Sulfonyl-bridged pyrenones

Abstract

The present invention relates to sulfonyl-bridged pyrenones, in particular to sulfonyl-bridged pyrenones in the form of compounds of general formula (I) or isomer forms thereof, wherein R is a C1-C6-alkyl group, a halogen, a nitro group, an aryl group, an aryloxysulfonyl group, a hydroxyl group, a C1-C6-alkoxy group, an aryloxy group, an optionally alkyl-or acyl-substituted amino group, an optionally alkyl-or aryl-substituted aminosulfonyl group, or a fused alicyclic or heterocyclic group; the invention also relates to a method for the production thereof and to the use thereof for the bulk colouring of plastics.

Description

Technical Field

[0001] The present invention relates to sulfonyl-bridged perinone and its isomeric forms, to a process for their production, and to their use in injection-molded products based on plastics, in particular in injection-molded products for the food industry. Background Art

[0002] Plastics that can be processed by injection molding are also widely used in the food industry. For example, EP 0 366 382 A1 teaches the use of polyamides for producing food and beverage cans.

[0003] WO 2019 / 069292 A1 describes the use of polyethylene terephthalate (PET) for producing beverage bottles by blow molding, in particular injection blow molding or stretch blow molding. In principle, polyesters such as PET can alternatively be processed by injection molding, extrusion or blown film. In the form of B1520 FC R01 (FC=food contact), BASF SE offers a polybutylene terephthalate with high flowability which has been specially developed for food packaging and is notable for its stiffness, strength, and thermal and chemical stability.

[0004] However, for aesthetic reasons or to differentiate their contents, plastic-based articles intended for food contact may be colored with dyes. However, until recently, the dyes commonly used were no longer desirable in sensitive applications such as food contact, as they were suspected of posing a health risk; C. Barciela et al., Food and Chemical Toxicology, Vol. 178, August 2023, 113935, pp. 1-12.

[0005] DE 43 27 855 A1 discloses, inter alia, optionally substituted phenylsulfonyl-bridged phthalocyanine dyes based on optionally substituted 1,8-diaminonaphthalene for the bulk coloring of plastics. By dissolving these phthalocyanine dyes in the monomer components of the plastic and intimately mixing them, transparent or soft bright orange to purple colors with good heat resistance, light fastness, and weathering resistance are obtained. DE 43 27 855 A1 makes no statement regarding the use of such phthalocyanine dyes in injection-molded products based on plastics, in particular in injection-molded products for the food industry. The phthalocyanine dyes according to DE 43 27 855 A1 are not red. Summary of the Invention

[0006] It was therefore an object of the present invention to provide novel red dyes which firstly have a high thermal stability for processing with plastics by injection molding, but at the same time have low migration properties compared to dyes which can usually be used in plastics intended for food contact.

[0007] This object is achieved by the subject matter of the present invention in the form of sulfonyl-bridged pyrenones of the general formula (I) or their isomers

[0008]

[0009] in

[0010] R is C1-C6-alkyl, aryl, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group.

[0011] In particular, this object is achieved by the subject matter of the present invention in the form of the optionally substituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthaloperin-12-one.

[0012] In addition to their red color, the sulfonyl-bridged pyrenones of formula (I) and their isomeric forms, in particular the optionally substituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one, surprisingly have a particularly high thermal stability, which makes them particularly suitable for injection molding of plastics and, according to C. Barciela et al., Food and Chemical Toxicology, Vol. 178, August 2023, 113935, pp. 1-12, are notable for their particularly low migration properties in or from plastics compared to dyes typically used in the food sector. Thermal stability is an important prerequisite for dyes used in plastics that can be processed by injection molding. In injection molding, the polymer melt is forced through an open mold and a gate or gate system in the form of a molding cavity under high pressure, typically in the range of 500 to 2000 bar and at a temperature in the range of 200°C to 300°C; see:

[0013] https: / / www.kunststoffe.de / a / grundlagenartikel / spritzgiessen-254055.

[0014] For the sake of clarity, it should be noted that the scope of the present invention encompasses all definitions and parameters cited below in general terms or specified in preferred ranges in any desired combination. This also relates to the combination of the individual components of the stated amounts associated with the methods and uses claimed in the present invention. Unless otherwise stated, the standards cited in the context of this application relate to the current versions on the application date of the present invention. Unless otherwise stated, the reported percentages are weight percentages. Peri-position arrangement actually refers to the 1,8 arrangement in naphthalene. This meaning of peri-position arrangement is applicable to arylidenes with more than two mutually fused phenyl rings in the literature and in the context of this application.

[0015] An aryl group or an aryl radical (abbreviated as Ar) is an organic chemical group having an aromatic basic skeleton. Aryl is therefore a general term for monoatomic radicals derived from aromatic hydrocarbons by removing a ring-bonded hydrogen atom. Most aryls are derived from benzene (C6H6); the simplest aryl group, which is preferred according to the invention, is the phenyl group (Ph), (-C6H5).

[0016] An alkyl group or an alkyl group is part of a molecule consisting of carbon atoms and hydrogen atoms bonded to one another. The simplest alkyl group is the methyl group -CH3. Other alkyl groups preferred according to the invention are the ethyl group -CH2-CH3 or the n-propyl group -CH2-CH2-CH3. The general formula of an alkyl group in chain form is C n H 2n+1 .

[0017] Acyl or acyl group refers to a functional group having the general structure R-(C=O)-, where R is an organic group, preferably an alkyl, aryl or heteroaromatic group, or a hydrogen atom. Acyl groups are present in compounds such as aldehydes, carboxylic acids, or carboxylic acid derivatives, especially phosgene, in which, in a formal sense, an OH group, a hydrogen atom or a chlorine atom has been replaced by a free radical.

[0018] For the sake of clarification, it should also be noted that Formula (I) reflects only one of several possible isomers. Formula (I) reflects only one of several possible isomers, where an isomer, according to https: / / de.wikipedia.org. / wiki / Isomerie, refers to the occurrence of two or more compounds with the same empirical formula and molecular weight, but differing in the bonding or spatial arrangement of the atoms and represented by different structural formulas. The sulfonyl-bridged pyrenones of Formula (I) of the present invention are positional isomers, where the same functional group can be located at different positions, in this case, at position 9 or 10 of the pyrenone structure. For the sake of clarification, it should also be noted that the particularly preferred optionally substituted sulfonyl bis-12H-phthalopyrin-12-ones according to the present invention take the form of their 10,10', 9,9', or 9,10 isomers.

[0019] In the context of the present invention, "optionally substituted" or "unsubstituted" refers to the optionally substituted or unsubstituted naphthalene-1,8-diamine or naphthyl group to be used in the process according to the invention, or to the two naphthyl groups present therein in the sulfonyl-bridged pyrenone or the particularly preferred sulfonylbis-12H-phthalopyrin-12-one of formula (I) according to the invention. The two naphthyl groups may preferably have one to a maximum of twelve identical or different substituents. In this case, the naphthalene-1,8-diamine to be used in the process according to the invention has at least one further substituent in addition to the amino group required for the reaction with 5,5-sulfonylbis(isobenzofuran-1,3-dione). Preferably, for this purpose, at least one substituent should be selected from the group consisting of chlorine, bromine, nitro, methoxy, NH2, benzyloxy, hydroxy, -SO2O(C6H5), -SO2N(CH3)2, -SO2NHCH3, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, NHCOCH3, -N(C2H5)2 and phenyl.

[0020] Preferred implementations of the present invention

[0021] Isomers or isomeric forms of 10,10′-sulfonyl-bridged pyrenone which are preferred according to the invention are 9,9′-sulfonyl-bridged pyrenone, 10,9-sulfonyl-bridged pyrenone and 9,10-sulfonyl-bridged pyrenone.

[0022] Particularly preferred isomers or isomeric forms of the present invention of optionally substituted sulfonylbis-12H-phthalpyrin-12-one are optionally substituted 10,10′-sulfonylbis-12H-phthalpyrin-12-one, optionally substituted 9,10-sulfonylbis-12H-phthalpyrin-12-one and optionally substituted 9,9-sulfonylbis-12H-phthalpyrin-12-one.

[0023] The present invention preferably relates to unsubstituted 10,10′-sulfonylbis-12H-phthalpyrin-12-one of formula (II), unsubstituted 9,10-sulfonylbis-12H-phthalpyrin-12-one of formula (III) and unsubstituted 9,9-sulfonylbis-12H-phthalpyrin-12-one of formula (IV).

[0024]

[0025]

[0026] The substituted isomers of the sulfonylbis-12H-phthalpyrin-12-one of formula (II), (III) and (IV) which are particularly preferred according to the invention are notable for at least one substituent on at least one of the two naphthyl groups. The two naphthyl groups may preferably have one to a maximum of twelve identical or different substituents. Preferred substituents are selected from the group consisting of chlorine, bromine, nitro, methoxy, NH 2 , benzyloxy, hydroxyl, -SO 2 O(C 6 H 5 ), -SO 2 N(CH 3 ) 2 , -SO 2 NHCH 3 , methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, NHCOCH 3 , -N(C 2 H 5 ) 2 and phenyl.

[0027] In the context of the present invention, preferred plastics are those used in injection molding, extrusion or blow molding, especially in injection molding. These are preferably thermoplastics, more preferably vinyl polymers, polyesters, polyolefins or polyamides. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylates or polyvinyl chloride. Preferred polyesters are polyethylene terephthalate, polybutylene terephthalate, polycarbonate or cellulose esters. Preferred polyamides are nylon-6 or nylon-6,6.

[0028] The present invention preferably relates to sulfonyl-bridged pyrenones of the general formula (I) or isomers thereof

[0029]

[0030] wherein R is a C1-C6-alkyl group, an aryl group, an optionally alkyl- or acyl-substituted amino group, an optionally alkyl- or aryl-substituted aminosulfonyl group, or a fused alicyclic or heterocyclic group, and has a color distance ΔE of <20 from the L*a*b* coordinates of a color number starting with "3" in the RAL color card.

[0031] More preferably, the present invention relates to a sulfonyl-bridged pyrenone of formula (I) or an isomer thereof, wherein R is

[0032]

[0033] In an alternative or preferred embodiment, the present invention relates to a sulfonyl-bridged pyrenone of formula (I), wherein at least one of the phenyl rings in the pyrenone structure has at least one substituent from the group consisting of chloro, bromo, nitro, methoxy, NH2, benzyloxy, hydroxyl, -SO2O(C6H5), -SO2N(CH3)2, -SO2NHCH3, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, NHCOCH3, -N(C2H5)2 or phenyl.

[0034] The sulfonyl group preferably bridges two identical pyrenone structures. According to the invention, very particularly preferably, the sulfonyl group bridges two 12H-phthalpyrin-12-one groups to one another, 12H-phthalpyrin-12-one itself being known from EP 1 245 645 A1 as the dye Solvent Orange 60 [CAS No. 6925-69-5]. Its synthesis is described in EP 780 444 A2, Example 1. The result of the sulfonyl bridging of two 12H-phthalpyrin-12-one groups according to the invention is a dye having the empirical formula C 36 H 18 Sulfonyl-bridged pyrenone dyes of the formula (II) of N4O4S, which are very particularly preferred according to the invention, and 10,10′-sulfonylbis-12H-phthalpyrin-12-one and its isomers.

[0035]

[0036] Isomers of 10,10′-sulfonylbis-12H-phthalpyrin-12-one preferred according to the invention are 9,9′-sulfonylbis-12H-phthalpyrin-12-one, 10,9-sulfonylbis-12H-phthalpyrin-12-one and 9,10-sulfonylbis-12H-phthalpyrin-12-one.

[0037] Table 1: RAL color card

[0038] In the context of the present invention, red is understood to mean a color having a color number starting with "3" in the RAL color system according to https: / / de.wikipedia.org / wiki / RAL-Farbe#Rot in the RAL color chart. More specifically, at the filing date of the present invention, the following distinction is made between red hues:

[0039]

[0040]

[0041]

[0042] This table shows the device-independent CIE L*a*b* color values ​​for red, corresponding to the RAL value: L* represents lightness, a* describes the color's position on the red-green axis, and b* describes the color's position on the yellow-blue axis, using D65 standard light and a 10° field of view for a standard observer. The color model is standardized in EN ISO 11664-4, "Colorimetry - Part 4: CIE 1976 L*a*b* Colorspace." For more information on the L*a*b* color space (also known as CIELAB), see: https: / / de.wikipedia.org / wiki / Lab-Farbraum. Each color in the color space is defined by its position with Cartesian coordinates {L*, a*, b*}. The a*b* coordinate plane is constructed using the theory of opponents. Green and red are at opposite ends of the a* axis, while the b* axis runs from blue to yellow. Complementary hues are 180° opposite each other; all achromatic colors are arranged in the middle (coordinate origin a*=0, b*=0).

[0043] The L* axis describes the lightness (brightness) of a color, with values ​​ranging from 0 to 100. On the chart, it is positioned perpendicular to the a*b* plane at the origin. Since all achromatic colors (gray shades) are contained between the endpoints of black (L*=0) and white (L*=100), it can also be called the neutral gray axis. The a* axis describes the green or red component of a color, with negative values ​​representing green and positive values ​​representing red. The b* axis describes the blue or yellow component of a color, with negative values ​​representing blue and positive values ​​representing yellow.

[0044] The a* value ranges from approximately -170 to +100, and the b* value ranges from -100 to +150, with the maximum value only reached at medium brightness in some hues. The CIELAB color entity has its maximum range in the medium brightness region, but this varies in height and size depending on the color range.

[0045] However, according to the present invention, red-like hues are also included, which have a color distance ΔE<20 from the L*a*b* coordinates of the color number of red starting with "3" in the RAL color chart.

[0046] According to the invention, preferred are red sulfonyl-bridged pyrenones of the general formula (I) or isomers thereof, which have a color distance ΔE <20 from the L*a*b* coordinates of a red color number starting with "3" on the RAL color chart and have a yellow hue with a*>0 and b*≥25. Therefore, the following applies to the hue angle h: h° 最小值 =14° and h° 最大值<90°, including all color positions in between.

[0047] Particularly preferred are optionally substituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one, which, according to the color model in EN ISO 11664-4, have a color distance ΔE of <20 from the L*a*b* coordinates of a color number beginning with “3” on the RAL color scale. According to the color model in EN ISO 11664-4, a color number beginning with “3” on the RAL color scale represents red.

[0048] Particularly preferred are optionally substituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one, which, according to the color model in EN ISO 11664-4, have a color distance ΔE<20 from the L*a*b* coordinates of a color number starting with “3” on the RAL color chart, have a yellow hue defined as a*>0 and b*≥25, which means that the following applies for the hue angle h: h° 最小值 =14° and h° 最大值 <90°, including all color positions in between.

[0049] Also particularly preferred are unsubstituted 10,10′, 9,9′, or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one, which, according to the color model in EN ISO 11664-4, have a color distance ΔE of <20 from the L*a*b* coordinates of a color number beginning with “3” on the RAL color chart. According to the color model in EN ISO 11664-4, a color number beginning with “3” on the RAL color chart represents red.

[0050] Finally, particularly preferred are unsubstituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one, which, according to the color model in EN ISO 11664-4, have a color distance ΔE<20 from the L*a*b* coordinates of the color numbers starting with “3” on the RAL color chart, have a yellow hue defined by a*>0 and b*≥25, which means that the following applies to the hue angle h: h° 最小值 =14° and h° 最大值 <90°, including all color positions in between.

[0051] method

[0052] One possible synthetic route for preparing sulfonyl-bridged pyrenones of formula (I) and their isomeric forms is the reaction or condensation of sulfonyl-substituted isobenzofurandiones with at least one aromatic diamine from the group consisting of naphthalene-1,8-diamine, chloronaphthalene-1,8-diamine, dichloronaphthalene-1,8-diamine, methylnaphthalene-1,8-diamine, dimethylnaphthalene-1,8-diamine, methoxynaphthalene-1,8-diamine, ethoxynaphthalene-1,8-diamine, acetamido-1,8-naphthalenediamine, and 1,8-diaminoacenaphthylene. Particularly preferred is naphthalene-1,8-diamine. This synthetic route is particularly preferred for preparing the unsubstituted sulfonyl-bridged pyrenones of formula (II) and their isomeric forms, which are particularly preferred according to the present invention, in which 5,5-sulfonylbis(isobenzofuran-1,3-dione) is reacted with naphthalene-1,8-diamine.

[0053] It is preferred to use at least 2 moles of the optionally substituted aromatic diamine per mole of 5,5-sulfonyl-bridged isobenzofurandione. In some embodiments, greater than 2 moles of the optionally substituted aromatic diamine may also be used, although stoichiometric use of the reactants is preferred.

[0054] Since at least two moles of optionally substituted aromatic diamine are used per mole of sulfonyl-substituted isobenzofurandione to synthesize the sulfonylbis-12H-phthalpyrin-12-ones of the present invention, it is also possible to prepare sulfonylbis-12H-phthalpyrin-12-ones in which the two 1,8-naphthyl groups have different substitutions. In this case, "differently substituted" means substitution at different positions on the corresponding naphthyl groups and / or the different substituents on the corresponding naphthyl groups are selected from the group consisting of chloro, bromo, nitro, methoxy, NH2, benzyloxy, hydroxyl, -SO2O(C6H5), -SON(CH3)2, -SONHCH3, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, NHCOCH3, -N(C2H5)2, and phenyl. These reactants can be directly condensed by melting appropriate molar equivalents of the reactants together at a temperature ranging from 120°C to 250°C.

[0055] Preference is given to converting the reactants in a solvent at a temperature in the range of 110° C. to 220° C., optionally under pressure, wherein the water of reaction can be removed by distillation. For the condensation, preference is given to using at least one solvent selected from the group consisting of chlorobenzene, o-dichlorobenzene, trichlorobenzene, xylene, dimethylformamide, N-methylpyrrolidone, glacial acetic acid, propionic acid, phenol, cresol, phenoxyethanol, glycols and their mono- and dialkyl ethers, alcohols, in particular methanol, ethanol, isopropanol, water and aqueous solvents, in particular dilute sulfuric acid. According to the invention, particular preference is given to using phenol.

[0056] In one embodiment, the reaction can be carried out by adding at least one acidic catalyst. In this case, it is preferred to use a catalyst selected from the group consisting of zinc chloride, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, organic acids.

[0057] The reaction mixture for preparing the sulfonyl-bridged pyrenones of formula (I) and their isomeric forms, in particular for preparing the optionally substituted sulfonylbis-12H-phthalopyrin-12-ones in their 10,10', 9,9', or 9,10 isomeric forms, is preferably worked up by dilution with an alcohol, preferably methanol, ethanol, propanol, or butanol. Aromatic diluents, preferably chlorobenzene or toluene, may also be used. The process according to the invention provides the sulfonyl-bridged pyrenones of formula (I) and their isomeric forms, preferably in yields of 85% to 95% of theoretical value.

[0058] The sulfonyl-bridged pyrenones of the formula (I) according to the invention and their isomeric forms, in particular the optionally substituted sulfonylbis-12H-phthalopyrin-12-ones in the form of their 10,10′, 9,9′ or 9,10 isomers, are very suitable for the mass coloring of plastics. In this context, mass coloring more particularly refers to processes in which the dye is introduced into the molten plastic mass, preferably with the aid of an extruder, or in which the dye is added directly to the reactants for producing the particular plastic, preferably the corresponding monomers before polymerization.

[0059] Particularly preferred plastics to be colored by the sulfonyl-bridged pyrenones of formula (I) according to the invention and their isomeric forms, in particular by the optionally substituted sulfonylbis-12H-phthalopyrin-12-ones in the form of their 10,10′, 9,9′ or 9,10 isomers, are thermoplastics suitable for injection molding, preferably vinyl polymers, polyesters, polyolefins or polyamides, in particular plastics suitable for injection molding. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylates or polyvinyl chloride. Preferred polyesters are polyethylene terephthalate, polybutylene terephthalate, polycarbonates or cellulose esters. Preferred polyamides are nylon-6 or nylon-6,6.

[0060] Very particularly preferred plastics to be colored by the sulfonyl-bridged pyrenones of the formula (I) according to the invention and appropriate isomers, in particular by optionally substituted sulfonylbis-12H-phthalopyrin-12-one in the form of its 10,10′, 9,9′ or 9,10 isomers, are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylates, polyethylene terephthalate, nylon-6 or nylon-6,6.

[0061] The sulfonyl-bridged pyrenones of formula (I) and suitable isomers to be used according to the invention as dyes, in particular the optionally substituted sulfonylbis-12H-phthalpyrin-12-ones in the form of their 10,10′, 9,9′ or 9,10 isomers, are preferably used in finely divided form, optionally with additional use of at least one dispersant.

[0062] If the sulfonyl-bridged pyrenone of formula (I) and its isomers, especially the optionally substituted sulfonylbis-12H-phthalopyrin-12-ones in their 10,10′, 9,9′, or 9,10 isomers, to be used as dyes according to the present invention are used after polymerization of the corresponding plastic, they are mixed or ground in dry form with the granulated plastic, and this mixture is preferably plasticized and homogenized on a mixing drum or in a screw system. Alternatively, the sulfonyl-bridged pyrenone of formula (I) and its isomers, especially the optionally substituted sulfonylbis-12H-phthalopyrin-12-ones in their 10,10′, 9,9′, or 9,10 isomers, to be used as dyes according to the present invention can be added to the melt of the plastic and uniformly distributed therein by stirring. This pre-colored plastic is then typically or preferably further processed by spinning to produce bristles or filaments, or by extrusion, blow molding, or injection molding to produce shaped articles.

[0063] Since the sulfonyl-bridged pyrenones of formula (I) and the appropriate isomers thereof, in particular the optionally substituted sulfonylbis-12H-phthalopyrin-12-ones in the form of their 10,10′, 9,9′ or 9,10 isomers, to be used as dyes according to the invention are stable to polymerization catalysts, in particular peroxides, these can also be added to the monomer reactants of the corresponding plastic and the colored monomer reactants are then polymerized in the presence of polymerization additives. For this purpose, the sulfonyl-bridged pyrenones of formula (I) according to the invention and their isomers, in particular the optionally substituted sulfonylbis-12H-phthalopyrin-12-ones in the form of their 10,10′, 9,9′ or 9,10 isomers, are preferably dissolved in the monomer reactants of the particular plastic or intimately mixed therewith. Preferably, the sulfonyl-bridged pyrenones of the formula (I) according to the invention and their isomeric forms, in particular the optionally substituted sulfonylbis-12H-phthalopyrin-12-ones in the form of their 10,10′, 9,9′ or 9,10 isomers, are used for coloring the plastics or polymers mentioned in amounts in the range from 0.0001% to 1% by weight, in particular in the range from 0.01% to 0.5% by weight, these amounts being in each case based on the amount of the plastic or polymer.

[0064] By adding pigments that are insoluble in certain plastics or polymers, especially titanium dioxide, correspondingly valuable pastel colors can be achieved. These insoluble pigments, especially titanium dioxide, are preferably used in an amount ranging from 0.01% to 10% by weight, preferably from 0.1% to 5% by weight, based on the amount of the polymer.

[0065] According to the invention, it is also possible to use mixtures of different sulfonyl-bridged pyrenones according to the invention and / or mixtures of sulfonyl-bridged pyrenones of the formula (I) according to the invention and their isomeric forms, in particular mixtures of optionally substituted sulfonylbis-12H-phthalpyrin-12-one in the form of its 10,10′, 9,9′ or 9,10 isomers with other dyes and / or inorganic or organic pigments.

[0066] Other uses

[0067] The present invention relates to the use of sulfonyl-bridged pyrenones of the formula (I) and the corresponding isomers for the bulk coloration of plastics with simultaneously reduced migration properties in the plastics, in particular to the use of optionally substituted sulfonylbis-12H-phthalpyrin-12-ones in the form of their 10,10′, 9,9′ or 9,10 isomers for the bulk coloration of plastics with simultaneously reduced migration properties in the plastics, the migration properties being determinable in accordance with DIN 53775-3.

[0068] The plastics are preferably those used in injection molding, extrusion or blow molding. The plastics are preferably vinyl polymers, polyesters, polyolefins or polyamides, particularly preferably nylon-6 or polycarbonate.

[0069] These are preferably plastics for injection molding. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylates or polyvinyl chloride. Preferred polyesters are polyethylene terephthalate, polybutylene terephthalate, polycarbonate or cellulose esters. Preferred polyamides are nylon-6 or nylon-6,6.

[0070] The use preferably relates to sulfonyl-bridged pyrenones of formula (I) and isomers thereof, wherein R is a group

[0071]

[0072] Particularly preferred is the use of 10,10′-sulfonylbis-12H-phthalopyrin-12-one and its isomers. Particularly preferably, in this case, all naphthyl groups are unsubstituted. Therefore, this use preferably relates to the unsubstituted 10,10′, 9,9′, or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one. Alternatively, the present invention relates to the use of sulfonyl-bridged pyrenones of formula (I) and the corresponding isomers as dyes for bulk coloring of plastics, while simultaneously increasing the thermal stability of polymer compositions based on these dyes in these plastics, and in particular to the use of optionally substituted sulfonylbis-12H-phthalopyrin-12-ones in the form of their 10,10′, 9,9′, or 9,10 isomers as dyes for bulk coloring of plastics, while simultaneously increasing the thermal stability of polymer compositions based on these dyes in these plastics, the thermal stability being determined according to DIN EN 12877. The plastics are preferably those for injection molding, blow molding or extrusion, especially those for injection molding. Preferred plastics are vinyl polymers, polyesters, polyolefins or polyamides, particularly preferably nylon-6 or polycarbonate. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylates or polyvinyl chloride. Preferred polyesters are polyethylene terephthalate, polybutylene terephthalate, polycarbonate or cellulose esters. Preferred polyamides are nylon-6 or nylon-6,6.

[0073] The use preferably relates to sulfonyl-bridged pyrenones of formula (I) and isomers thereof, wherein R is a group

[0074]

[0075] Particularly preferred is 10,10'-sulfonylbis-12H-phthalopyrin-12-one and its isomers.

[0076] The present invention preferably relates to the use of optionally substituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one for the mass coloring of plastics in order to achieve a color distance ΔE of <20 between the L*a*b* coordinates of a color number beginning with “3” on the RAL color chart according to the color model in EN ISO 11664-4 and the color number beginning with “3” on the RAL color chart. The color number beginning with “3” on the RAL color chart represents red.

[0077] Preference is given to the use of optionally substituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one for the mass coloring of plastics in order to achieve a yellow hue defined by a*>0 and b*≥25 according to the color model in EN ISO 11664-4 and the L*a*b* coordinates of the color numbers starting with “3” in the RAL color chart with a color distance ΔE<20, which means that the following applies to the hue angle h: h° 最小值 =14° and h° 最大值 <90°, including all color positions in between.

[0078] Particularly preferred is the use of optionally substituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one for the mass coloring of plastics in order to achieve a color distance ΔE of <20 between the L*a*b* coordinates of the color model in EN ISO 11664-4 and the color numbers starting with “3” on the RAL color chart, while at the same time increasing the thermal stability of polymer compositions based on these isomers of sulfonylbis-12H-phthalopyrin-12-one in plastics, the thermal stability being determined in accordance with DIN EN 12877, the increase in thermal stability observed for the plastics examined in the context of the present invention being within the processing limits of the polymer compositions examined.

[0079] The plastic is preferably also a plastic for injection molding, blow molding or extrusion, especially for injection molding. The plastic is also preferably a vinyl polymer, polyester, polyolefin or polyamide, particularly preferably nylon 6 or polycarbonate. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are also polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylates or polyvinyl chloride. Preferred polyesters are polyethylene terephthalate, polybutylene terephthalate, polycarbonate or cellulose esters. Preferred polyamides are also nylon 6 or nylon 6,6. This use also preferably relates to unsubstituted 10,10′-sulfonylbis-12H-phthalopyrin-12-one and its 9,9′ and 9,10 isomers.

[0080] product

[0081] Finally, the present invention also relates to extruded, blow-molded or injection-molded products based on at least one sulfonyl-bridged pyrenone of the general formula (I) or an isomeric form thereof

[0082]

[0083] in

[0084] R is C1-C6-alkyl, aryl, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group, and

[0085] At least one plastic, preferably at least one thermoplastic, more preferably at least one plastic from the group consisting of vinyl polymers, polyesters, polyolefins, and polyamides. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylates, or polyvinyl chloride. Preferred polyesters are polyethylene terephthalate, polybutylene terephthalate, polycarbonates, or cellulose esters. Preferred polyamides are nylon 6 or nylon 6,6.

[0086] Preferred are those extruded, blown or injection-molded products based on sulfonyl-bridged pyrenones of the general formula (I) or their isomers, in which R is Very particularly preferred are extruded, blown or injection-molded products based on 10,10′-sulfonylbis-12H-phthalpyrin-12-one and its isomers.

[0087] The present invention more particularly relates to extruded, blow-molded or injection-molded products, preferably for food contact, based on at least one optionally substituted sulfonylbis-12H-phthalopyrin-12-one in the form of its 10,10′, 9,9′ or 9,10 isomers and at least one plastic, preferably at least one thermoplastic, more preferably at least one plastic from the group consisting of vinyl polymers, polyesters, polyolefins and polyamides. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylates or polyvinyl chloride. Preferred polyesters are polyethylene terephthalate, polybutylene terephthalate, polycarbonates or cellulose esters. Preferred polyamides are nylon-6 or nylon-6,6.

[0088] Preferred are those extruded, blow-molded or injection-molded products, preferably for food contact, which are based on the unsubstituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthalpyrin-12-one.

[0089] Particularly preferred are extruded, blow-molded or injection-molded products, preferably extruded, blow-molded or injection-molded products for food contact, which are based on the unsubstituted 10,10′, 9,9′ or 9,10 isomers of sulfonylbis-12H-phthalopyrin-12-one and have a color distance ΔE of <20 from the L*a*b* coordinates of the color model in EN ISO 11664-4 to the color numbers starting with “3” on the RAL color chart. Very particular preference is given to extruded, blow-molded or injection-molded products which additionally have a yellow hue defined by a*>0 and b*≥25, which means that the following applies to the hue angle h: h° 最小值 =14° and h° 最大值 <90°, including all color positions in between. DETAILED DESCRIPTION

[0090] Examples

[0091] Example 1

[0092] 63g of phenol was melted at a temperature of 80°C. 5.27g (32.7mmol) of 1,8-diaminonaphthalene was added thereto, and the mixture was stirred for 30 minutes. Subsequently, 6.32g (16.8mmol) of 5,5-sulfonylbis(isobenzofuran-1,3-dione) was introduced. This reaction mixture was heated to 135°C and maintained at this temperature for 6 hours, and the resulting reaction water was distilled off. The reaction mixture was then cooled to 100°C within 1.5h, and 65g of methanol was added. The reaction mixture was further stirred for 10 hours and cooled to 30°C. The reaction product was separated using a suction filter and first washed with 40g of methanol and then with 400g of water. After drying in a vacuum drying cabinet at 80° C. and 150 mbar, an isomer mixture comprising predominantly 10,10′-sulfonylbis-12H-phthalopyrin-12-one of the formula (II) was obtained in a yield of 99% with a red color close to RAL 3028.

[0093]

[0094]

[0095] The sulfonyl-bridged 10,10'-sulfonylbis-12H-phthalopyrin-12-one dye of formula (II) as shown in the reaction scheme represents only one form of the possible isomers that may occur in the synthesis.

[0096] As a demonstration of the improved properties described herein, corresponding polymer compositions were first produced by compounding polycarbonate (polymer composition 1) and nylon-6 (polymer composition 2) with 10,10'-sulfonylbis-12H-phthalopyrin-12-one and its isomers. To this end, the individual components were mixed in a twin-screw extruder (Leistritz LSM 30-34 from Leistritz AG (Nuremberg, Germany) at temperatures between 240°C and 260°C, extruded, cooled until pelletizable, and granulated. After drying (typically at 80°C in a vacuum drying cabinet for two days), these pellets were processed by injection molding at temperatures ranging from 240°C to 300°C to produce standard test specimens for the corresponding tests.

[0097] In the context of the present invention, a 60·40·2 mm thick film based on thermoplastic polycarbonate and nylon-6 is used according to standard DIN 53775-3. 3 The migration of 10,10'-sulfonylbis-12H-phthalopyrin-12-one and its isomers was examined. This was done by using a 10,10'-sulfonylbis-12H-phthalopyrin-12-one with the empirical formula C 36 H 18 The sulfonyl-bridged pyrenone-stained test specimen of N4O4S was clamped at a pressure of 4 N / cm 2 The migration was accomplished by applying a pressure of 1 100 nm between two uncolored test specimens at a temperature of 80° C. for 24 h and then visually assessing the migration based on the dye residue on the initially colorless test specimens.

[0098] Also in the context of the present invention, the thermal stability of the molding compounds described in Table 1 which have been pigmented with 10,10′-sulfonylbis-12H-phthalopyrin-12-one and its isomers is determined by 60·40·2 mm 3 The panels were evaluated according to standard DIN EN 12877.

[0099] Component A): Polycarbonate ( 2800, from Covestro AG (Germany)

[0100] Component B): Nylon-6 ( B30S, from Lanxess Deutschland GmbH (Cologne, Germany)

[0101] Component C): Isomers of 10,10′-sulfonylbis-12H-phthalpyrin-12-one according to Example 1

[0102] Table 2

[0103]

[0104] The results in Table 2 for 10,10′-sulfonylbis-12H-phthalopyrin-12-one and its isomers do not show any significant migration into or out of polymer compositions 1 and 2, and the polymer plates based on 10,10′-sulfonylbis-12H-phthalopyrin-12-one and its isomers, as well as polycarbonate and nylon-6, are noteworthy for their very high thermal stability, which extends to the processing limits of the polymer compositions examined.

Claims

1. A sulfonyl-bridged pyrenone of formula (I) or an isomeric form thereof It is characterized in that R is C1-C6-alkyl, aryl, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group.

2. The sulfonyl-bridged pyrenone according to claim 1, characterized in that R is a group 3. The sulfonyl-bridged pyrenone according to claim 1 or 2, characterized in that At least one of the benzene rings has at least one substituent selected from the group consisting of chlorine, bromine, nitro, methoxy, NH2, benzyloxy, hydroxyl, -SO2O(C6H5), -SO2N(CH3)2, -SO2NHCH3, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, NHCOCH3, -N(C2H5)2 and phenyl.

4. Sulfonyl-bridged pyrenone according to one or more of claims 1 to 3, characterized in that The sulfonyl-bridged pyrenone is 10,10'-sulfonylbis-12H-phthalpyrin-12-one.

5. Sulfonyl-bridged pyrenone according to one or more of claims 1 to 4, characterized in that These sulfonyl-bridged pyrenones have a color distance ΔE of <20 from the L*a*b* coordinates of the red color numbers starting with "3" on the RAL color card.

6. The sulfonyl-bridged pyrenone according to claim 5, characterized in that These sulfonyl-bridged pyrenones have a yellow hue where a*>0 and b*≥25.

7. Use of sulfonyl-bridged pyrenones of formula (I) or isomeric forms thereof for the bulk coloring of plastics, in R is C1-C6-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C1-C6-alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group.

8. The use of the sulfonyl-bridged pyrenone according to claim 7, characterized in that At least one of the benzene rings has at least one substituent from the following group: chlorine, bromine, nitro, methoxy, NH2, benzyloxy, hydroxyl, -SO2O(C6H5), -SO2N(CH3)2, -SO2NHCH3, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, NHCOCH3, -N(C2H5)2 or phenyl.

9. The use of the sulfonyl-bridged pyrenone according to claim 7 or 8, characterized in that The sulfonyl bridge is disubstituted by the same group.

10. The use of the sulfonyl-bridged pyrenone according to claim 9, characterized in that This sulfonyl bridge bridges two identical 12H-phthalopyrin-12-one groups to one another.

11. The use of the sulfonyl-bridged pyrenone according to claim 10, characterized in that The sulfonyl-bridged pyrenone is 10,10'-sulfonylbis-12H-phthalpyrin-12-one.

12. Use according to one or more of claims 7 to 11, characterized in that The plastics to be colored are thermoplastics for extrusion, blow molding or injection molding, preferably vinyl polymers, polyesters, polyolefins or polyamides.

13. The use according to claim 12, characterized in that Polyolefin means polyethylene or polypropylene, vinyl polymer is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile terpolymer, polymethacrylate or polyvinyl chloride, polyester means polyethylene terephthalate, polybutylene terephthalate, polycarbonate or cellulose ester, and polyamide is nylon-6 or nylon-6,6.

14. Use according to one or more of claims 7 to 13, characterized in that At the same time, the migration properties in these plastics, measurable according to DIN 53775-3, are reduced.

15. Use according to one or more of claims 7 to 13, characterized in that At the same time, the thermal stability of the dyes in these plastics, which can be determined according to DIN EN 12877, increases.

16. A process for producing a sulfonyl-bridged pyrenone of formula (I) or an isomeric form thereof, in R is C1-C6-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C1-C6-alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group, It is characterized in that The sulfonyl-substituted isobenzofurandione is reacted with at least one aromatic diamine selected from the group consisting of naphthalene-1,8-diamine, chloronaphthalene-1,8-diamine, dichloronaphthalene-1,8-diamine, methylnaphthalene-1,8-diamine, dimethylnaphthalene-1,8-diamine, methoxynaphthalene-1,8-diamine, ethoxynaphthalene-1,8-diamine, acetamidonaphthalene-1,8-diamine and 1,8-diaminoacenaphthylene, preferably naphthalene-1,8-diamine.

17. An extruded, blow-molded or injection-molded product based on at least one sulfonyl-bridged pyrenone of formula (I) or an isomer thereof in R is C1-C6-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C1-C6-alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group, and At least one plastic, preferably at least one thermoplastic, more preferably at least one plastic from the group consisting of vinyl polymers, polyesters, polyolefins and polyamides.

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