Sulfonyl-bridged perinones

Abstract

To provide sulfonyl-bridged perinones.SOLUTION: The invention relates to sulfonyl-bridged perinones in the form of compounds of the general formula (I) or isomeric forms thereof in which 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-on cycloaliphatic or heterocyclic group, to a process for production thereof and to the use thereof for bulk colouring of plastics.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to sulfonyl-bridged perinones and their isomeric forms, processes for their preparation, and their use in plastic-based injection-molded products, especially injection-molded products for the food industry. [Background technology]

[0002] Plastics that can be processed by injection molding find wide application in the food industry. For example, US Pat. No. 5,623,999 teaches the use of polyamides to manufacture cans for food and beverages.

[0003] Patent Document 2 describes the use of polyethylene terephthalate (PET) for producing beverage bottles by blow molding, in particular by injection blow molding or stretch blow molding. In principle, polyesters such as PET can be processed by injection molding, extrusion, or film blow molding, respectively. BASF SE offers a highly flowable polybutylene terephthalate specially developed for food packaging purposes in the form of Ultradur® B1520 FC R01 (FC = Food Contact), which is notable for its stiffness, strength, and thermal and chemical stability.

[0004] However, plastic-based articles that come into contact with food may be colored with dyes for aesthetic reasons or to otherwise distinguish their contents, but at present, due to suspicions that they may be harmful to health, dyes that have been conventionally used up to now are no longer desirable in sensitive applications, such as in contact with food (Non-Patent Document 1).

[0005] Patent Document 3 discloses, inter alia, optionally substituted benzenesulfonyl-bridged phthaloperinone dyes based on optionally substituted 1,8-diaminonaphthalene for bulk coloring plastics. By dissolving and homogeneously mixing these phthaloperinone dyes in the monomer components of plastics, transparent or muted bright orange-purple colors with good heat resistance and good light and weather resistance are obtained. Patent Document 3 makes no mention of the use of such phthaloperinone dyes in plastic-based injection-molded products, especially those for the food industry. The benzenesulfonyl-bridged phthaloperinone dyes described in Patent Document 3 are not red in color. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] European Patent Application Publication No. 0 366 382 A1 [Patent Document 2] International Publication No. 2019 / 069292A1 Brochure [Patent Document 3] DE 43 27 855 A1 [Non-patent literature]

[0007] [Non-Patent Document 1] C.Barciela et al.,Food and Chemical Toxicology,Volume 178,August 2023,113935,page1~12 Summary of the Invention [Problem to be solved by the invention]

[0008] The object of the present invention was therefore firstly to provide novel red dyes which have high thermal stability for co-processing with plastics by injection moulding methods, but at the same time have low migration properties compared to dyes customarily used in plastics that come into contact with food. [Means for solving the problem]

[0009] That object is achieved by the subject matter of the present invention, which is in the form of a sulfonyl-bridged perinone of general formula (I) or an isomer thereof, [ka] During the ceremony, R is C1-C6-alkyl, aryl, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused-on alicyclic or heterocyclic group.

[0010] More particularly, the object is achieved by the subject matter of the invention in the form of the 10,10', 9,9' or 9,10 isomers of sulfonylbis-12H-phthaloperin-12-ones, which may be optionally substituted.

[0011] Apart from their red color, the sulfonyl-bridged perinones of formula (I) and their isomeric forms, in particular the 10,10', 9,9', or 9,10 isomers of optionally substituted sulfonylbis-12H-phthaloperin-12-one, surprisingly have particularly high thermal stability, making them particularly suitable for use in the injection molding of plastics. In addition, they are notable for their particularly low tendency to migrate into or out of plastics, compared to dyes commonly used in the food industry, such as those described in C. Barciela et al., Food and Chemical Toxicology, Volume 178, August 2023, 113935, pages 1-12. Thermal stability is an important prerequisite for dyes used in plastics that can be molded by injection molding. In the injection molding process, a polymer melt is forced at high pressures, typically in the range of 500-2000 bar and temperatures in the range of 200°C-300°C, through a gate or a system of gates in an injection mold in the form of an open-ended extrusion die and a molding cavity; see: https: / / www.kunststoffe.de / a / grundlagenartikel / spritzgiessen-254055.

[0012] For clarity, it should be noted that the scope of the present invention encompasses all definitions and parameters cited below as general or preferred ranges in any desired combination. This also relates to the combination of the stated amounts of the individual components in the processes and uses described in the present invention. Unless otherwise specified, standards cited in connection with this application refer to the latest edition as of the filing date of the present application. Unless otherwise specified, the stated percentages are weight percents. The peri arrangement actually refers to the 1,8 coordination in naphthalene. This connotation of peri arrangement also applies to arylenes having three or more mutually fused benzene rings, both in the literature and in the context of this application.

[0013] An aryl or aryl group, abbreviated as Ar, is an organic chemical group with an aromatic-based backbone. Thus, aryl is a general term for a single atom radical derived from an aromatic hydrocarbon by removing one hydrogen atom attached to the ring. Most aryl groups are derived from benzene (CH), and the simplest aryl group (which is preferred in this invention) is the phenyl group (Ph, i.e., -CH).

[0014] An alkyl or alkyl group is a part of a molecule consisting of carbon and hydrogen atoms bonded together. The simplest alkyl group is the methyl group (-CH3). Further alkyl groups preferred in the present invention are the ethyl group (-CH2-CH3) or the n-propyl group (-CH2-CH2-CH3). The general formula for an alkyl group in the form of a chain is C n H 2n+1 is.

[0015] 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, or carboxylic acids, or carboxylic acid derivatives, especially carbonyl chlorides, where formally an OH group, a hydrogen atom, or a chlorine atom is replaced by a radical.

[0016] For the sake of clarity, it should be noted that formula (I) represents only one of several possible isomers. While formula (I) represents only one of several possible isomers, an isomer, according to https: / / de.wikipedia.org. / wiki / Isomerie, represents the existence of two or more compounds that have the same empirical formula and molecular mass but differ in the bonding or spatial arrangement of atoms, and thus can be represented by different structural formulas. The sulfonyl-bridged perinones of formula (I) of the present invention are positional isomers, meaning that the same functional group can be located at different positions, in this case the 9- or 10-position of the perinone structure. For the sake of clarity, it should also be noted that the optionally substituted sulfonylbis-12H-phthaloperin-12-ones that are particularly preferred in the present invention take the form of their 10,10', 9,9', or 9,10 isomers.

[0017] The terms "optionally substituted" or "unsubstituted" in the context of the present invention relate to the optionally substituted or unsubstituted naphthalene-1,8-diamine or naphthyl group used in the process of the present invention, or to the two naphthyl groups present in the sulfonyl-bridged perinone of formula (I) of the present invention or the particularly preferred sulfonylbis-12H-phthaloperin-12-one. The two naphthyl groups may preferably carry from one to up to 12 identical or different substituents. In this case, the naphthalene-1,8-diamine used in the process of the present 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 following groups: chlorine, bromine, nitro, methoxy, NH, benzyloxy, hydroxy, -SOO(CH), -SON(CH), -SONHCH, methyl, ethyl, n-propyl, isopropyl, n-, sec-, tert-butyl, NHCOCH, -N(CH), and phenyl. DETAILED DESCRIPTION OF THE INVENTION

[0018] Preferred Embodiments of the Invention Preferred isomers or isomeric forms of 10,10'-sulfonyl-bridged perinone in the present invention are 9,9'-sulfonyl-bridged perinone, 10,9-sulfonyl-bridged perinone, and 9,10-sulfonyl-bridged perinone.

[0019] Particularly preferred isomers or isomeric forms of optionally substituted sulfonylbis-12H-phthaloperin-12-one of the present invention are optionally substituted 10,10'-sulfonylbis-12H-phthaloperin-12-one, optionally substituted 9,10-sulfonylbis-12H-phthaloperin-12-one, and optionally substituted 9,9-sulfonylbis-12H-phthaloperin-12-one.

[0020] The present invention preferably relates to unsubstituted 10,10'-sulfonylbis-12H-phthaloperin-12-one of formula (II), unsubstituted 9,10-sulfonylbis-12H-phthaloperin-12-one of formula (III), and unsubstituted 9,9-sulfonylbis-12H-phthaloperin-12-one of formula (IV). [ka]

[0021] The substituted isomers of sulfonylbis-12H-phthaloperin-12-one of formulas (II), (III), and (IV), which are particularly preferred in the present invention, are notable for having at least one substituent on at least one of the two naphthyl groups. These two naphthyl groups may preferably have from 1 to a maximum of 12 identical or different substituents. Preferred substituents are to be selected from the following groups: chlorine, bromine, nitro, methoxy, NH, benzyloxy, hydroxy, -SO(C6H5), -SON(CH3), -SONHCH3, methyl, ethyl, n-propyl, isopropyl, n-, sec-, tert-butyl, NHCOCH3, -N(C2H5)2, and phenyl.

[0022] In the context of the present invention, preferred plastics are those used in injection molding, extrusion, or blow molding, especially injection molding. They 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, polycarbonates, or cellulose esters. Preferred polyamides are nylon-6 or nylon-6,6.

[0023] The present invention relates preferably to sulfonyl-bridged perinones of general formula (I) or isomers thereof, which have a color difference ΔE of less than 20 in the L*a*b* coordinates from the color number starting with "3" on the RAL color chart, [ka] In the formula, 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.

[0024] The present invention is more preferably directed to a compound in which R is of the formula: [ka] or an isomer thereof.

[0025] In an alternative or preferred embodiment, the present invention relates to sulfonyl-bridged perinones of formula (I) in which at least one of the phenyl rings in the perinone structure bears at least one substituent from the following group: chlorine, bromine, nitro, methoxy, NH, benzyloxy, hydroxy, —S0(C6H5), —S0N(CH3), —S0NHCH3, methyl, ethyl, n-propyl, isopropyl, n-, sec-, tert-butyl, NHCOCH3, —N(C2H5)2, or phenyl.

[0026] Preferably, the sulfonyl group bridges two identical perinone structures. Very particularly preferred in the present invention is a sulfonyl group bridging two 12H-phthaloperin-12-one groups to each other, where 12H-phthaloperin-12-one itself is also known from EP 1 245 645 A1 as Solvent Orange 60 dye [CAS No. 6925-69-5]. Its synthesis is described in EP 780 444 A2, Example 1. The sulfonyl-bridged result of two 12H-phthaloperin-12-one groups in the present invention is represented by the empirical formula C, which is very particularly preferred in the present invention. 36 H 18 Sulfonyl-bridged perinone dyes of formula (II) with N4O4S are 10,10'-sulfonylbis-12H-phthaloperin-12-one and their isomers. [ka]

[0027] Preferred isomers of 10,10'-sulfonylbis-12H-phthaloperin-12-one in the present invention are 9,9'-sulfonylbis-12H-phthaloperin-12-one, 10,9-sulfonylbis-12H-phthaloperin-12-one, and 9,10-sulfonylbis-12H-phthaloperin-12-one.

[0028] In the context of the present invention, red is understood to mean any color in the RAL color system described at https: / / de.wikipedia.org / wiki / RAL-Farbe#Rot that has a color number on the RAL color chart starting with "3." More specifically, at the time of filing the present application, the following distinctions are made between red hues:

[0029] [Table 1]

[0030] This table gives the device-independent CIE L values ​​for each RAL value for red. * a * b * The color values ​​are shown here, but the L * represents the brightness, and a * indicates the color coordinate on the red-green axis, and b * represents the color coordinates on the yellow-blue axis. The color model is based on EN ISO 11664-4 "Colorimetry - Part 4: CIE 1976, L * a * b * It is standardized in the "Color Space". * a * b *For more information on color spaces (and more specifically: CIELAB), see: https: / / de.wikipedia.org / wiki / Lab-Farbraum. Each color in the color space is represented by a rectangular coordinate system, L * , a * , b *}. Therefore, a * b * The coordinate plane is constructed using opponent color theory: green and red are opposite each other, a * Located at both ends of the axis, from blue to yellow is b * The axis. Complementary hues are on opposite sides of each other at an angle of 180°, and all achromatic colors are centered between them (the coordinate origin, a * =0, b * =0).

[0031] L * The axis represents the brightness (intensity) of the color, with a value from 0 to 100. In the coordinate system, it is a * b * It stands perpendicular to the surface. It can also be called the neutral gray axis, because all achromatic colors (gray hues) are connected to the black (L * =0) and White (L * = 100). * The axis indicates the green or red component of the color, where negative values ​​represent green and positive values ​​represent red. * The axis represents the blue or yellow component of the color, where negative values ​​represent blue and positive values ​​represent yellow.

[0032] a * The value is between approximately -170 and +100, b * The values ​​span between -100 and +150, but their maximum value is only achieved at mid-luminance for certain hues. The CIELAB color space has its maximum range in the mid-luminance region, but this varies in height and magnitude depending on the color range.

[0033] However, in the present invention, red-like hues having a color difference ΔE of less than 20 in the L*a*b* coordinates from color numbers starting with "3" on the RAL color chart for red are also included.

[0034] Preferred in the present invention are red sulfonyl-bridged perinones of general formula (I) or isomers thereof, which have a color difference ΔE of less than 20 in the L*a*b* coordinates from the color numbers starting with "3" on the RAL color chart for red, and * >0 and b * ≧25. Therefore, the following applies for the hue angle h: minimum = 14 degrees and h° maximum < 90 degrees (including all colour loci in between).

[0035] Particularly preferred are the 10,10', 9,9' or 9,10 isomers of optionally substituted sulfonylbis-12H-phthaloperin-12-ones, which have a color difference ΔE of less than 20 in the L*a*b* coordinates from the color numbers starting with "3" on the RAL color chart, according to the color model in EN ISO 11664-4. According to the color model in EN ISO 11664-4, the color numbers starting with "3" on the RAL color chart represent red.

[0036] Specifically, particularly preferred are those having a color difference ΔE of less than 20 in the L*a*b* coordinates from the color number starting with "3" on the RAL color chart according to the color model in EN ISO 11664-4, * >0 and b * The 10,10', 9,9', or 9,10 isomer of an optionally substituted sulfonylbis-12H-phthaloperin-12-one having a yellow hue defined as ≧25, which means that the following can apply for the hue angle h: minimum = 14 degrees and h° maximum < 90 degrees (including all color trajectories in between).

[0037] Also particularly preferred are the 10,10', 9,9', or 9,10 isomers of unsubstituted sulfonylbis-12H-phthaloperin-12-ones having a color difference ΔE of less than 20 in the L*a*b* coordinates from the color numbers starting with "3" on the RAL color chart according to the color model in EN ISO 11664-4. According to the color model in EN ISO 11664-4, the color numbers starting with "3" on the RAL color chart represent red.

[0038] Finally, particularly preferred are those which, according to the color model in EN ISO 11664-4, have a color difference ΔE of less than 20 in the L*a*b* coordinates from the color numbers starting with "3" on the RAL color chart, and * >0 and b * The 10,10', 9,9', or 9,10 isomer of unsubstituted sulfonylbis-12H-phthaloperin-12-one has a yellow hue defined as ≧25, which means that the following can apply for the hue angle h: minimum = 14 degrees and h° maximum < 90 degrees (including all color trajectories in between).

[0039] process One possible synthetic route for preparing the sulfonyl-bridged perinones of formula (I) and their isomeric forms is the reaction, i.e., condensation, of a sulfonyl-substituted isobenzofurandione with at least one aromatic diamine from the following group: naphthylene-1,8-diamine, chloronaphthylene-1,8-diamine, dichloronaphthylene-1,8-diamine, methylnaphthylene-1,8-diamine, dimethylnaphthylene-1,8-diamine, methoxynaphthylene-1,8-diamine, ethoxynaphthylene-1,8-diamine, acetamino-1,8-naphthylenediamine, and 1,8-diaminoacenaphthylene. Naphthylene-1,8-diamine is particularly preferred. This synthetic route is particularly suitable for preparing the unsubstituted sulfonyl-bridged perinones of formula (II) and their isomeric forms, which are particularly preferred in the present invention, by reacting 5,5-sulfonylbis(isobenzofuran-1,3-dione) with naphthalene-1,8-diamine.

[0040] It is preferred to use at least 2 moles of optionally substituted aromatic diamine per mole of 5,5-sulfonyl-bridged isobenzofurandione. In some embodiments, more than 2 moles of optionally substituted aromatic diamine can be used, but it is still preferred to use the reactants in stoichiometric amounts.

[0041] Since at least 2 moles of an optionally substituted aromatic diamine are used per mole of sulfonyl-substituted isobenzofurandione to synthesize the sulfonylbis-12H-phthaloperin-12-one of the present invention, it is also possible to prepare sulfonylbis-12H-phthaloperin-12-ones in which the two 1,8-naphthyl groups have different substitutions. In this case, the term "different substitutions" refers to substitutions at different positions on each naphthyl group and / or different substituents on each naphthyl group from the following groups: chlorine, bromine, nitro, methoxy, NH, benzyloxy, hydroxy, -SO(CH), -SON(CH), -SON(CH), -SONHCH, methyl, ethyl, n-propyl, isopropyl, n-, sec-, tert-butyl, NHCOCH, -N(CH), and phenyl. The reactants can be condensed directly by melting the appropriate molar equivalents of the reactants together at temperatures ranging from 120°C to 250°C.

[0042] The reaction is preferably carried out in a solvent at a temperature ranging from 110°C to 220°C, optionally under pressure, whereby the water formed in the reaction can be removed by distillation. The condensation reaction preferably uses at least one solvent selected from the following group: chlorobenzene, o-dichlorobenzene, trichlorobenzene, xylene, dimethylformamide, N-methylpyrrolidone, glacial acetic acid, propionic acid, phenol, cresol, phenoxyethanol, glycols and their mono- and dialkyl ethers, alcohols, especially methanol, ethanol, and i-propanol, water, and aqueous solvents, especially dilute sulfuric acid. The use of phenol is particularly preferred in the present invention.

[0043] In one embodiment, the reaction can be carried out with the addition of at least one acid catalyst, in which case it is preferred to use a catalyst selected from the following group: zinc chloride, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, organic acids.

[0044] To prepare the sulfonyl-bridged perinones of formula (I) and their isomeric forms, in particular the optionally substituted sulfonylbis-12H-phthaloperin-12-ones in the form of their 10,10', 9,9', or 9,10 isomers, it is preferred to work up the reaction mixture by dilution with an alcohol, preferably methanol, ethanol, propanol, or butanol. Aromatic diluents, preferably chlorobenzene or toluene, can also be used. The process of the present invention preferably provides the sulfonyl-bridged perinones of formula (I) and their isomeric forms in yields of 85% to 95% of the theoretical yield.

[0045] The sulfonyl-bridged perinones of formula (I) and their isomeric forms, in particular the optionally substituted sulfonylbis-12H-phthaloperin-12-ones in the form of their 10,10', 9,9', or 9,10 isomers, of the present invention have excellent applicability for bulk coloring of plastics. By "bulk coloring" is meant more specifically here either the incorporation of the dye into the molten plastic material, preferably using an extruder, or the direct addition of the dye to the reactants for producing the particular plastic, preferably the respective monomers prior to polymerization.

[0046] Particularly preferred plastics for coloring by means of the sulfonyl-bridged perinones of formula (I) and their isomeric forms according to the present invention, especially by means of the sulfonylbis-12H-phthaloperin-12-ones in the form of their optionally substituted 10,10', 9,9', or 9,10 isomers, are thermoplastics usable in injection molding processes, preferably vinyl polymers, polyesters, polyolefins, or polyamides, especially 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, polycarbonates, or cellulose esters. Preferred polyamides are nylon-6 or nylon-6,6.

[0047] Very particularly preferred plastics for coloring by means of the sulfonyl-bridged perinones of formula (I) according to the invention and of the appropriate isomers, in particular by means of the sulfonylbis-12H-phthaloperin-12-ones in the form of their 10,10', 9,9' or 9,10 isomers, which may be optionally substituted, are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylate, polyethylene terephthalate, nylon-6 or nylon-6,6.

[0048] The sulfonyl-bridged perinones of formula (I) and the appropriate isomeric forms, in particular the optionally substituted sulfonylbis-12H-phthaloperin-12-ones in the form of their 10,10', 9,9' or 9,10 isomers, used as dyes in the present invention are preferably employed in finely dispersed form, optionally with the additional use of at least one dispersing agent.

[0049] When the sulfonyl-bridged perinones of formula (I) and the appropriate isomeric forms thereof, particularly in the form of their 10,10', 9,9', or 9,10 isomers, used as dyes in the present invention, are used after the polymerization of the respective plastic, it is preferred to dry mix or grind them with the pelletized plastic and then plasticize and homogenize the mixture in a mixing roll or screw system. Alternatively, the sulfonyl-bridged perinones of formula (I) and the isomeric forms thereof, particularly in the form of their 10,10', 9,9', or 9,10 isomers, used as dyes in the present invention, can be added to the molten plastic material and homogenously dispersed therein by stirring. Such pre-pigmented plastic is then typically or preferably further processed by spinning to obtain bristles or filaments, or by extrusion, blow molding, or injection molding to obtain molded articles.

[0050] The sulfonyl-bridged perinones of formula (I) and suitable isomers, especially the optionally substituted sulfonylbis-12H-phthaloperin-12-ones in the form of their 10,10', 9,9', or 9,10 isomers, used as dyes in the present invention are stable to polymerization catalysts, especially peroxides, so that they can be added to the monomeric reactants of the respective plastic and then polymerized in the presence of a polymerization catalyst. For this purpose, it is preferred to dissolve or thoroughly mix the sulfonyl-bridged perinones of formula (I) and its isomeric forms, especially the optionally substituted sulfonylbis-12H-phthaloperin-12-ones in the form of their 10,10', 9,9', or 9,10 isomers, of the present invention in the monomeric reactants of the particular plastic. The sulfonyl-bridged perinones of formula (I) and their isomeric forms, in particular the optionally substituted sulfonylbis-12H-phthaloperin-12-ones in the form of their 10,10', 9,9' or 9,10 isomers, according to the invention are preferably used to color the aforementioned plastics or polymers in amounts ranging from 0.0001% to 1% by weight, in particular from 0.01% to 0.5% by weight, in each case based on the amount of plastic or polymer.

[0051] The corresponding useful muted shades can be obtained by adding pigments that are insoluble in certain plastics or polymers, in particular titanium dioxide, which are preferably used in amounts ranging from 0.01% to 10% by weight, preferably from 0.1% to 5% by weight, based on the amount of polymer.

[0052] It is also possible in the present invention to use mixtures of different inventive sulfonyl-bridged perinones and / or mixtures of inventive sulfonyl-bridged perinones of formula (I) and their isomeric forms, in particular mixtures of sulfonylbis-12H-phthaloperin-12-ones, optionally substituted, in the form of their 10,10', 9,9' or 9,10 isomers, together with other dyes and / or inorganic or organic pigments.

[0053] Further Uses The present invention relates to the use of sulfonyl-bridged perinones of formula (I) and corresponding isomers, in particular sulfonylbis-12H-phthaloperin-12-ones in the form of their optionally substituted 10,10', 9,9' or 9,10 isomers, for bulk coloring plastics and simultaneously reducing their migration properties (determinable in accordance with DIN 53775-3) in said plastics.

[0054] The plastic is preferably one that is used in injection molding, extrusion or blow molding processes. The plastic is preferably a vinyl polymer, polyester, polyolefin or polyamide, particularly preferably nylon-6 or polycarbonate.

[0055] They are preferred if they are plastics suitable for injection molding. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile terpolymer, polymethacrylate, or polyvinyl chloride. Preferred polyesters are polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or cellulose ester. Preferred polyamides are nylon-6 or nylon-6,6.

[0056] The use preferably relates to a sulfonyl-bridged perinone of formula (I) or an isomer thereof, in which R is the following group: [ka] Particularly preferred is the use of 10,10'-sulfonylbis-12H-phthaloperin-12-one and its isomers. In this case, it is particularly preferred that all naphthyl groups are unsubstituted. The use therefore preferably relates to the unsubstituted 10,10', 9,9', or 9,10 isomer of sulfonylbis-12H-phthaloperin-12-one. Alternatively, the present invention also relates to the use of sulfonyl-bridged perinones of formula (I) and corresponding isomers, in particular the use of optionally substituted sulfonylbis-12H-phthaloperin-12-one in the form of their 10,10', 9,9', or 9,10 isomers, as dyes for bulk coloring plastics and simultaneously improving the thermal stability (determinable according to DIN EN 12877) of polymer compositions based on the dye in those plastics. These plastics are preferably suitable for injection molding, blow molding, or extrusion, particularly 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, polycarbonates, or cellulose esters. Preferred polyamides are nylon-6 or nylon-6,6.

[0057] The use preferably relates to sulfonyl-bridged perinones of formula (I) or isomers thereof, in which R is the following group: [ka] Particularly preferred is 10,10'-sulfonylbis-12H-phthaloperin-12-one and its isomers.

[0058] The present invention preferably relates to the use of the 10,10', 9,9' or 9,10 isomer of optionally substituted sulfonylbis-12H-phthaloperin-12-one for the bulk coloration of plastics to achieve a color difference ΔE of less than 20 in the L*a*b* coordinates from the color numbers starting with "3" on the RAL color chart, according to the color model in EN ISO 11664-4. The color numbers starting with "3" on the RAL color chart represent red.

[0059] Preferably, a color difference ΔE of less than 20 is achieved in the L*a*b* coordinates from the color numbers starting with "3" on the RAL color chart according to the color model in EN ISO 11664-4, and * >0 and b * The use of the 10,10', 9,9' or 9,10 isomer of optionally substituted sulfonylbis-12H-phthaloperin-12-one for bulk coloring plastics to have a yellow hue defined as ≧25, which means that for the hue angle h, the following can apply: h° minimum = 14 degrees and h° maximum < 90 degrees (including all color trajectories in between).

[0060] Particularly preferred is the use of optionally substituted 10,10', 9,9' or 9,10 isomers of sulfonylbis-12H-phthaloperin-12-one for bulk coloring plastics in order to achieve a color difference ΔE of less than 20 in the L*a*b* coordinates from color numbers starting with "3" on the RAL color chart according to the color model in EN ISO 11664-4, while at the same time improving the thermal stability (measurable according to DIN EN 12877) of polymer compositions based on these isomers of sulfonylbis-12H-phthaloperin-12-one in plastics, where in the context of the present invention the improvement in thermal stability observed in plastics is considered within the processing limits of the thermal stability of the polymer compositions considered.

[0061] These plastics are again preferably for injection molding, blow molding, or extrusion, particularly injection molding. The plastics are again preferably vinyl polymers, polyesters, polyolefins, or polyamides, particularly preferably nylon-6 or polycarbonate. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are again 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 again nylon-6 or nylon-6,6. This use also preferably relates to unsubstituted 10,10'-sulfonylbis-12H-phthaloperin-12-one and its 9,9' and 9,10 isomers.

[0062] product Finally, the present invention further provides at least one sulfonyl-bridged perinone of general formula (I) or its isomeric forms, [ka] [In the formula, 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 At least one plastic, preferably at least one thermoplastic, more preferably at least one plastic from the group of vinyl polymers, polyesters, polyolefins, and polyamides The present invention also relates to extrusion-molded, blow-molded, or injection-molded products based on the above. Preferred polyolefins are polyethylene or polypropylene. Preferred vinyl polymers are polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile terpolymer, polymethacrylate, or polyvinyl chloride. Preferred polyesters are polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or cellulose ester. Preferred polyamides are nylon-6 or nylon-6,6.

[0063] Preferably, R is a group [ka] and extrusion-, blow- or injection-molded products based on sulfonyl-bridged perinones of general formula (I) or their isomers. Very particular preference is given to extrusion-, blow- or injection-molded products based on 10,10'-sulfonylbis-12H-phthaloperin-12-one and its isomers.

[0064] More specifically, the present invention relates to extruded, blown, or injection-molded products, preferably food contact extruded, blown, or injection-molded products, based on at least one optionally substituted sulfonylbis-12H-phthaloperin-12-one in the form of its 10,10', 9,9', or 9,10 isomer, 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.

[0065] Preferred are those extruded, blow-molded, or injection-molded products based on the 10,10', 9,9', or 9,10 isomer of unsubstituted sulfonylbis-12H-phthaloperin-12-one, preferably extruded, blow-molded, or injection-molded products that come into contact with food.

[0066] Particularly preferred are extrusion-, blow- or injection-molded products, preferably food-contact extrusion-, blow- or injection-molded products, based on the 10,10', 9,9' or 9,10 isomer of unsubstituted sulfonylbis-12H-phthaloperin-12-one, which have a color difference ΔE of less than 20 in the L*a*b* coordinates according to the color model in EN ISO 11664-4 from the color numbers starting with "3" on the RAL color chart. Very particular preference is given to extrusion-, blow- or injection-molded products, preferably food-contact extrusion-, blow- or injection-molded products, which in addition are * >0 and b *Those extruded, blow molded, or injection molded products having a yellow hue defined as a hue angle, h°, of ≥ 25, which means that the following formula is applicable for the hue angle, h°: minimum = 14 degrees and h° maximum < 90 degrees (including all color trajectories in between). [Example]

[0067] Example 1 63 g of phenol was melted at a temperature of 80°C. 5.27 g (32.7 mmol) of 1,8-diaminonaphthalene was added, and the mixture was stirred for 30 minutes. 6.32 g (16.8 mmol) of 5,5-sulfonylbis(isobenzofuran-1,3-dione) was then introduced. The reaction mixture was heated to 135°C and maintained at this temperature for 6 hours, with the water produced in the reaction being distilled off. The reaction mixture was then cooled to 100°C within 1.5 hours, and 65 g of methanol was added. The reaction mixture was stirred for an additional 10 hours and cooled to 30°C. The reaction product was isolated using a suction funnel and washed first with 40 g of methanol and then with 400 g of water. After drying in a vacuum drying cabinet at 80°C and 150 mbar, an isomeric mixture essentially containing 10,10'-sulfonylbis-12H-phthaloperin-12-one of formula (II) was obtained in 99% yield and had a red color similar to that of RAL3028. [ka]

[0068] The sulfonyl-bridged 10,10'-sulfonylbis-12H-phthaloperin-12-one dye of formula (II), as shown in the reaction scheme, represents only one form of isomer that may be produced in this synthesis.

[0069] To demonstrate the performance improvements described herein, corresponding polymer compositions were first prepared by compounding polycarbonate (polymer composition 1) and nylon-6 (polymer composition 2) with 10,10'-sulfonylbis-12H-phthaloperin-12-one and its isomers. The individual components were mixed in a twin-screw extruder (Leistritz LSM 30-34, Leistritz AG, Nuremberg, Germany) at temperatures between 240°C and 260°C, extruded, cooled until pelletizable, and pelletized. After drying (typically at 80°C for 2 days in a vacuum drying cabinet), the pellets were processed by injection molding at temperatures ranging from 240°C to 300°C to obtain standard test specimens for the respective tests.

[0070] In the context of the present invention, the migration of 10,10'-sulfonylbis-12H-phthaloperin-12-one and its isomers was measured in accordance with standard DIN 53775-3 on a 60 x 40 x 2 mm 3D glass tube based on the thermoplastics polycarbonate and nylon-6. 3 This was tested using a plaque of the empirical formula C 36 H 18 A specimen dyed with sulfonyl-bridged perinone with N4O4S was placed between two undyed specimens at a pressure of 4 N / cm 2 The test was carried out by clamping at a temperature of 80° C. for 24 hours, and the migration due to dye residue on the initially colorless test specimens was evaluated visually.

[0071] The thermal stability of the molding compounds pigmented with 10,10'-sulfonylbis-12H-phthaloperin-12-one and its isomers as described in Table I, as well as in the context of the present invention, was determined according to the standard DIN EN 12877 in a 60 x 40 x 2 mm 3 The results were evaluated by means of a plaque.

[0072] Component A): Polycarbonate (Makrolon® 2800, manufactured by Covestro AG, Germany) Component B): Nylon-6 (Durethan® B30S, manufactured by Lanxess Deutschland GmbH (Cologne, Germany)) Component C): Isomer of 10,10'-sulfonylbis-12H-phthaloperin-12-one described in Example 1

[0073] [Table 2]

[0074] The results in Table 2 for 10,10'-sulfonylbis-12H-phthaloperin-12-one and its isomers show no visible migration into or out of polymer compositions 1 and 2, and polymer plaques based on 10,10'-sulfonylbis-12H-phthaloperin-12-one and its isomers, as well as polycarbonate and nylon-6, are characterized by extremely high thermal stability, up to the processing limits of the tested polymer compositions.

Claims

1. General formula (I) or its isomeric forms: 【Chemical Formula 1】 [In the formula, R is C １ ~C ６ -alkyl, aryl, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group. of sulfonyl-bridged perinones.

2. R is, 【Chemistry 2】 2. The sulfonyl-bridged perinone of claim 1, wherein the perinone is a group represented by the formula:

3. At least one phenyl ring is selected from the group consisting of chlorine, bromine, nitro, methoxy, NH ２ , benzyloxy, hydroxy, -SO ２ O (C ６ H ５ ), -SO ２ N (CH ３ ) ２ , -SO ２ NHCH ３ , methyl, ethyl, n-propyl, isopropyl, n-, sec-, tert-butyl, NHCOCH ３ , -N(C ２ H ５ ) ２ 3. The sulfonyl-bridged perinone according to claim 1 or 2, characterized in that it has at least one substituent from the group consisting of phenyl and phenyl.

4. The sulfonyl-bridged perinone according to any one of claims 1 to 3, characterized in that it is 10,10'-sulfonylbis-12H-phthaloperin-12-one.

5. 5. The sulfonyl-bridged perinones according to any one of claims 1 to 4, characterized in that they have a color difference ΔE of less than 20 in the L*a*b* coordinates from color numbers starting with "3" on the RAL color chart for red.

6. a ＊ >0 and b ＊ 6. The sulfonyl-bridged perinone of claim 5, characterized in that it has a yellow hue of ≧25.

7. Formula (I) or its isomeric forms for bulk coloring plastics: 【Chemistry 3】 [In the formula, R is C １ ~C ６ -Alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C １ ~C ６ -alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group. The use of sulfonyl-bridged perinones.

8. At least one phenyl ring is selected from the group consisting of chlorine, bromine, nitro, methoxy, NH ２ , benzyloxy, hydroxy, -SO ２ O (C ６ H ５ ), -SO ２ N (CH ３ ) ２ , -SO ２ NHCH ３ , methyl, ethyl, n-propyl, isopropyl, n-, sec-, tert-butyl, NHCOCH ３ , -N(C ２ H ５ ) ２ 8. Use of sulfonyl-bridged perinones according to claim 7, characterized in that they have at least one substituent from the group of: or phenyl.

9. Use of sulfonyl-bridged perinones according to claim 7 or 8, characterized in that the sulfonyl-bridges in formula (I) are disubstituted by identical groups.

10. 10. Use of a sulfonyl-bridged perinone according to claim 9, characterized in that the sulfonyl-bridge in formula (I) bridges two identical 12H-phthaloperin-12-one groups together.

11. Use of a sulfonyl-bridged perinone according to claim 10, characterized in that it is the use of 10,10'-sulfonylbis-12H-phthaloperin-12-one.

12. Use according to any one of claims 7 to 11, characterized in that the plastic to be pigmented is a thermoplastic for extrusion, blow molding or injection molding processes, preferably a vinyl polymer, polyester, polyolefin or polyamide.

13. 13. The use according to claim 12, characterized in that polyolefin means polyethylene or polypropylene, vinyl polymer means 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 any one of claims 7 to 13, characterized in that at the same time the migration properties of the plastics, measurable according to DIN 53775-3, are reduced.

15. Use according to any one of claims 7 to 13, characterized in that at the same time the thermal stability of the dye, measurable according to DIN EN 12877, in the plastic is improved.

16. Formula (I) or its isomeric forms: 【Chemistry 4】 [In the formula, R is C １ ~C ６ -Alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C １ ~C ６ -alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group.

1. A process for preparing a sulfonyl-bridged perinone of formula:

1. A process for preparing a sulfonyl-bridged perinone, comprising reacting a sulfonyl-substituted isobenzofurandione with at least one aromatic diamine selected from the group consisting of naphthylene-1,8-diamine, chloronaphthylene-1,8-diamine, dichloronaphthylene-1,8-diamine, methylnaphthylene-1,8-diamine, dimethylnaphthylene-1,8-diamine, methoxynaphthylene-1,8-diamine, ethoxynaphthylene-1,8-diamine, acetaminonaphthylene-1,8-diamine, and 1,8-diaminoacenaphthylene, preferably naphthylene-1,8-diamine.

17. General formula (I): 【Chemistry 5】 [In the formula, R is C １ ~C ６ -Alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C １ ~C ６ -alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused alicyclic or heterocyclic group. or an isomer thereof, and At least one plastic, preferably at least one thermoplastic, more preferably at least one plastic from the group of vinyl polymers, polyesters, polyolefins, and polyamides Extruded, blow molded or injection molded products based on

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