Specific annelated naphthopyran isomeric combinations

Abstract

The present invention relates to combinations of certain photochromic annelated naphthopyran isomers according to formula (I) and formula (II) and their incorporation into thiourethane polymers.

Description

[Technical Field]

[0001] The present invention relates to a combination of special photochromic annelated naphthopyran isomers according to the following formulas (I) and (II) and their incorporation into thiourethane polymers. These phototropic polymers are characterized by very stable and aesthetically pleasing darkening hues. In addition, this method allows for the realization of phototropic products that darken deeply and lighten very quickly. [Background technology]

[0002] Thiourethane polymers are the most widely used materials for plastic eyeglass lenses, with refractive indices above 1.60. The higher the refractive index, the thinner the corrective eyeglass lenses can be. In contrast to acrylate polymers, the dense, three-dimensional polymer matrix of the thiourethane thermosetting polymers used in plastic eyeglass lenses does not allow for long-wavelength UV radiation to open the (colorless) naphthopyran type to form the (colored) merocyanine type (see also Figure 1). This means that no darkening of the thiourethane polymers upon UV exposure can be observed. For this reason, surface coating with photochromic lacquers, especially using spin coating, has been the preferred method for producing phototropic plastic eyeglass lenses with higher refractive indices. However, this process requires complex and expensive technical systems and can only produce a relatively small number of products per unit time, resulting in relatively high production costs.

[0003] US Pat. No. 5,629,499 is the first to describe a method for producing internally colored phototropic thiourethane polymers, which primarily involves the use of special polyether additives. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] European Patent Application No. 3351573 Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is therefore to provide a system which, in particular by incorporation into thiourethane polymers, leads to phototropic polymers characterized by very stable and aesthetically darkened hues, without the need for the special additives required in Patent Document 1. It can also be said here that incorporation can be achieved in particular by internal coloration. [Means for solving the problem]

[0006] This object is solved by the subject matter characterized in the claims.

[0007] In particular, a novel combination of two different specific photochromic annelated naphthopyrans according to the following general formula (I) and general formula (II): [ka] (In formula (I) and formula (II), n represents an integer of 0 to 1, and p represents an integer of 10 to 50. The radicals R1, R2, and R3 are each independently hydrogen, bromine, chlorine, fluorine, a (C1-C6) alkyl radical, a (C3-C7) cycloalkyl radical, a (C1-C6) thioalkyl radical, a (C1-C6) alkoxy radical, a trifluoromethyl radical, a phenyl radical, a 4-methoxyphenyl radical, a phenoxy radical, a 4-methoxyphenoxy radical, a benzyl radical, a 4-methoxybenzyl radical, a benzyloxy radical, a 4-methoxybenzyloxy radical, a biphenyl radical, a biphenyloxy radical, a naphthyl radical, a naphthoxy radical, a diphenylamino radical, a (4-methoxyphenyl)-phenylamino radical, a bis(4-methoxyphenyl)amino radical, a (4-ethoxyphenyl)-phenylamino radical, a bis(4-ethoxyphenyl)amino radical, a 10,10-dimethyl-9,10-dihydroxybenzoyl ... Do a substituent selected from a tetrahydroacridine radical, a phenothiazinyl radical, a phenoxazinyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical, or a 10,11-dihydro-dibenz[b,f]azepinyl radical; or the radicals R1 and R2 together are -V-(CH2) m represents a group of the formula -W-, where V and W are independently selected from a -O-, -S-, -NC6H5-, -CH2-, -C(CH3)2-, -C(C2H5)2- or -C(C6H5)2- group, and m represents an integer from 1 to 3, with the proviso that when this number is 2 or 3, the benzene ring may be annelated to two adjacent CH2 groups, and further, when V or W represent -CH2-, they may together with each adjacent CH2 group represent an annelated benzene ring, the radicals R4 and R5 each independently represent a substituent selected from hydrogen, bromine, chlorine, fluorine, a (C1-C6) alkyl radical, a (C3-C7) cycloalkyl radical, a (C1-C6) thioalkyl radical, a (C1-C6) alkoxy radical, a trifluoromethyl radical, a phenyl radical, a phenoxy radical, a benzyl radical or a benzyloxy radical, or radicals R4 and R5 together are -X-(CH2) q represents a group of the formula -Y-, where X and Y are independently selected from the group -O-, -S-, -NC6H5-, -CH2-, -C(CH3)2-, -C(C2H5)2- or -C(C6H5)2-, and q represents an integer from 1 to 3, with the proviso that when this number is 2 or 3, the benzene ring may also be annelated to two adjacent CH2 groups, and further, when X or Y represent -CH2-, they may also, together with each adjacent CH2 group, represent an annelated benzene ring; the radicals R6, R7 and R8 each independently represent a substituent selected from hydrogen, a (C1-C6) alkyl radical, a (C3-C7) cycloalkyl radical, a (C1-C6) alkoxy radical, a phenyl radical or a benzyl radical; or the radicals R6 and R7 together, or R7 and R8 together, form an annelated benzene ring, which may be unsubstituted, monosubstituted or disubstituted, in which the substituents may be selected from hydrogen, a (C1-C6) alkyl radical, a (C1-C6) alkoxy radical, a phenyl radical or a benzyl radical, or the radicals R6 and R7 together, or R7 and R8 together, form an anelated naphthalene ring system, an anelated benzofuran ring system, an anelated benzothiophene ring system, an anelated 3,3-dimethylindene ring system, or an anelated 2H-chromene ring system; Radical R9, R 10 and R 11 each independently represents a substituent selected from a (C1-C6) alkyl radical or a phenyl radical).

[0008] In a preferred embodiment, in formula (I) and formula (II), the radicals R1, R2 and R3 are each independently hydrogen, bromine, chlorine, fluorine, and a (C1-C6) alkyl radical, a (C3-C7)-cycloalkyl radical, a (C1-C6)-thioalkyl radical, a (C1-C6)-alkoxy radical, a trifluoromethyl radical, a phenyl radical, a 4-methoxyphenyl radical, a phenoxy radical, a 4-methoxyphenoxy radical, a benzyl radical, a 4-methoxybenzyl radical, a benzyloxy radical, a 4-methoxybenzyloxy radical, a biphenyl radical, a biphenyloxy radical, a naphthyl radical, a naphthoxy radical, a diphenylamino radical, a (4-methoxyphenyl)phenylamino radical, a bis(4-methoxyphenyl)amino radical, a (4-ethoxyphenyl)phenylamino radical, a bis(4-ethoxyphenyl)amino radical, a 10,10-dimethyl-9,10-dihydroxybenzoyl ... Do and represents a substituent selected from a dihydroacridine radical, a phenothiazinyl radical, a phenoxazinyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical, or a 10,11-dihydro-dibenz[b,f]azepinyl radical.

[0009] In yet another preferred embodiment, in formula (I) and formula (II), the radicals R4 and R5 each independently represent a substituent selected from hydrogen, bromine, chlorine, fluorine, a (C1-C6) alkyl radical, a (C3-C7) cycloalkyl radical, a (C1-C6) thioalkyl radical, a (C1-C6) alkoxy radical, a trifluoromethyl radical, a phenyl radical, a phenoxy radical, a benzyl radical or a benzyloxy radical.

[0010] In yet another preferred embodiment, in formula (I) and formula (II), the radicals R6, R7 and R8 each independently represent a substituent selected from hydrogen, a (C1-C6) alkyl radical, a (C3-C7)-cycloalkyl radical, a (C1-C6)-alkoxy radical, a phenyl radical or a benzyl radical.

[0011] Preferably, in formula (I) and formula (II), the radicals R, R 10 and R 11 each independently represents a substituent selected from a (C1-C6) alkyl radical or a phenyl radical. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 shows a synthetic scheme for producing compounds used in accordance with the present invention and methods for exciting them. [Figure 2] FIG. 1 is an illustration of the darkening hue of compounds used in accordance with the present invention. [Figure 3] FIG. 1 shows a comparison of the phototropic performance of compounds used according to the invention with reference compounds that are very similar in structure. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention is based on the surprising finding that a novel combination of a photochromic anelated 2H-naphthopyran according to formula (I) and a new photochromic anelated 3H-naphthopyran according to formula (II) can achieve excellent photochromic properties when incorporated into a thiourethane polymer. The compounds of formula (II) according to the present invention are geometric isomers of the 2H-naphthopyran according to formula (I). The substituents R6 to R 11 The two rings having the formula (I) are annelated to naphthopyran units. The phototropic thiourethane polymers produced based on this combination are characterized by very stable and aesthetically darkening hues. In addition, phototropic products that darken deeply and lighten very quickly can be realized. In addition, the compounds combined according to the present invention have very good durability.

[0014] In contrast to Patent Document 1, which requires the use of special polyether additives to produce internally colored phototropic thiourethane polymers, the present invention solves the problem of incorporation into thiourethane polymers by using this novel combination of two different photochromic annelated naphthopyran isomers specially tailored according to Formulas (I) and (II), thereby achieving highly stable and aesthetically pleasing darkening hues. The two naphthopyran isomers have different darkening hues and complement each other when combined, producing, for example, aesthetically pleasing gray or brown shades. Here, the 3H-naphthopyran isomer of Formula (II), with its yellow-orange to red hue, is a very important component for achieving aesthetically pleasing brown shades, but is equally important as a counterpart to the predominantly blue (blue-purple to blue-green) darkening 2H-naphthopyran isomer of Formula (I) for achieving aesthetically pleasing gray shades (see Figure 2). This combination of isomers is also particularly advantageous because it is relatively easy to match the lightening rates of each other by selecting appropriate substituents, which is extremely important when used as a mixture such that the darkening hue remains constant throughout the excitation and lightening cycle.

[0015] Compounds according to formula (I) having oxygen-containing substituents R4 and R5 were first proposed in EP 3807258 for use in all kinds of plastics.

[0016] As previously mentioned, in contrast to conventional photochromic dyes that do not darken when incorporated into dense thiourethane thermosetting polymers upon exposure to UV light, the naphthopyran isomers of the present invention possess excellent depth of darkening due to the long poly(propyleneoxy) chains (p≧10 in Formulas (I) and (II)), which are optionally covalently bonded to the photochromic dye via succinate ester bridges. Clearly, the presence of the long poly(propyleneoxy) chains alters the immediate dye environment, either sterically (changes the surrounding network density) or electronically (changes the surrounding polarity), in such a way that the formation of the excited (colored) form by ring-opening of the unexcited (colorless) form can readily occur under long-wavelength UV light. The long poly(propyleneoxy) chains are located near the photosensitive center of the photochromic dye, and therefore near the bond cleavage site upon excitation or the bond restoration site upon lightening (see Figure 1), thus providing efficient shielding from the thiourethane polymer. A key aspect of the present invention is the unexpected finding that the polarity of the long poly(propyleneoxy) chains is absolutely crucial for good photochromic properties: Even with roughly the same chain length, more polar poly(ethyleneoxy) chains and more non-polar paraffin chains both exhibit significantly poorer phototropic performance (see Figure 3) or do not darken at all upon UV exposure.

[0017] The compounds according to formula (I) and formula (II) used in accordance with the present invention have three non-hydrogen substituents R to R on two non-aromatic carbon atoms. 11 The presence of R has very good durability. The corresponding compounds with less than three non-hydrogen substituents are easily oxidized at this site to form colored oxidation products, resulting in significantly poorer durability (see Table 4 below). In fact, three substituents are optimal here. 11 The four non-hydrogen substituents in the compounds according to formula (I) and formula (II) used according to the present invention are unfavorable for steric reasons, since further substituents on the carbon atom according to strongly prevent the ring opening of the (colorless) naphthopyran form by long wavelength UV radiation to form the excited (colored) form, and therefore only weak darkening can be observed upon UV exposure.

[0018] However, in contrast to Patent Document 1, the scope of the present invention is not limited to the provision of uniformly internally colored thiourethane polymers using the combination according to the invention, but also includes, in particular, two-component systems in which a 0.1 mm to 1 mm thin phototropic thiourethane functional layer is polymerized onto a polymer substrate (sprue method). In addition to attractive production costs, this method has the great advantage that, in contrast to uniformly internally colored products, excellent UV protection for spectacle wearers can be easily achieved by incorporating any amount of UV absorber into the polymer substrate. This is not possible with uniformly internally colored phototropic thiourethane polymers, because the incorporated UV absorber removes the long-wavelength UV light required for darkening from the photochromic dye. In this respect, the present invention also includes sandwich systems in which a 0.1 mm to 1 mm thin phototropic thiourethane functional layer is located between two polymer bodies.

[0019] Furthermore, the scope of the present invention is not limited to the presence of two naphthopyran isomers in the thiourethane polymer. In addition to the combination according to the present invention, other photochromic dyes (different from those of formula (I) and formula (II)), permanent dyes (for pre-colored products), and additives can be used to improve product properties.

[0020] The compounds used according to the present invention are synthesized from the corresponding annelated naphthopyrans having a 4-hydroxy substituent on the benzene ring, which is attached to the carbon atom next to the pyran oxygen. According to the synthetic scheme in Figure 1, the compounds used or combined according to the present invention are then produced. This method is the same for compounds according to formula (I) and formula (II). In this respect, Figure 1 shows only the pyran ring with two aryl substituents.

[0021] When n represents the number 0, commercially available polypropylene glycol monobutyl ether (p≧10 in formulas (I) and (II)) is first activated as the tosylate (Ts). The chain length has a Gaussian distribution, i.e., there is a mixture of chain lengths distributed around a maximum. This is then covalently attached to the annelated naphthopyran using standard Williamson ether synthesis.

[0022] When n represents the number 1, the reaction is first carried out with succinic anhydride. The free carboxyl group of the succinic acid unit is then activated with carbonyldiimidazole (CDI), which allows a very mild ester synthesis with polypropylene glycol monobutyl ether.

[0023] The excitation mechanism (bond cleavage by long-wavelength UV light, creating the colored form) is also shown in Figure 1. Lightening back to the unexcited naphthopyran form is purely thermal.

[0024] To measure the spectroscopic and photochromic properties, the compounds according to formula (I) and formula (II) used according to the present invention are incorporated into optical thiourethane polymers, i.e., those suitable for commercial plastic eyeglass lenses. For this purpose, the photochromic dye is dissolved in the liquid isocyanate component of the thiourethane polymer, and the thiol component and a polyaddition initiator are added, followed by thermal polymerization using a temperature program. The phototropic performance (darkening and lightening behavior) and darkening hue of the test specimens (2 mm thick flat glass) thus prepared are then determined using a standard measurement method at 23 ° C according to DIN EN ISO 8980-3.

[0025] FIG. 2 shows the darkening hue of the compounds used in accordance with the present invention. * / b *The color coordinates are clearly shown. The molecular structures of the compounds shown in Figure 2 are listed in Tables 1 and 2. Compounds 1, 2, and 3 used in accordance with the present invention are described by formula (III), and compounds 4, 5, and 6 used in accordance with the present invention are described by formula (IV). Formula (III) represents a subgroup of formula (I), and formula (IV) represents a subgroup of formula (II).

[0026] a * / b * Negative a in the color coordinate system * The value represents the green darkening hue, and a positive a * The value represents the red hue. * The value represents the blue hue, and positive b * The value represents the yellow hue. Then, the resulting mixed colors, for example purple or orange, can be found in the area between the respective axes (i.e., between the blue and red axes, or between the yellow and red axes). The further the measurement point is from the coordinate origin, which by definition represents the absence of color (i.e., a gray hue), the more intense the color. Measurement points closer to the coordinate origin represent dull hues such as bluish gray or greenish gray. A special feature are brown hues, which are a mixture of various basic colors. Aesthetic browns (e.g., maroon) are a * / b * It has been empirically shown that this can be seen in the area of ​​region B of the color coordinate system.

[0027] The darkening hues of the compounds according to formula (III) used in accordance with the present invention lie close to the blue axis. The hues range from blue-green (compound 1) to blue (compound 2) to blue-violet (compound 3). Due to the complexity of their molecular structures, it was nearly impossible to predict the exact color in advance. In contrast, the darkening hues of the compounds according to formula (IV) used in accordance with the present invention are found between the yellow and red axes, ranging from yellow-orange (compound 4) to orange (compound 5) to red (compound 6). This gradient is as expected. The stronger the donor R2 (i.e., the more electron-rich it is), the bathochromic shift of the longest wavelength absorption maximum of the excited form occurs, from approximately 450 nm for compound 4 to approximately 470 nm for compound 5 and approximately 530 nm for compound 6.

[0028] As mentioned at the beginning, the subject of the present invention is a combination, mixture, or system of a dye according to formula (III) or formula (I) with a dye according to formula (IV) or formula (II), which, when properly matched with each other, produces an aesthetically pleasing darkening hue. For example, to achieve an aesthetically pleasing gray hue, the combination of compound 1 and compound 5 provided by the present invention can be incorporated into a polymer, which, together with an appropriate mixing ratio, produces a hue close to the coordinate origin in region A (see Figure 2). This is also possible when compound 2 is combined with compound 4. In these combinations, it is always important that the lightening rates of the partners match; otherwise, an undesirable color shift during lightening would occur (e.g., from gray to brown if the blue partner lightens faster than orange). Therefore, the lightening rates of the aforementioned combination pairs (1 + 5 or 2 + 4) are adjusted to each other (see Tables 1 and 2). This adjustment is within the technical skill of those skilled in the art.

[0029] In some cases, it may be advantageous to use combination pair 3+6 as a blend with one of the other two pairs to achieve the exact darkening hue desired. For example, an aesthetic brown darkening hue can be easily achieved, whereas mixing combination pair 3+6 alone does not produce an aesthetic neutral hue (the mixture of blue-purple compound 3 and red compound 6 is purple).

[0030] Tables 1 and 2 below show the molecular structures of compounds according to formula (III) and formula (IV), as shown in Figure 2, and their lightening rates after 2 minutes at 23°C in thiourethane polymer.

[0031] Compound 2 according to the present invention in Table 1 has an indeno ring formation as the substituents R4 and R5. The aliphatic carbon atom (having two methyl substituents) of the 3,3-dimethylindene subunit is bonded via R5, and the benzene ring is bonded via R4. Compound 3 according to the present invention in Table 1 has a 1,2-ethylenedioxy group as the substituents R4 and R5. [ka]

[0032] [Table 1] [ka]

[0033] [Table 2]

[0034] The lightening behavior from a fully darkened state of the compounds used according to the invention is also listed in Tables 1 and 2.

[0035] The percentage relative increase in transmittance after 2 minutes of lightening is defined as a measure of the lightening behavior normalized to the overall photochromic stroke of full lightening. This quantity of practical relevance for describing photochromic kinetics is the relative lightening R 2min It is called:

number

[0036] The percentage values ​​specified are calculated from the transmittance data of phototropic kinetic measurements at 23°C according to DIN EN ISO 8980-3. In a first step, the difference in transmittance between the state after 2 minutes of light exposure and the previously achieved darkened state is determined. In a second step, the difference in transmittance between the lightened (unexcited) state and the darkened state is determined. The ratio of the difference between the two transmittance values ​​is multiplied by 100 to obtain the percentage value. 50%R2min A value of 20%R means that after 2 minutes of lightening, half of the photochromic stroke relative to the fully lightened state has already been completed. The higher the percentage value, the faster the lightening. Commercially available phototropic plastic eyeglass lenses achieve a 20%R after 2 minutes of lightening. 2min ~35%R 2min , i.e., thanks to the combination according to the invention, it is possible to achieve phototropic high refractive index plastic spectacle lenses with hitherto unrealizable lightening speeds in combination with excellent darkening depths. Excellent darkening depths are important because such fast lightening speeds have hitherto only been effective in conjunction with significantly weaker darkening.

[0037] Figure 3 shows a comparison of the phototropic performance of compounds used in accordance with the present invention with reference compounds that are very similar in structure. The molecular structures of the compounds according to formula (V) shown in Figure 3 are listed below in Table 3. The comparison very clearly shows the improvement achieved by the present invention. [ka]

[0038] [Table 3]

[0039] Evaluation of phototropic performance includes the depth of darkening upon standard exposure to long wavelength UV light and the speed of lightening at 23° C. The lower the transmittance (or higher the absorption) of a photochromic dye after UV exposure and the faster the dye returns to its initial unexcited state, the better.

[0040] Compounds 1 and 7 used in accordance with the present invention differ only in the length of the poly(propyleneoxy) chain. According to the present invention, both dyes exhibit excellent darkening and lightening behavior. Shorter chains (p≈16) remain effective. However, at poly(propyleneoxy) chain lengths less than about 10 (p<10), a significant decrease in phototropic performance can be observed. It is therefore evident that it is no longer possible to effectively shield the dye from the thiourethane environment.

[0041] It is interesting to compare the properties of Reference Compound 1 and Reference Compound 2. Reference Compound 1 does not have a long chain attached, whereas Reference Compound 2 has a chain of substantially the same length as Compound 1 used according to the invention, but with a more polar ethyleneoxy unit (R 12 Both reference compounds have very poor phototropic performance, which is due to the dyes with longer poly(propyleneoxy) chains (R 12 It is clear that only the dyes (=Me; Me is a common chemical abbreviation for the methyl group) are suitable for incorporation into the thiourethane polymers according to the present invention. However, there are limitations, as shown by Reference Compound 3. Reference Compound 3 has an N-morpholinyl substituent at this position, in contrast to Compound 1 used according to the present invention, which has a diphenylamino substituent at the radical R2 in formula (V). The darkening of Reference Compound 3 is significantly reduced because a significant portion of this photochromic dye decomposes during polymerization. This is due to the reactive basic morpholine unit, which reacts with the isocyanate component of the thiourethane polymer during polymerization. On the other hand, the non-basic diphenylamino substituents of Compounds 1 and 7 used according to the present invention are inactive in this respect. Therefore, these dyes can be easily incorporated into thiourethane polymers. Generally, only dyes with non-basic substituents, such as alkyl, aryl, alkyloxy, aryloxy, or diarylamino substituents, are suitable for this purpose; dyes with dialkylamino or arylalkylamino substituents are not.

[0042] Table 4 below shows an example of a comparison of the radiation resistance of compound 5 used according to the invention with a structurally very similar reference compound according to formula (VI).

[0043] Residual photochromic stroke P after weathering test * is defined as a measure of radiation resistance:

number

[0044] Table 4 shows a comparison of the durability of Compound 5 used according to the present invention with Reference Compound 4 and Reference Compound 5. [ka]

[0045] [Table 4]

[0046] Residual photochromic stroke P after weathering test * The photochromic stroke of the undamaged specimen was measured by the ratio of the absorbance before and after the durability test, and is expressed as a percentage of the photochromic stroke of the undamaged specimen. The specimen was exposed to an irradiance of 700 W / m in a commercially available weathering test device. 2 The lamps are exposed to concentrated radiation for 50 hours using a xenon arc lamp. Measurements are carried out at 23°C in accordance with the DIN EN ISO 8980-3 standard. The higher the percentage value specified, the lower the performance loss.

[0047] Compound 5 provided in accordance with the present invention has three methyl substituents R, R on two non-aromatic carbon atoms. 10 and R 11 The presence of α- and β-hydroxybenzoates results in very good radiation resistance. Similar compounds with more hydrogen atoms at these two positions, such as Reference Compound 4 and Reference Compound 5, are easily oxidized at these positions to form colored oxidation products, resulting in significantly poorer radiation resistance.

[0048] As mentioned above, the scope of the present invention is not limited to the incorporation of the photochromic annelated naphthopyran isomer combinations according to the present invention into thiourethane polymers. In addition, other photochromic dyes can be used. In addition, permanent dyes (for pre-colored products) and additives can be used to improve product properties.

[0049] The scope of the present invention is not limited to uniformly internally colored thiourethane polymers, but also primarily includes two-component systems in which a 0.1 mm to 1 mm thin phototropic thiourethane functional layer is polymerized onto a polymer substrate (sprue method). The present invention also includes sandwich systems in which a 0.1 mm to 1 mm thin phototropic thiourethane functional layer is located between two polymer bodies.

[0050] A further subject of the present invention relates to the use of the annelated naphthopyran isomer combinations according to the invention for incorporation into thiourethane polymers, in particular for ophthalmic use in lenses and glasses for all types of spectacles, for example corrective spectacles, driving spectacles, ski goggles, sunglasses, motorcycle goggles, for visors for protective helmets and the like, and for sun protection applications in the vehicle and construction sectors in the form of windows, protective screens, covers, roofs, etc.

[0051] Another subject of the present invention is novel photochromic anelated naphthopyrans according to the following general formula (II): [ka] (In the formula, n represents an integer of 0 to 1, and p represents an integer of 10 to 50. The radicals R1, R2, and R3 are each independently hydrogen, bromine, chlorine, fluorine, a (C1-C6) alkyl radical, a (C3-C7) cycloalkyl radical, a (C1-C6) thioalkyl radical, a (C1-C6) alkoxy radical, a trifluoromethyl radical, a phenyl radical, a 4-methoxyphenyl radical, a phenoxy radical, a 4-methoxyphenoxy radical, a benzyl radical, a 4-methoxybenzyl radical, a benzyloxy radical, a 4-methoxybenzyloxy radical, a biphenyl radical, a biphenyloxy radical, a naphthyl radical, a naphthoxy radical, a diphenylamino radical, a (4-methoxyphenyl)-phenylamino radical, a bis(4-methoxyphenyl)amino radical, a (4-ethoxyphenyl)-phenylamino radical, a bis(4-ethoxyphenyl)amino radical, a 10,10-dimethyl-9,10-dihydroxybenzoyl ... Do or the radicals R1 and R2 together represent a substituent selected from the group consisting of a tetrahydroacridine radical, a phenothiazinyl radical, a phenoxazinyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical, or a 10,11-dihydro-dibenz[b,f]azepinyl radical; or m represents a group of the formula -W-, where V and W are independently selected from a -O-, -S-, -NC6H5-, -CH2-, -C(CH3)2-, -C(C2H5)2- or -C(C6H5)2- group, and m represents an integer from 1 to 3, with the proviso that when this number is 2 or 3, the benzene ring may be annelated to two adjacent CH2 groups, and further, when V or W represent -CH2-, they may together with each adjacent CH2 group represent an annelated benzene ring, the radicals R4 and R5 each independently represent a substituent selected from hydrogen, fluorine, a (C1-C6) alkyl radical, a (C1-C6) alkoxy radical, a phenyl radical, a phenoxy radical, a benzyl radical or a benzyloxy radical, the radicals R6, R7 and R8 each independently represent a substituent selected from hydrogen, a (C1-C6) alkyl radical, a (C3-C7) cycloalkyl radical, a (C1-C6) alkoxy radical, a phenyl radical or a benzyl radical; or the radicals R6 and R7 together, or R7 and R8 together, form an annelated benzene ring, which may be unsubstituted, monosubstituted or disubstituted, in which the substituents may be selected from hydrogen, a (C1-C6) alkyl radical, a (C1-C6) alkoxy radical, a phenyl radical or a benzyl radical, or the radicals R6 and R7 together, or R7 and R8 together, form an anelated naphthalene ring system, an anelated benzofuran ring system, an anelated benzothiophene ring system, an anelated 3,3-dimethylindene ring system, or an anelated 2H-chromene ring system; Radical R9, R 10 and R 11 each independently represents a substituent selected from a (C1-C6) alkyl radical or a phenyl radical).

[0052] As far as the preferred embodiments of these novel photochromic annelated naphthopyrans according to general formula (II) are concerned, the above considerations apply.

Claims

1. A combination of two different photochromic annelated naphthopyrans according to the following general formula (I) and general formula (II): 【Chemistry 1】 (In formula (I) and formula (II), n represents an integer of 0 to 1, and p represents an integer of 10 to 50. Radical R １ , R ２ and R ３ are each independently hydrogen, bromine, chlorine, fluorine, (C １ ~C ６ ) alkyl radical, (C ３ ~C ７ ) cycloalkyl radical, (C １ ~C ６ )-thioalkyl radical, (C １ ~C ６ a substituent selected from a 4-methoxyphenyl radical, a 4-methoxyphenoxy radical, a 4-alkoxy radical, a trifluoromethyl radical, a phenyl radical, a 4-methoxyphenyl radical, a phenoxy radical, a 4-methoxyphenoxy radical, a benzyl radical, a 4-methoxybenzyl radical, a benzyloxy radical, a 4-methoxybenzyloxy radical, a biphenyl radical, a biphenyloxy radical, a naphthyl radical, a naphthoxy radical, a diphenylamino radical, a (4-methoxyphenyl)-phenylamino radical, a bis(4-methoxyphenyl)amino radical, a (4-ethoxyphenyl)-phenylamino radical, a bis(4-ethoxyphenyl)amino radical, a 10,10-dimethyl-9,10-dihydroacridine radical, a phenothiazinyl radical, a phenoxazinyl radical, a phenazinyl radical, a carbazolyl radical, a 1,2,3,4-tetrahydrocarbazolyl radical, or a 10,11-dihydro-di-benz[b,f]azepinyl radical, or the radical R １ and R ２ Together, they are -V-(CH ２ ) ｍ -W- (wherein V and W are independently -O-, -S-, -NC ６ H ５ -, -CH ２ -, -C(CH ３ ) ２ -, -C(C ２ H ５ ) ２ - or - C (C ６ H ５ ) ２ - groups, and m represents an integer of 1 to 3, provided that when this number is 2 or 3, the benzene ring is ２ V or W may be annelated to a group, and they may also be -CH ２ When - represents, each adjacent CH ２ which together with the group may represent an annelated benzene ring, Radical R ４ and R ５ are each independently hydrogen, bromine, chlorine, fluorine, (C １ ~C ６ ) alkyl radical, (C ３ ~C ７ ) cycloalkyl radical, (C １ ~C ６ ) thioalkyl radical, (C １ ~C ６ ) represents a substituent selected from an alkoxy radical, a trifluoromethyl radical, a phenyl radical, a phenoxy radical, a benzyl radical or a benzyloxy radical, or the radical R ４ and R ５ Together, they are -X-(CH ２ ) ｑ -Y- (wherein X and Y are independently -O-, -S-, -NC ６ H ５ -, -CH ２ -, -C(CH ３ ) ２ -, -C(C ２ H ５ ) ２ - or - C (C ６ H ５ ) ２ - groups, and q represents an integer of 1 to 3, provided that when this number is 2 or 3, the benzene ring is ２ Further, X or Y may be annelated to a group, and they may be -CH ２ When - represents, each adjacent CH ２ which together with the group may represent an annelated benzene ring, Radical R ６ , R ７ and R ８ are each independently hydrogen, (C １ ~C ６ ) alkyl radical, (C ３ ~C ７ ) cycloalkyl radical, (C １ ~C ６ ) represents a substituent selected from an alkoxy radical, a phenyl radical or a benzyl radical; or the radical R ６ and R ７ together or R ７ and R ８ together form an annelated benzene ring which may be unsubstituted, monosubstituted or disubstituted, where the substituents are hydrogen, (C １ ~C ６ ) alkyl radical, (C １ ~C ６ ) can be selected from alkoxy radicals, phenyl radicals or benzyl radicals; or the radical R ６ and R ７ together or R ７ and R ８ together form an anelated naphthalene ring system, an anelated benzofuran ring system, an anelated benzothiophene ring system, an anelated 3,3-dimethylindene ring system, or an anelated 2H-chromene ring system; Radical R ９ , R １０ and R １１ are each independently １ ~C ６ ) represents a substituent selected from an alkyl radical or a phenyl radical).

2. In the formula (I) and formula (II), The radical R １ , R ２ and R ３ are each independently hydrogen, bromine, chlorine, fluorine, (C １ ~C ６ ) alkyl radical, (C ３ ~C ７ ) cycloalkyl radical, (C １ ~C ６ )-thioalkyl radical, (C １ ~C ６ )-alkoxy radical, trifluoromethyl radical, phenyl radical, 4-methoxyphenyl radical, phenoxy radical, 4-methoxyphenoxy radical, benzyl radical, 4-methoxybenzyl radical, benzyloxy radical, 4-methoxybenzyloxy radical, biphenyl radical, biphenyloxy radical, naphthyl radical, naphthoxy radical, diphenylamino radical, (4-methoxyphenyl)-phenylamino radical, bis(4-methoxyphenyl)amino radical, (4-ethoxyphenyl)-phenylamino radical, bis(4-ethoxyphenyl)amino radical, 10,10-dimethyl-9,10-dihydroacridine radical, phenothiazinyl radical, phenoxazinyl radical, phenazinyl radical, carbazolyl radical, 1,2,3,4-tetrahydrocarbazolyl radical, or 10,11-dihydro-di-benz[b,f]azepinyl radical, The radical R ４ and R ５ are each independently hydrogen, bromine, chlorine, fluorine, (C １ ~C ６ ) alkyl radical, (C ３ ~C ７ ) cycloalkyl radical, (C １ ~C ６ ) thioalkyl radical, (C １ ~C ６ ) represents a substituent selected from an alkoxy radical, a trifluoromethyl radical, a phenyl radical, a phenoxy radical, a benzyl radical or a benzyloxy radical, The radical R ６ , R ７ and R ８ are each independently hydrogen, (C １ ~C ６ ) alkyl radical, (C ３ ~C ７ ) cycloalkyl radical, (C １ ~C ６ ) represents a substituent selected from an alkoxy radical, a phenyl radical or a benzyl radical, and The radical R ９ , R １０ and R １１ are each independently １ ~C ６ ) represents a substituent selected from an alkyl radical or a phenyl radical.

3. 3. The combination of claim 1 or 2, further comprising one or more additional components selected from photochromic dyes, permanent dyes or additives other than those of formula (I) and formula (II).

4. In the formula (I) and the formula (II), the radical R ９ , R １０ and R １１ are each independently １ ~C ６ 3. The combination according to claim 1 or 2, wherein R represents a substituent selected from the group consisting of: ) alkyl radicals.

5. 3. Use of a combination according to claim 1 or 2 for incorporation into a thiourethane polymer.

6. Use of the combination according to claim 5 for ophthalmic applications in spectacles, for visors or for sun protection applications in the vehicle or construction sector.

7. Use of a combination as claimed in claim 5 for ophthalmic applications in lenses or glasses for corrective spectacles, driving spectacles, ski goggles, sunglasses or motorcycle goggles, for visors in protective helmets or for sun protection applications in the form of windows, protective screens, covers or roofs in the vehicle or construction sector.

8. A phototropic thiourethane polymer comprising the combination of claim 1 or 2.

9. 9. A phototropic product based on a thiourethane polymer according to claim 8, which is a two-component system in which a 0.1 mm to 1 mm thin phototropic thiourethane functional layer based on a thiourethane polymer is polymerized on a polymer substrate, or a sandwich system in which a 0.1 mm to 1 mm thin phototropic thiourethane functional layer based on a thiourethane polymer is disposed between two polymer bodies.

10. Photochromic anelated naphthopyrans according to the following general formula (II): 【Chemistry 2】 (In the formula, n represents an integer of 0 to 1, and p represents an integer of 10 to 50. Radical R １ , R ２ and R ３ are each independently hydrogen, bromine, chlorine, fluorine, (C １ ~C ６ ) alkyl radical, (C ３ ~C ７ ) cycloalkyl radical, (C １ ~C ６ )-thioalkyl radical, (C １ ~C ６ or a substituent selected from the radical R １ and R ２ Together, they are -V-(CH ２ ) ｍ -W- (wherein V and W are independently -O-, -S-, -NC ６ H ５ -, -CH ２ -, -C(CH ３ ) ２ -, -C(C ２ H ５ ) ２ - or - C (C ６ H ５ ) ２ - groups, and m represents an integer of 1 to 3, provided that when this number is 2 or 3, the benzene ring is ２ V or W may be annelated to a group, and they may also be -CH ２ When - represents, each adjacent CH ２ and the radical R ４ and R ５ are each independently hydrogen, fluorine, (C １ ~C ６ ) alkyl radical, (C １ ~C ６ ) represents a substituent selected from an alkoxy radical, a phenyl radical, a phenoxy radical, a benzyl radical or a benzyloxy radical, Radical R ６ , R ７ and R ８ are each independently hydrogen, (C １ ~C ６ ) alkyl radical, (C ３ ~C ７ ) cycloalkyl radical, (C １ ~C ６ ) represents a substituent selected from an alkoxy radical, a phenyl radical, or a benzyl radical, or the radical R ６ and R ７ together or R ７ and R ８ together form an annelated benzene ring which may be unsubstituted, monosubstituted or disubstituted, where the substituents are hydrogen, (C １ ~C ６ ) alkyl radical, (C １ ~C ６ ) can be selected from alkoxy radicals, phenyl radicals or benzyl radicals; or the radical R ６ and R ７ together or R ７ and R ８ together form an anelated naphthalene ring system, an anelated benzofuran ring system, an anelated benzothiophene ring system, an anelated 3,3-dimethylindene ring system, or an anelated 2H-chromene ring system; Radical R ９ , R １０ and R １１ are each independently １ ~C ６ ) represents a substituent selected from an alkyl radical or a phenyl radical).

Images