm, and a peak based on carbon of an alkene and alkyne in the vicinity of δ80 to 140 ppm. , A peak based on carbon of an alkyl group and an alkylene group appears in the vicinity of δ20-80 ppm.

  The method for producing the chromene compound of the present invention is not particularly limited and may be obtained by any synthesis method. For example, the chromene compound represented by the formula (1) can be preferably produced by the following method.

  That is, the following formula (6)

^{{R 1, R 2, R} 5, R 7, R 14, R 15 in the formula has the same meaning as defined before following formula (1). }
And a hydroxy-fluorenone derivative represented by the following formula (7):

^{R 3, ^{R 4} in the formula is as defined in previous following formula (1). }
Can be suitably produced by a method of reacting with a propargyl alcohol derivative represented by the above in the presence of an acid catalyst.

  The method for synthesizing the hydroxy-fluorene derivative represented by the formula (6) and the propargyl alcohol derivative represented by the formula (7) is not particularly limited. The hydroxy-fluorene derivative represented by the formula (6) is, for example, the following formula (8)

^{{R 5, R 7, R} 14, and ^{R 15} in the formula has the same meaning as defined before following formula (1). }
Is converted into an amine by a method such as Curtius rearrangement, Hofmann rearrangement or Lossen rearrangement, and then converted from a diazonium salt to bromide by a Sandmeyer reaction or the like, and the obtained bromide is converted to magnesium or lithium. To prepare an organometallic reagent, which is represented by the following formula (9)

{Wherein, ^{R 1} and ^{R 2} have the same meanings as before following formula (1). }
And the following formula (10):

^{{R 1, R 2, R} 5, R 7, R 14 in the formula, and ^{R 15} are the same as defined before following formula (1). }
Can be synthesized by reacting the alcohol body under neutral to acidic conditions at 10 to 120 ° C. for 10 minutes to 2 hours to spirodify the alcohol.

  The reaction ratio between the organometallic reagent prepared in the above reaction and the ketone represented by the formula (10) is adopted from a wide range, but is generally from 1:10 to 10: 1 (molar ratio). Selected. The reaction temperature is usually preferably from −10 to 70 ° C., and as the solvent, an aprotic organic solvent such as diethyl ether, tetrahydrofuran, benzene, toluene or the like is used.

  Thereafter, the obtained alcohol is spirolated under neutral to acidic conditions. Acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina and the like as an acid catalyst at this time are 0.1 to 10 parts by weight with respect to 100 parts by weight of the alcohol body represented by the formula (10). It is preferable to use within a range. The reaction temperature is preferably 10 to 120 ° C., and as the solvent, for example, acetic acid, tetrahydrofuran, benzene, toluene and the like are used.

Further, propargyl alcohol derivative represented by the front following formula (7) can be synthesized, for example, by reacting a metal acetylene compound ketone derivatives and such as lithium acetylide corresponding to the general formula (7).

The reaction of an acid reacted with 2 previous following formula (6) compounds represented by the compound represented by the formula (7), for example, performed as follows.

That is, the reaction ratio of these two compounds is selected from a wide range, but is generally selected from a range of 1:10 to 10: 1 (molar ratio). Further, sulfuric acid catalyst, benzenesulfonic acid, p- toluenesulfonic acid, acidic alumina or the like is used, the sum of the previous above formula with a compound represented by (6) the compound represented by (7) (reaction substrate) 100 It is used in the range of 0.1 to 10 parts by weight with respect to parts by weight. The reaction temperature is usually preferably from 0 to 200 ° C., and as the solvent, an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene or the like is used.

  The method for purifying the product is not particularly limited. For example, the product can be purified by silica gel column purification and recrystallization.

The chromene compound of the present invention is well soluble in common organic solvents such as toluene, chloroform, and tetrahydrofuran. When the chromene compound represented by the formula (1) is dissolved in such a solvent , the solution is generally colorless and transparent, and quickly develops color when irradiated with sunlight or ultraviolet light, and reversibly and rapidly when the light is blocked. It exhibits a good photochromic effect that returns to colorless.

  Moreover, the chromene compound of the present invention exhibits similar photochromic properties even in a polymer solid matrix. Such a polymer solid matrix is not particularly limited as long as the chromene compound of the present invention is uniformly dispersed, and optically preferably, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, poly Mention may be made of thermoplastic resins such as ethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane and polycarbonate.

  Further, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2 , 2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane and other polyacrylic acid and polymethacrylate compounds; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxy succinate, Diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol car And polyvalent allyl compounds such as trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene Thioacrylic acid and polyvalent thiomethacrylic acid ester compounds; glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3- (glycidyl-2-oxyethoxy) 2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3-glycidyloxy-2-hydroxypropyloxy) Examples include acrylic acid ester compounds such as 2-hydroxypropyl acrylate and methacrylic acid ester compounds; thermosetting resins obtained by polymerizing radical polymerizable polyfunctional monomers such as divinylbenzene.

  These monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride; acrylic acid such as methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate and 2-hydroxyethyl methacrylate And methacrylic acid ester compounds; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate; styrene, chlorostyrene, methylstyrene, Examples thereof include a copolymer with a radically polymerizable monofunctional monomer such as vinyl naphthalene, α-methylstyrene dimer, vinyl compound such as bromostyrene.

  There is no restriction | limiting in particular as a method to disperse | distribute the chromene compound of this invention in the said polymer solid matrix, A general method can be used. For example, the thermoplastic resin and the chromene compound are kneaded in a molten state and dispersed in the resin, or after the chromene compound is dissolved in the polymerizable monomer, a polymerization catalyst is added and polymerization is performed with heat or light. And a method of dispersing in the resin by dyeing a chromene compound on the surface of the thermoplastic resin and the thermosetting resin.

  The chromene compound of the present invention can be widely used as a photochromic material, for example, various kinds of storage materials, copy materials, printing photoreceptors, cathode ray tube storage materials, laser photosensitive materials, and holographic photosensitive materials in place of silver salt photosensitive materials. It can be used as various storage materials. In addition, the photochromic material using the chromene compound of the present invention can also be used as a material such as a photochromic lens material, an optical filter material, a display material, a light meter, and a decoration.

  For example, when used for a photochromic lens, there is no particular limitation as long as it is a method capable of obtaining uniform light control performance, and specifically, a polymer film obtained by uniformly dispersing the photochromic material of the present invention. Or a method in which the chromene compound of the present invention is dispersed in the polymerizable monomer and polymerized by a predetermined method, or this compound is dissolved in, for example, silicone oil. There is a method in which a lens surface is impregnated at 150 to 200 ° C. for 10 to 60 minutes, and the surface is further coated with a curable substance to form a photochromic lens. Furthermore, there is a method of applying the polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens. Furthermore, a coating agent comprising a polymerization curable composition containing the chromene compound of the present invention may be applied to the surface of the lens substrate to cure the coating film. At this time, the lens substrate may be subjected to surface treatment such as surface treatment with an alkaline solution or plasma treatment in advance, and further (with or without these surface treatments) the substrate and the coating film. Primers can also be applied to improve the adhesion.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1
The following 5-hydroxy- (7H) benzo (c) fluorene derivatives

1.0 g (0.0020 mol) and the following propargyl alcohol derivative

1.1 g (0.003 mol) was dissolved in 70 ml of toluene, 0.020 g of p-toluenesulfonic acid was further added, and the mixture was stirred for 1 hour with heating under reflux. After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel to obtain 1.1 g of a green powder product. The yield was 83%.

Elemental analysis of the product, C79.76%, H6.92%, N1.70 %, a _О11.59%, C79.78% calculated values of _C 55 _{H 57 NО 5,} H6.94 %, N 1.69% and O 11.59%.

  Further, when a proton nuclear magnetic resonance spectrum was measured, as shown in FIG. 1, a peak of 18H based on methyl and methylene protons of a tetramethylcyclohexane ring in the vicinity of δ1.0 to 3.0 ppm, δ3.0 to 4.0 ppm. A 20H peak based on a morpholino group methylene proton and a methoxy group methyl proton was observed in the vicinity, and a 19H peak based on an aromatic proton and an alkene proton was observed in the vicinity of δ 5.6 to 9.0 ppm.

Further, when the ¹³ C-nuclear magnetic resonance spectrum was measured, it showed a peak based on the aromatic ring carbon in the vicinity of δ110 to 160 ppm, a peak based on the alkene carbon in the vicinity of δ80 to 140 ppm, and a peak based on the carbon of the alkyl in δ20 to 60 ppm. It was.

  From the above results, it was confirmed that the isolated product was a compound represented by the following structural formula.

Examples 2-20
The chromene compounds shown in Tables 1 to 7 were synthesized in the same manner as in Example 1. About the obtained product, as a result of structural analysis using the means for structure confirmation similar to Example 1, it confirmed that it was a compound shown by structural formula shown in Tables 1-7. Table 8 shows elemental analysis values of these compounds and calculated values obtained from the structural formulas of the respective compounds. Further, FIG. 1 shows a characteristic spectrum of ¹ H-NMR spectrum.

Examples 21-40 and Comparative Examples 1-4
The chromene compound obtained in Example 1 was mixed with a polymerizable monomer, applied to the surface of the lens substrate, polymerized, and then evaluated for physical properties. The photochromic polymerizable composition includes a radical polymerizable monomer 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane / polyethylene glycol diacrylate (average molecular weight 532) / trimethylolpropane trimethacrylate / polyester oligomer. Hexaacrylate (Daicel UCB, EB-1830) / glycidyl methacrylate was blended at a blending ratio of 50 parts by weight / 10 parts by weight / 10 parts by weight / 10 parts by weight / 10 parts by weight, respectively. After adding 1 part by weight of the chromene compound obtained in Example 1 to 90 parts by weight of the radical polymerizable monomer mixture and mixing well, 1-hydroxycyclohexyl phenyl ketone as a polymerization initiator was reduced to 0. 5 parts by weight, 5 parts by weight of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate as a stabilizer, and 7 parts by weight of γ-methacryloyloxypropyltrimethoxysilane as a silane coupling agent And 3 parts by weight of N-methyldiethanolamine were added and mixed well.

  Subsequently, about 2 g of the mixed solution obtained by the above method was spin-coated on the surface of a lens substrate (CR39: allyl resin plastic lens; refractive index = 1.50) using a MIKASA spin coater 1H-DX2. The surface-coated lens is irradiated with a metal halide lamp with an output of 120 mW / cm 2 in a nitrogen gas atmosphere for 3 minutes to cure the coating film, and then heat-treat with a 120 ° C. incubator. A photochromic cured thin film was obtained.

  The obtained photochromic cured thin film (film thickness: 30 μm) was used as a sample, and a Xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics was added to this at 20 ° C. ± 1 ° C. via an aeromass filter (manufactured by Corning). The sample was irradiated for 120 seconds with a beam intensity of 365 nm = 2.4 mW / cm 2 and 245 nm = 24 μW / cm 2 on the polymer surface for color development, and the photochromic characteristics of the sample were measured. The photochromic characteristics were evaluated as follows.

  (1) Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development determined by a spectrophotometer (instant multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The harmful maximum absorption wavelength is related to the color tone at the time of color development.

  (2) Initial coloration {ε (0)}: Absorbance in a non-irradiated state at the maximum absorption wavelength. For example, in an optical material such as an eyeglass lens, the lower this value, the better the photochromic property.

  (3) Color density {ε (120) −ε (0)}: difference between the absorbance {ε (120)} after light irradiation for 120 seconds and the above ε (0) at the maximum absorption wavelength. It can be said that the higher this value, the better the photochromic properties.

  (4) Yellow / blue ratio: the ratio of the maximum absorption wavelength in the yellow peripheral region to the maximum absorption wavelength in the blue peripheral region in the color density obtained in (3). It can be said that the closer this value is to 1, the higher the double peak property.

  (5) Color development sensitivity (sec.): Time until the absorbance of the sample at the maximum wavelength reaches saturation due to light irradiation. It can be said that the shorter this time, the better the color development sensitivity.

  (6) Fading half-life [t1 / 2 (min.)]: When light irradiation is stopped after 120 seconds of light irradiation, the absorbance of the sample at the maximum wavelength is {ε (120) −ε (0)}. Time required to drop to 1/2 of The shorter the time, the faster the fading speed and the better the photochromic properties.

  (7) Residual rate (%) = {(A50 / A0) × 100}: In order to evaluate the durability of color development by light irradiation, the following deterioration acceleration test was conducted. That is, the obtained polymer (sample) was accelerated and deteriorated for 50 hours by a Xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. Thereafter, the color density was evaluated before and after the test, the color density before the test (A0) and the color density after the test (A50) were measured, and the value of {(A50 / A0) × 100} was determined as the residual ratio ( %) And used as an index of durability of color development. The higher the remaining rate, the higher the durability of coloring.

  (8) Degree of color change (ΔYI) = YI (50) −YI (0): In order to evaluate the durability of the color tone when not irradiated with light, the samples before and after the above-described deterioration acceleration test The color difference was measured using a color difference meter (SM-4) manufactured by KK). The degree of color change due to deterioration was evaluated by obtaining a difference {ΔYI} obtained by subtracting the color value {YI (0)} before the test from the color value {YI (50)} after the test. . The smaller the ΔYI, the higher the durability of the color tone when no light is irradiated.

  Further, a photochromic polymer was obtained in the same manner as described above except that the compounds obtained in Examples 2 to 20 were used as the chromene compound, and the characteristics thereof were evaluated. The results are summarized in Tables 9-10.

  Further, for comparison, the following formulas (A), (B), (C), (D)

In the same manner, a photochromic polymer was obtained using the compound represented by formula (1), and its characteristics were evaluated. The results are shown in Table 11.

  In the photochromic polymers in Examples 21 to 40 using the chromene compound of the present invention, compared with the photochromic polymers of Comparative Examples 1, 2, 3 and 4, all of color development sensitivity, fading speed and durability of photochromic properties were obtained. Excellent in terms.

This figure is a proton nuclear magnetic resonance spectrum of the chromene compound of Example 1.

Claims (4)

The chromene compound shown by following formula (1).

{Where R is ¹ And R ² Are bonded to each other to form a spiro bond at position 13 of the indeno (2,1-f) naphtho (1,2) pyran structure,

(Wherein the carbon atom represented by 13 refers to the 13th carbon atom of the indeno (2,1-f) naphtho (1,2-b) pyran structure),
R ³ And R ⁴ Each independently represents an unsubstituted aryl group, an aryl group having an alkoxy group, an aryl group having a morpholino group, or a 2,6-dimethylpiperidino group or 2,2,6,6-tetramethylpiperidi An aryl group having
R ⁵ Is a hydrogen atom or an alkoxy group,
R ⁷ Is an alkyl group, a cycloalkyl group, an alkoxy group, an unsubstituted aryl group, an acyl group, a halogen atom, -O (C) OCH ₃ Or a trifluoromethyl group,
R ¹⁴ Is an alkoxy group, a morpholino group, an aryl group having a morpholino group, or a 2,6-dimethylpiperidino group;
R ¹⁵ Is a hydrogen atom, an unsubstituted aryl group, an aryl group having an alkyl group, an aryl group having an alkoxy group, a 2,6-dimethylpiperidino group, or a morpholino group. } A photochromic composition comprising the chromene compound according to claim 1 . A photochromic optical article having, as a constituent member, a polymer molded body in which the chromene compound according to claim 1 is dispersed. An optical article having, as a constituent member, an optical base material in which at least one surface is coated with a polymer film in which the chromene compound according to claim 1 is dispersed.

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