Combinations of specific annelated naphthopyran isomers

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 formula (I) and formula (II) and their incorporation into thiourethane polymers. These phototropic polymers are characterized by very stable and aesthetic darkening hues. In addition, in this way phototropic products that darken deeply and lighten very quickly can be realized. [Background technology]

[0002] Thiourethane polymers are the most widespread materials for plastic spectacle lenses with a high refractive index of 1.60 or more. The higher the refractive index, the thinner the corrective spectacle lenses can be. In contrast to acrylate polymers, it is not yet possible to incorporate photochromic dyes into thiourethane polymers, since the dense three-dimensional polymer matrix of thiourethane thermosetting polymers used for plastic spectacle lenses does not have room for ring-opening of the (colorless) naphthopyran type by long-wavelength UV radiation 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, until now, surface coating with photochromic lacquers, especially using spin coating, has been the preferred method for producing phototropic plastic spectacle lenses with higher refractive index. However, this process has the disadvantages of requiring complex and expensive technological systems and of relatively high production costs, since only relatively few products can be produced per unit time.

[0003] US Pat. No. 5,399,433 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, results in phototropic polymers characterised by very stable and aesthetically pleasing darkening hues, without the need for special additives as is essential in WO 2005 / 023336. It can also be said here that incorporation can be achieved in particular by internal colouration. [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 each independently represent 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 naphthyloxy radical, a phenyl ... a substituent selected from the group consisting of a silyl 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 radicals R1 and R2 together are -V-(CH2) m represents a -W- group, 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 also be annelated to two adjacent CH2 groups, and further, V or W, when they represent -CH2-, may also 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, X or Y, when they represent -CH2-, 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, mono- 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 annelated naphthalene ring system, an annelated benzofuran ring system, an annelated benzothiophene ring system, an annelated 3,3-dimethylindene ring system or an annelated 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 ... and represents a substituent selected from the group consisting of dicarbazone, 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, and 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 description of the drawings]

[0012] [Figure 1] FIG. 1 shows synthetic schemes for producing compounds used in accordance with the present invention and methods for exciting them. [Diagram 2] FIG. 2 is an illustration of the darkening hues of the compounds used in accordance with the present invention. [Diagram 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 PREFERRED EMBODIMENTS

[0013] The present invention is based on the surprising finding that a novel combination of a photochromic annelated 2H-naphthopyran according to formula (I) and a new photochromic annelated 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 are annelated to naphthopyran units. The phototropic thiourethane polymers produced based on this combination are characterized by very stable and aesthetic 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 US Pat. No. 5,999,363, 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 formula (I) and formula (II), which allows the realization of very stable and aesthetic darkening hues. The two naphthopyran isomers have different darkening hues and complement each other when combined, producing, for example, aesthetic gray or brown shades. Here, the 3H-naphthopyran isomer of formula (II), which has a yellow-orange to red hue, is a very important component for realizing aesthetic brown shades, but is equally important as a counterpart to the mainly blue (blue-purple to blue-green) darkening 2H-naphthopyran isomer of formula (I) for realizing aesthetic gray shades (see FIG. 2). This combination of isomers is also particularly advantageous because it is relatively easy to match the lightening rates with one another 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 plastics of all kinds.

[0016] As already mentioned, in contrast to conventional photochromic dyes that do not darken when introduced into dense thiourethane thermosetting polymers when exposed to UV light, the naphthopyran isomers according to the present invention have excellent depth of darkening due to the long poly(propyleneoxy) chains (p≧10 in formula (I) and formula (II)) attached thereto, which are optionally covalently bonded to the photochromic dye via succinate ester bridges. Apparently, the presence of the long poly(propyleneoxy) chains changes the immediate dye environment, either sterically (change in the surrounding network density) or electronically (change in the surrounding polarity), in such a way that the formation of the excited (colored) form by ring opening of the non-excited (colorless) form can easily occur by long-wavelength UV light. The long poly(propyleneoxy) chains are located close to the photosensitive center of the photochromic dye, and therefore close to the bond cleavage site upon excitation or bond recovery site upon lightening (see FIG. 1), and therefore can provide efficient shielding from the thiourethane polymer. An important 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: with nearly identical chain lengths, more polar poly(ethyleneoxy) chains and more non-polar paraffinic chains both exhibit significantly poorer phototropic performance (see FIG. 3) or do not darken at all upon UV exposure.

[0017] The compounds according to formula (I) and (II) used according to the invention have three non-hydrogen substituents R9 to R 11 The corresponding compounds with less than three non-hydrogen substituents have significantly worse durability because they are easily oxidized at this site to form colored oxidation products (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 invention are disadvantageous 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 a weak darkening can be observed upon UV exposure.

[0018] However, in contrast to WO 02 / 06363, the scope of the present invention is not limited to the provision of homogeneously 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 on a polymer substrate (sprue method). In addition to attractive manufacturing costs, this method has the great advantage that, in contrast to homogeneously internally colored products, excellent UV protection for spectacle wearers can be easily achieved by introducing any amount of UV absorber into the polymer substrate. This is not possible with homogeneously internally colored phototropic thiourethane polymers, since the introduced 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-hydroxyl substituent on the benzene ring, which is attached to the carbon atom next to the pyran oxygen. According to the synthesis scheme in Figure 1, the compounds used or combined according to the present invention are produced therefrom. The method is the same for the 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 formula (I) and formula (II)) is first activated as a tosylate (Ts). The chain length has a Gaussian distribution, i.e. there is a mixture with various chain lengths distributed around a maximum. This is followed by covalent attachment to an anelated 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 unit is then activated with carbonyldiimidazole (CDI), which allows a very mild ester synthesis with polypropylene glycol monobutyl ether.

[0023] The excitation scheme (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] In order 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. suitable for commercial plastic ophthalmic lenses. For this purpose, the photochromic dye is dissolved in the liquid isocyanate component of the thiourethane polymer, and after adding the thiol component and the polyaddition initiator, it is thermally polymerized using a temperature program. The phototropic performance (darkening and lightening behavior) and the darkening hue of the test specimens thus prepared (2 mm thick flat glass) 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 according to the 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. Compound 1, Compound 2 and Compound 3 used in accordance with the present invention are described by formula (III), and Compound 4, Compound 5 and Compound 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, with positive a * The value represents the red hue. * The value represents the blue hue, with positive b * The value represents a yellow hue. The resulting mixed colors, e.g. purple or orange, can then 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 an absence of color (i.e. a gray hue), the more intense the color becomes. 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. chestnut) 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 according to the invention are located near 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 the molecular structure, it was almost impossible to predict the exact color in advance. In contrast, the darkening hues of the compounds according to formula (IV) used according to the invention are found between the yellow and red axes, with hues 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 is from about 450 nm for compound 4 to about 470 nm for compound 5 to about 530 nm for compound 6.

[0028] As mentioned at the beginning, the subject of the present invention is a combination or mixture or system of dyes according to formula (III) or formula (I) and dyes according to formula (IV) or formula (II) that, when properly matched with each other, obtain an aesthetic darkening hue. For example, to achieve an aesthetic gray hue, a combination of compound 1 and compound 5 provided according to the present invention can be introduced into a polymer, which together, in a suitable mixing ratio, produce a hue close to the coordinate origin in area A (see FIG. 2). This is also possible when compound 2 is combined with compound 4. In these combinations, it is always important that the lightening speed of the partners is consistent, otherwise an undesirable color shift would occur during lightening (for example, from gray to brown, if the blue partner lightens faster than orange). Therefore, the lightening speeds 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 the person 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 combination pair 3+6 when mixed alone does not produce an aesthetic neutral hue (blue-purple compound 3 mixed with red compound 6 is purple).

[0030] Tables 1 and 2 below show the molecular structures of the compounds according to formula (III) and formula (IV) as shown in FIG. 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 through R5, and the benzene ring is bonded through 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 given in Tables 1 and 2.

[0035] The percentage relative increase in transmission 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 referred to as:

number

[0036] The percentage values ​​specified are calculated from the transmittance data of a phototropic kinetic measurement at 23°C according to DIN EN ISO 8980-3. In a first step, the transmittance difference between the state after 2 minutes of light exposure and the previously achieved dark state is determined. In a second step, the transmittance difference between the lighted (non-excited) state and the dark 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 to the fully lightened state has already been completed. The higher the percentage value, the faster the lightening. Commercially available phototropic plastic eyeglass lenses have 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 a lightening speed that was not possible to achieve up to now, in combination with an excellent depth of darkening. The excellent depth of darkening is important, since such a high lightening speed was previously only effective in conjunction with a significantly weaker darkening.

[0037] Figure 3 shows a comparison of the phototropic performance of the compounds used according to 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 in Table 3 below. 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 photochromic dye's transmittance (or the higher its absorption) after UV exposure and the faster the dye returns to its initial unexcited state, the better.

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

[0041] A comparison of the properties of Reference Compound 1 and Reference Compound 2 is interesting. 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 contains a more polar ethyleneoxy unit (R 12 Both reference compounds have very poor phototropic performance, which is due to the dye with longer poly(propyleneoxy) chains (R 12 It is clearly shown that only the dyes =Me; Me is a common chemical abbreviation for the methyl group) are suitable for incorporation into the thiourethane polymer according to the 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 invention, which has a diphenylamino substituent as radical R2 in formula (V). The darkening of reference compound 3 is greatly reduced, since a significant part of this photochromic dye decomposes during polymerization. The reason for this is 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 invention are inactive in this respect. These dyes can therefore be easily incorporated into the thiourethane polymer. Generally, only dyes with non-basic substituents, such as alkyl, aryl, alkyloxy, aryloxy or diarylamino substituents, are suitable for this, but not dyes with dialkylamino or arylalkylamino substituents.

[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 irradiance of 700 W / m2 in a commercially available weathering test device. 2 The material is exposed to concentrated radiation for 50 hours using a xenon arc lamp. The measurements are carried out at 23 °C in accordance with the DIN EN ISO 8980-3 standard. The higher the specified percentage value, 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 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, and therefore have 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 combination according to the present invention into thiourethane polymer.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 also not limited to uniformly internally colored thiourethane polymers, but 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 invention relates to the use of the anelated naphthopyran isomer combinations according to the invention for incorporation into thiourethane polymers, in particular for ophthalmic applications in lenses and glasses for all kinds of spectacles, for example corrective spectacles, driving spectacles, ski goggles, sunglasses, motorcycle goggles, for visors such as for protective helmets, and for sun protection applications in the form of windows, protective screens, covers, roofs, etc. in the vehicle and construction sectors.

[0051] Another subject of the present invention is novel photochromic annelated 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 each independently represent 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, or a diphenylamino radical. or the radicals R1 and R2 taken together represent a substituent selected from the group consisting of -V-(CH2) m represents a -W- group, 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 also be annelated to two adjacent CH2 groups, and further, V or W, when they represent -CH2-, may also 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, mono- 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 annelated naphthalene ring system, an annelated benzofuran ring system, an annelated benzothiophene ring system, an annelated 3,3-dimethylindene ring system or an annelated 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 ) a 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, Or the radical R １ and R ２ In total, -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, m represents an integer from 1 to 3, provided that when the value is 2 or 3, the benzene ring is separated by two adjacent CH ２ V or W may be annelated to a -CH group. 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 ) a cycloalkyl radical, (C １ ~C ６ ) thioalkyl radical, (C １ ~C ６ ) a substituent selected from the group consisting of 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 from 1 to 3, provided that when this value is 2 or 3, the benzene ring is connected to two adjacent CH ２ X or Y may be annelated to a -CH group. 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 ) a cycloalkyl radical, (C １ ~C ６ ) 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, mono- or disubstituted, where the substituents are hydrogen, (C １ ~C ６ ) alkyl radical, (C １ ~C ６ ) 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 naphthalene ring system, an annelated benzofuran ring system, an annelated benzothiophene ring system, an annelated 3,3-dimethylindene ring system, or an annelated 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 the 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 ) a 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 ) a cycloalkyl radical, (C １ ~C ６ ) thioalkyl radical, (C １ ~C ６ ) a substituent selected from the group consisting of 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 ) a cycloalkyl radical, (C １ ~C ６ ) a substituent selected from an alkoxy radical, a phenyl radical or a benzyl radical, The radical R ９ , R １０ and R １１ Each of them is independently １ ~C ６ 2. The combination according to claim 1, wherein R 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 Each of them is independently １ ~C ６ ) alkyl radicals, preferably the radical R ９ , R １０ and R １１ A combination according to any one of claims 1 to 3, wherein each represents methyl.

5. Use of a combination according to any one of claims 1 to 4 for incorporation into thiourethane polymers, in particular for ophthalmic applications in lenses and glasses for spectacles of all kinds, such as corrective spectacles, driving spectacles, ski goggles, sunglasses, motorcycle goggles, for visors such as for protective helmets, and for sun protection applications in the form of windows, protective screens, covers, roofs, etc., in the vehicle and construction sector.

6. A phototropic thiourethane polymer comprising the combination according to any one of claims 1 to 4.

7. 7. A phototropic product based on thiourethane polymers according to claim 6, which is a two-component system in which a 0.1 mm to 1 mm thin phototropic thiourethane functional layer based on thiourethane polymers is polymerized onto a polymer substrate, or a sandwich system in which a 0.1 mm to 1 mm thin phototropic thiourethane functional layer based on thiourethane polymers is disposed between two polymer bodies.

8. A photochromic annelated naphthopyran 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 ) a 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, or the radical R １ and R ２ In total, -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, m represents an integer from 1 to 3, provided that when the value is 2 or 3, the benzene ring is separated by two adjacent CH ２ V or W may be annelated to a -CH group. 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, fluorine, (C １ ~C ６ ) alkyl radical, (C １ ~C ６ ) a substituent selected from the group consisting of 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 ) a cycloalkyl radical, (C １ ~C ６ ) 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, mono- or disubstituted, where the substituents are hydrogen, (C １ ~C ６ ) alkyl radical, (C １ ~C ６ ) 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 naphthalene ring system, an annelated benzofuran ring system, an annelated benzothiophene ring system, an annelated 3,3-dimethylindene ring system, or an annelated 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).

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