A polymeric photochromic dye having at least one and no more than four naphthopyran subunits and multiple polyether chains.

Abstract

The present invention relates to novel polymeric photochromic dyes having at least one and four or fewer naphthopyran subunits and a plurality of polyether chains, the use thereof, and phototropic acrylates, allyl carbonates, ureas, urethanes, or thiourethane polymers containing them, and phototropic products.

Description

Technical Field

[0001] The present invention relates to novel polymeric photochromic dyes having at least one and at most four naphthopyran subunits and a plurality of polyether chains, phototropic acrylates, allyl carbonates, ureas, urethanes, or thiourethane polymers containing them, phototropic products, and the use of these photochromic dyes.

Background Art

[0002] Thiourethane polymers are by far the most widely used materials for plastic eyeglasses having a higher refractive index of 1.60 or more. The higher the refractive index, the thinner the corrective eyeglass lenses can be manufactured. However, heretofore, it has been impossible to directly incorporate a photochromic dye into a thiourethane polymer without using special additives and exhibit acceptable phototropic properties (a combination of deep darkening upon exposure to sunlight and rapid brightening after the exposure ends). The reason for this is that the dense, three-dimensionally crosslinked polymer matrix of the thiourethane thermosetting polymer used for high-quality plastic eyeglass lenses leaves no room for the photochromic dye to undergo a reversible conversion induced by long-wavelength UV radiation from its colorless ground state to its darkened state. Therefore, conventional photochromic dyes either do not darken or darken only to a very small extent in a thiourethane thermosetting polymer under sunlight. For this reason, surface coating by a photochromic coating, mainly by spin coating, has been the best method for manufacturing phototropic plastic eyeglasses having a higher refractive index heretofore. However, this method has the disadvantages of requiring complex and expensive technical equipment, being able to manufacture only a relatively small number of products per unit time, and as a result, having a relatively high manufacturing cost.

[0003] Various types of dyes that reversibly change color when irradiated with long-wavelength UV light, particularly sunlight, have long been known. This is due to the fact that these photochromic dye molecules are converted by light energy from their colorless ground state ("closed state") to a darkened state ("open state") with selective bond cleavage, and from there, when the energy supply is interrupted, they reform the previously cleaved bonds to return to the colorless ground state. The most widely used type of dye for use in photochromic glasses is naphthopyran systems, in particular naphthopyran systems having more fused aromatic rings that absorb longer wavelengths in both the closed and colored open states due to a larger conjugated system. Benzene rings with additional crosslinks at the ortho position are typically used for fusion. In the compounds according to the present invention shown below, the benzene ring is fused via a single-atom crosslink (having R7 substituents and R8 substituents) or a diatom crosslink (having R7 substituents, R8 substituents, and R 10 The R9 substituent is fused via a substituent.

[0004] When a single-atom bridge is present, the five-membered ring is fused to the naphthopyran ("indenonaphthopyran"). Examples can be found in Patent Documents 1 and 2. Patent Documents 3, 4, 5, 6, 7, and 8 describe compounds in which at least one further ring system is fused to the indenonaphthopyran core structure. Patent Document 9 describes a doubly indeno-fused naphthopyran system having longer-chain polyether substituents to improve phototropic properties.

[0005] When diatomic bridges are present, a six-membered ring fused to naphthopyran ("dihydronaphthonaftopyran") is formed, as described in Patent Documents 10, 11, and 12. Such compounds having longer-chain polyether substituents are also described in the aforementioned Patent Document 9. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] European Patent No. 0792468 [Patent Document 2] European Patent No. 0906366 [Patent Document 3] European Patent No. 0912908 [Patent Document 4] European Patent Application Publication No. 2457915 [Patent Document 5] European Patent Application Publication No. 2471794 [Patent Document 6] European Patent No. 2684886 [Patent Document 7] European Patent No. 2788340 [Patent Document 8] European Patent No. 2872517 [Patent Document 9] European Patent No. 3807258 [Patent Document 10] European Patent No. 1119560 [Patent Document 11] European Patent Application Publication No. 2829537 [Patent Document 12] European Patent No. 3010924 [Overview of the project] [Problems that the invention aims to solve]

[0007] Therefore, the present invention is based on the objective of providing a novel photochromic dye that, by being directly incorporated into thiourethane thermosetting polymers in particular, yields a phototropic polymer characterized by excellent phototropic properties without the essential need for any special additives. With the help of the novel photochromic dye, excellent photochromic properties (a combination of extremely deep darkening upon exposure to sunlight and extremely rapid lightening after exposure) can be achieved not only in the high refractive index range but also in low refractive index lenses, independently of the matrix. [Means for solving the problem]

[0008] This objective is achieved by the invention characterized in the claims. [Brief explanation of the drawing]

[0009] [Figure 1] The synthesis scheme for the compound according to the present invention having two naphthopyran subunits to which condition (1) applies is shown. [Figure 2] The synthesis scheme of the compound according to the present invention, to which condition (2) is applied, is shown. [Figure 3] This document shows the phototropic performance of three compounds according to the present invention, compared with appropriate reference compounds from the prior art (Patent Document 9).

[0010] The present invention is based on the remarkable finding that certain photochromic dye molecules containing one to four naphthopyran subunits and having multiple polyether chains at different points on the molecule exhibit excellent matrix-independent phototropic properties in all types of plastic eyewear, in contrast to systems having only one naphthopyran subunit and one polyether chain, such as those described in the aforementioned Patent Document 9. Furthermore, this is achieved without the need for special additives, whereas dyes having only one naphthopyran subunit and one longer-chain polyether substituent exhibit unacceptable phototropic properties in densely crosslinked thiourethane thermosetting polymers without the help of special additives.

[0011] European Patent No. 2714767 describes a photochromic dye having two (or more) naphthopyran subunits linked to each other by a polymeric polyester chain. Furthermore, European Patent No. 2705071 describes a photochromic dye having two (or more) naphthopyran subunits linked to each other by various types of polymeric polymer chains. However, since the compounds described in these two documents also contain only one linear polymer chain, they do not exhibit acceptable phototropic properties in a thiourethane thermosetting polymer without the additional use of additives. In contrast, in the compounds according to the present invention, when two or more naphthopyran subunits are present in the molecule, the subunits are linked to each other only by relatively short linkers, while a plurality of polymeric polyether chains are each bonded to the "outside" of the molecule. Thereby, these longer-chain polyether substituents encapsulate the photochromic naphthopyran subunits very efficiently, whereby they can be completely shielded from each plastic lens polymer matrix. Thereby, for the first time, excellent photochromic properties can be realized without depending on the matrix even in a highly crosslinked thiourethane thermosetting polymer.

[0012] Therefore, according to the present invention, there is provided a novel polymeric photochromic dye having at least one and at most four naphthopyran subunits and a plurality of polyether chains according to the following formula (I),

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0013] The present invention further relates to a photochromic acrylate, allyl carbonate, urea, urethane, or thiourethane polymer containing one or more of the above photochromic dyes.

[0014] The present invention also relates in particular to a phototropic product based on such a thiourethane polymer, wherein the product is a two-component system in which a thin 0.1 mm to 1 mm thick phototropic polythiourethane functional layer based on a thiourethane polymer is polymerized on a polymer substrate, or a sandwich system in which a thin 0.1 mm to 1 mm thick phototropic polythiourethane functional layer based on a thiourethane polymer is arranged between two polymer bodies.

[0015] The present invention further relates to the use of photochromic dyes according to the present invention in the incorporation of thiourethane polymers, particularly for ophthalmic purposes, for all kinds of eyeglasses, such as corrective eyeglasses, driving glasses, ski goggles, sunglasses, and motorcycle goggles, for protective helmet visors, etc., and for lenses and glass for sun protection purposes in the vehicle and construction sectors in the form of windows, protective visors, covers, roofs, etc.

[0016] The compounds according to the present invention are characterized in that the photochromic naphthopyran subunit is located in the spatial proximity of two or more polyether chains. The arrangement of these subunits around a central tetrahedral carbon atom allows the entire system to be spatially encapsulated from the polymer matrix. This spatial shielding of the phototropic naphthopyran subunit, with the help of longer-chain polyether substituents, enables matrix-independent phototropic properties for the first time, which specifically means that phototropic properties can be achieved in thiourethanes, urethanes, ureas, acrylates, and allyl carbonates using the compounds according to the present invention.

[0017] Previously, achieving good phototropic properties required the use of specially adapted polymer matrices with lower density crosslinking, associated with lower hardness, or the addition of special additives. These additives, along with the dyes, form domain systems that locally soften the polymer matrix. However, the formation of these domains is highly material-specific and can only be realized in certain polymer matrices. However, the special structure of the compound according to the present invention allows longer-chain polyether substituents to be positioned near the pyran ring of the photochromic naphthopyran subunit. This is where the greatest structural change occurs during photochromic switching, specifically when ring-opening to the colored form or ring-closing back to the colorless form. Since the loose arrangement of linear polyether chains ("random coils") has minimal intramolecular interactions, this ring-opening and ring-closing of the photochromic center is not hindered. Therefore, the photochromic properties of the dyes according to the present invention can be realized even in highly crosslinked polymer matrices such as thiourethane polymers.

[0018] Due to the special structure of the pigments and their "separation" from the surrounding polymer matrix, the photochromic pigments according to the present invention can achieve excellent darkening when exposed to sunlight and extremely rapid lightening after the exposure is complete.

[0019] The bonding of the naphthopyran subunit to the central tetrahedral carbon atom in equation (I) occurs directly (when n=p=0), via the succinyloxy bridge (when n=1 and p=0), or via the ethyleneoxy-succinyloxy bridge (when n=p=1).

[0020] The use of succinyloxybridges is advantageous in that, when using modern coupling reagents, ester bonds can be formed at very mild reaction temperatures (including room temperature), i.e., without thermal stress on the molecules during heating and the resulting thermal decomposition reactions. Other coupling reactions, such as Williamson ether synthesis, require higher reaction temperatures and harsher reaction conditions (e.g., the use of strong bases).

[0021] The use of an ethylene oxy bridge between the naphthopyran subunit and the succinyl oxy bridge is generally necessary when seeking to achieve a higher lightening rate. In the case of naphthopyran systems, lightening from a darkened state is generally faster the better the electron-donating properties of the substituents on the two benzene rings bonded to the carbon atom adjacent to the pyran oxygen. Therefore, it is advantageous to use two strong electron-donating alkoxy substituents, as the acyl oxy substituent of the succinyl oxy bridge directly bonded to the naphthopyran subunit is too weak an electron donor and therefore often results in an insufficient lightening rate. The same applies to the succinyl oxy bridge (when r=1) as a link between the naphthopyran subunit and a longer-chain polyether substituent in the compounds according to the present invention to which condition (1) applies.

[0022] The compounds according to the present invention to which condition (1) applies have one to four naphthopyran subunits and a total of two to four longer-chain polyether substituents (distributed across groups A and B). The latter are either coupled to adjacent naphthopyran subunits via optional ethylene-oxy (when q=1) and succinyl-oxy bridges (when r=1), or, if there are fewer than four naphthopyran subunits in the molecule, optionally directly and additionally bonded to the central tetrahedral carbon atom of formula (I) as group B, specifically linked via a succinyl-oxy bridge. This non-optional succinyl-oxy bridge at group B is also present for synthetic reasons. The coupling of longer-chain polyether substituents to the central tetrahedral carbon atom is achieved here via ester bridges under very mild reaction conditions.

[0023] The compounds according to the present invention to which condition (2) applies have one or two naphthopyran subunits and two or three longer-chain polyether substituents. The latter are each linked to the naphthopyran subunit via a central tetrahedral carbon atom as group B. In contrast to condition (1), the further longer-chain polyether substituents are not bonded to the naphthopyran subunit, and only the "smaller" substituent R6 is bonded, which can, with its help, influence the darkening color and lightening rate.

[0024] For the synthesis of the compounds according to the present invention, in principle, suitable naphthopyran starting compounds known from the prior art can be used and reacted, for example, with a 1,3-bifunctional propane derivative (where m=m'=1) according to Figures 1 and 2 to form molecules having two naphthopyran subunits and at least two longer-chain polyether substituents.

[0025] Figure 1 shows a synthesis scheme for the compound according to the present invention having two naphthopyran subunits to which condition (1) is applied.

[0026] The starting compounds used here are naphthopyrans having a 4-hydroxy substituent on one of two benzene rings bonded to the carbon atom adjacent to the pyran oxygen, and a longer-chain polyether substituent bonded to the other benzene ring via an optional ethylene-oxy bridge (when q=1) and succinyl-oxy bridge (when r=1). Suitable polyether substituents include, in particular, commercially available longer-chain polypropylene glycol monobutyl ethers, but also polypropylene glycol / polyethylene glycol copolymers with monoalkyl caps. The chain lengths exhibit a Gaussian distribution, i.e., mixtures of different chain lengths distributed around a maximum value exist. Covalent coupling of two molecules of these naphthopyran starting compounds via the central tetrahedral carbon atom is carried out by Williamson ether synthesis using a 1,3-dibromopropane derivative (where m=m'=1). Alternatively, 1,2-dibromoethane (where R3=R4=H, m=1, and m'=0) can also be used.

[0027] When using the 2-(bromomethyl)-1,3-dibromopropane derivative (R3=CH2Br), three molecules of the naphthopyran starting compound can be converted into the compound according to the present invention containing three naphthopyran subunits. Therefore, four molecules of bis(2-bromomethyl)-1,3-dibromopropane (R3=R4=CH2Br) and the naphthopyran starting compound yield the compound according to the present invention having four naphthopyran subunits.

[0028] Figure 2 shows the synthesis scheme of the compound according to the present invention to which condition (2) is applied.

[0029] The starting compounds used here are naphthopyran starting compounds having a 4-succinyloxy substituent and an optional ethyleneoxy bridge (when p=1) on one of the two benzene rings bonded to the carbon atom adjacent to the pyran oxygen, and a para-substituted R6 on the other benzene ring. Covalent coupling of two molecules of these naphthopyran starting compounds via the central tetrahedral carbon atom is achieved by mild esterification using 1,1'-carbonyldiimidazole (CDI) and 1,3-propanediol derivatives having two longer-chain polyether substituents (R3=R4=group B). These 2,2-substituted 1,3-propanediol derivatives are relatively readily available from the inexpensive precursor pentaerythritol.

[0030] Figure 3 shows a comparison of the phototropic performance of three compounds according to the present invention with a suitable reference compound from the prior art (Patent Document 9). All compounds contain naphthopyran subunit "1". Naphthopyran subunits described in other claims exhibit completely similar behavior in such comparisons. The transmittance data in Figure 3 are from measurements performed at 23°C according to DIN EN ISO 8980-3.

[0031] Polythiourethane discs with a thickness of 2 mm were used for the measurements. These discs were manufactured by dissolving a photochromic dye in a liquid monomer mixture consisting of isocyanates and thiols suitable for high-quality plastic eyeglasses, and then thermally polymerizing it in a mold after the addition of a standard Sn catalyst.

[0032] Table 1 shows the specific molecular structures of the compounds shown in Figure 3. Compounds 1 and 2 according to the present invention are derived from Formula 1, Condition 1, and Compound 3 according to the present invention is derived from Formula 1, Condition 2.

[0033] [Table 1]

[0034] Compound 1 according to the present invention, shown in Table 1, has two naphthopyran subunits linked via a 1,3-propanediol bridge. The polypropylene glycol chains on each naphthopyran subunit are linked via glycol and succinyloxy bridges.

[0035] Compound 2 according to the present invention, shown in Table 1, has four naphthopyran subunits linked via a pentaerythritol bridge. The polypropylene glycol chain on each naphthopyran subunit is directly linked to the naphthopyran subunit via an ether bond.

[0036] Compound 3 according to the present invention, shown in Table 1, has two naphthopyran subunits linked to a pentaerythritol central molecule. The polypropylene glycol chain is bonded to each of the other two alcohol groups of pentaerythritol via succinyloxy bridges.

[0037] In contrast, the reference compound has only one polypropylene glycol chain and one naphthopyran subunit, and therefore reflects the prior art. Here, the naphthopyran subunit is identical to that of compounds 1 to 3 according to the present invention.

[0038] The results shown in Figure 3 clearly demonstrate that the precise structure of the naphthopyran subunit is of little importance in this invention. The reference compound exhibits virtually no phototropic properties and shows only minimal change in transmittance after irradiation with UV light. Phototropic properties of such compounds can only be expressed by using a highly adapted matrix or special additives.

[0039] In contrast, compounds 1, 2, and 3 according to the present invention exhibit good darkening depth with transmittance values ​​of less than 20% when fully excited. The arrangement of multiple naphthopyran subunits and polyether chains around a common center ensures an optimal environment for the dye, and therefore, photochromic properties can be exhibited without the use of special additives, even in polythiourethane polymers that are not optimized for this purpose.

[0040] In addition, the reference compound exhibits a relatively low transmittance value of only about 77% in the non-excited state. This indicates the presence of a colored ring-opened form of the photochromic dye that does not have the ability to return to a colorless ground state. This problem was also solved by compounds 1, 2, and 3 according to the present invention. This is because these dyes do not hinder the reverse reaction to a colorless ground state under non-irradiation conditions, making it possible to achieve much higher transmittance in the lightened state.

[0041] Compounds 1, 2, and 3 according to the present invention also exhibit very rapid lightening behavior.

[0042] These excellent photochromic properties (high transmittance in the lightened state, deep darkening upon exposure, and very rapid lightening) can be achieved not only in polythiourethane matrices but also in other matrices suitable for use in plastic eyewear, such as polyurethane, poly(meth)acrylate, or polyallyl carbonate. Therefore, a matrix-independent photochromic dye system that does not require additional additives is provided for the first time.

Claims

1. A photochromic dye having at least one and at most four naphthopyran subunits and a plurality of polyether chains according to the following formula (I), 【Chemistry 1】 However, condition (1) is that the radical R １ , R ２ , R ３ , and R ４ At least one and at most four of these represent the following group A having a longer-chain polyether substituent at the terminal end: 【Chemistry 2】 Remaining Radical R １ , R ２ , R ３ , and R ４ However, each independently represents one of the following groups B having a hydrogen, methyl radical, ethyl radical, phenyl radical, or longer-chain polyether substituent: 【Transformation 3】 Here, if there is only one group A in the molecule, then at least one of the remaining radicals must represent group B; Or, as condition (2), radical R １ , R ２ , R ３ , and R ４ Among at least one and at most two of them are, independently of each other, represented by the following group C: 【Chemistry 4】 Remaining Radical R １ , R ２ , R ３ , and R ４ At least two of these represent group B, and the remaining radicals can be selected from hydrogen, methyl radical, ethyl radical, or phenyl radical; Here, m, n, p, q, and r independently represent integers of 0 or 1, s represents an integer from 5 to 50, and t represents an integer from 0 to 3. Here, radical R in the repeating unit of chain length s ５ These represent, independently of each other, hydrogen or a methyl radical. Here, radical R ６ is hydrogen, 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, piperidinyl radical, 3,5-dimethylpiperidinyl radical, morpholinyl radical, 2,6-dimethylmorpholinyl radical, thiomorpholinyl radical, azacycloheptyl radical, indolinyl radical, 1,2,3,4-tetrahydroquinolinyl radical, 1,2,3,4-tetrahydroisoquinolinyl radical, diphenylamino radical, ((C １ ~C ６ )-alkoxyphenyl)-phenylamino radical, bis((C) １ ~C ６ Represents a substituent selected from )-alkoxyphenyl)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-dibenzo[b,f]azepinyl radical, Here, the stylized benzene ring labeled "naftopyran" represents one of the following four distinct naphthopyran subunits "1" through "4": 【Transformation 5】 Here, radical R ７ , R ８ , and R １０ (C １ ~C ６ ) - Represents a substituent selected from alkyl radicals or phenyl radicals, Radical R ９ (C １ ~C ６ )-alkyl radical, (C ３ ~C ７ )-cycloalkyl radical, (C １ ~C ６ ) represents a substituent selected from alkoxy radicals, benzyl radicals, or unsubstituted or monosubstituted phenyl radicals, wherein the substituent is fluorine, (C １ ~C ６ )-alkyl radical, or (C １ ~C ６ ) may be selected from alkoxy radicals, where k represents 0, 1, or 2. Alternatively, two adjacent R ９ The radicals combine to form a fused benzene ring which may be unsubstituted, monosubstituted, or disubstituted, and the substituent is (C １ ~C ６ )-alkyl radical, (C １ ~C ６ ) - May be selected from alkoxy radicals, phenyl radicals, or benzyl radicals, Alternatively, two adjacent R ９ The radicals combine to form a fused naphthalene ring system, a fused benzofuran ring system, a fused benzothiophene ring system, a fused 3,3-dimethylindene ring system, or a fused 2H-chromene ring system. Radical R １１ and R １２ These are, independently of each other, hydrogen, (C １ ~C ６ )-alkyl radical, (C ３ ~C ７ ) represents a substituent selected from a cycloalkyl radical, a trifluoromethyl radical, a benzyl radical, or an unsubstituted or monosubstituted phenyl radical, wherein the substituent is fluorine, (C １ ~C ６ )-alkyl radical, or (C １ ~C ６ ) - May be selected from alkoxy radicals, Or, radical R １１ and R １２ Together they form the base - (CH ２ ) ｊ This represents a negative value, where j is an integer from 1 to 3, except that if this value is 2 or 3, the benzene ring consists of two adjacent CH groups. ２ It may be fused to the base, Photochromic dye.

2. A photochromic dye according to claim 1, characterized by condition (1).

3. A photochromic dye according to claim 1, characterized by condition (2).

4. The photochromic dye according to any one of claims 1 to 3, wherein a stylized benzene ring labeled "naftopyran" is selected from one of the naphtopyran subunits "1", "2", or "3" described above.

5. The aforementioned radical R ９ However, they are independent of each other, (C １ ~C ６ )-alkyl radical, (C ３ ~C ７ )-cycloalkyl radical, (C １ ~C ６ ) represents a substituent selected from alkoxy radicals, benzyl radicals, or unsubstituted or monosubstituted phenyl radicals, wherein the substituent is fluorine, (C １ ~C ６ )-alkyl radical, or (C １ ~C ６ ) - A photochromic dye according to any one of claims 1 to 4, wherein k may be selected from alkoxy radicals, and k represents 0, 1, or 2.

6. The aforementioned radical R １１ and R １２ However, hydrogen, (C １ ~C ６ )-alkyl radical, (C ３ ~C ７ ) represents a substituent selected from a cycloalkyl radical, a benzyl radical, or an unsubstituted or monosubstituted phenyl radical, wherein the substituent is fluorine, (C １ ~C ６ )-alkyl radical, or (C １ ~C ６ ) - A photochromic dye according to any one of claims 1 to 5, which may be selected from alkoxy radicals.

7. A phototropic acrylate, allyl carbonate, urea, urethane, or thiourethane polymer comprising one or more photochromic dyes according to any one of claims 1 to 6.

8. A phototropic product based on a thiourethane polymer as described in claim 7, wherein the phototropic product is a two-component system in which a thin 0.1 mm to 1 mm thick phototropic polythiourethane functional layer based on the thiourethane polymer is polymerized on a polymer substrate, or a sandwich system in which a thin 0.1 mm to 1 mm thick phototropic polythiourethane functional layer based on the thiourethane polymer is arranged between two polymer bodies.

9. Use of a photochromic dye according to any one of claims 1 to 6, particularly for ophthalmic purposes, for all kinds of eyeglasses, such as corrective eyeglasses, driving glasses, ski goggles, sunglasses, and motorcycle goggles, for protective helmet visors, etc., and for lenses and glass for sun protection purposes in the vehicle and construction sectors in the form of windows, protective visors, covers, roofs, etc., in the form of a thiourethane polymer.

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