fluorescent whitening agent
Sustainable FWAs with smaller molecular weights and enhanced biodegradability address the environmental drawbacks of conventional agents, offering high quantum yields and stability.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- THOMAS SWAN & CO LTD
- Filing Date
- 2024-03-07
- Publication Date
- 2026-04-10
AI Technical Summary
Conventional fluorescent whitening agents (FWAs) are non-biodegradable, toxic in aquatic environments, and manufactured from fossil fuels, posing environmental concerns.
Development of FWAs derived from sustainable materials like citric acid, with smaller molecular weights and biodegradable structures, achieving comparable fluorescence performance to industry standards.
The new FWAs exhibit higher quantum yields, improved biodegradability, and stability, reducing environmental impact while maintaining optical brightness.
Smart Images
Figure 2026510770000001_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to fluorescent whitening agents (FWAs), optical brighteners, and specific uses.
Background Art
[0002] Industry standard FWAs in the laundry detergent industry include CAS 16090-02-1 (DAS-1), CAS 16470-24-9 (DAS-2), CAS 27344-41-8 (DSBP), and CAS 4404-43-7 (FB28). These and other conventional FWAs or optical brighteners have one or more of the following drawbacks. 1. Conventionally, they are manufactured from fossil fuels; 2. They are non-biodegradable; 3. They are toxic in the aquatic environment.
[0003] The present invention aims to provide an improved FWA or optical brightener in at least one of these aspects.
[0004] There is a recognition in the prior art that fluorophores can be synthesized from sustainable materials such as citric acid.
[0005] In this regard, RSC Adv., 2015, 5, 34795 discloses 4-oxo-1-thia-3a-aza-6-indanecarboxylic acid and 5-oxo-2,3-dihydro-5H-[1,3]oxazolo[3,2-a]pyridine-7-carboxylic acid via the condensation of citric acid with an amino acid or its derivative, but no potential uses are suggested. The first-mentioned compounds are also disclosed in CN108101929 and CN104530089 in the context of fluorescent imaging agents for medical use.
[0006] J.Mater.Chem.C,2015,3,5976-5984 discloses 1,2,3,5-tetrahydro-5-oxoimidazo[1,2-a]pyridine-7-carboxylic acid) and methyl 4-oxo-1-thia-3a-aza-6-indan carboxylate in connection with the production of fluorescent carbon nanoparticles from the thermal decomposition of citrate and amines. The first of these compounds is also disclosed in CN114507230 for use as a pharmaceutical intermediate. Methyl-4-oxo-1-thia-3a-aza-3,6-indancarboxylic acid is also disclosed in relation to fluorescent carbon nanoparticles in RSC Adv., 2022, 12, 19, 11640-11648 (Table 1 A-B).
[0007] CN109438479 discloses hexyl 4-oxo-1-thia-3a-aza-6-indan carboxylate and certain other indan carboxylate compounds in relation to their potential applications in fluorescence whitening, but does not specify the area of application.
[0008] Dimer and oligomeric indancarboxylate compounds are broadly disclosed in U.S. Patent Application Publication No. 2019 / 231909, but no indication of their applications is given.
[0009] Fluorescent imagers such as 1-(2-hydroxyethyl)-2,6-dioxo-1,3-dihydroisonicotinic acid and 1-oxo-1H-pyrido[2,1-b][1,3]benzothiazole-3-carboxylic acid are disclosed in International Publication No. 2016 / 164437.
[0010] The present invention aims to provide an FWA or optical gloss agent that has functionality comparable to the aforementioned industry standards but with fewer environmental drawbacks. [Overview of the Initiative]
[0011] According to a first aspect of the present invention, a fluorescent whitening agent or optical gloss agent of formula (I) having the following structure, [ka] In the formula, A is CR 1 R 2 (CH2) n and R 1 is H, CH2OH or COZ, and R 2 is H or CH2OH, and n is 1 or 2, or A is an optionally substituted aromatic or heteroaromatic ring condensed with N and X, and N and X are each bonded to adjacent carbon atoms on the ring; X is O, S or N-H; Y is Z or X’L; Each Z is independently OH, OM, OR 3 , O(CH2) q SO3M, NH2, NHOH, NHR 4 or NR 4 2, In the formula, M is selected from alkali metals or alkaline earth metals; R 3 represents a linear or branched alkyl, aryl, aralkyl, aralkyl, linear or branched alkyl alcohol, linear or branched alkyl alcohol polyol, hydroxyalkylamine, polyhydric alcohol, sugar, linear or branched alkyl ether, polyester having 2 to 1000 repeating units, or polyoxyalkylene chain having 2 to 1000 repeating units; q is 1 to 5; Each R 4 is independently selected from methyl, ethyl, propyl, C4-C 12 alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propanol, 1,3-dihydroxy-2-propanol, 2,3-dihydroxypropyl, cyanomethyl, 2-aminoethyl or dicaarbamoylmethyl; or NR 4 2 represents a heterocyclic ring, such as morpholine; and In the formula, when Y is X’L; X’ is O, S or N-H; and A fluorescent whitening agent or optical glossing agent is provided, wherein L represents a linker portion connecting m repeating units of formula I, which has X' defined above instead of Y.
[0012] In embodiments where A is an optionally substituted heteroaromatic ring, A is preferably a pyridine ring.
[0013] R 3 However, in embodiments representing linear or branched alkyl groups, R 3 The compound is preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or 2-ethylhexyl.
[0014] R 3 However, in embodiments representing alkyl alcohols, R 3 The alcohol is preferably selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, dodecanol, or stearyl or oleyl alcohol.
[0015] R 3 However, in embodiments representing an arrow, R 3 is preferably phenyl, and R 3 In embodiments where R represents Alkaline, 3 The compound is preferably selected from benzyl or ethylphenyl.
[0016] R 3 However, in embodiments representing linear or branched alkyl alcohols, R 3 It is preferably selected from 4-hydroxybutyl.
[0017] R 3 However, in embodiments representing linear or branched alcohol polyols, R 3 is preferably a diol or triol. In the most preferred case, R 3 This can be selected from 2,3-dihydroxypropyl or 2-hydroxy-1-(hydroxymethyl)ethyl.
[0018] R 3 However, in embodiments representing hydroxyalkylamines, R 3 The is preferably selected from triethanolamine, N-methyldiethanolamine, or triisopropanolamine.
[0019] R 3 However, in embodiments representing polyhydric alcohols, R 3 It is preferably glycerol.
[0020] R 3 However, in the embodiment representing sugar, R 3 Preferably, it is selected from dextrose, fructose, galactose, glucose, lactose, maltose, or sucrose.
[0021] R 3 However, in embodiments representing linear or branched alkyl ethers, R 2 Preferably, the compound is selected from 2-(2-hydroxyethoxy)ethyl, 2-(2-hydroxy-1-methylethoxy)-1-methylethyl, 2-[2-(2-hydroxy-1-methylethoxy)-1-methylethoxy]-1-methylethyl, 3-(3-hydroxypropoxy)propyl, 3-[3-(3-hydroxypropoxy)propoxy]propyl, 4-(4-hydroxybutoxy)butyl, 4-[4-(4-hydroxybutoxy)butoxy]butyl, 2-(2-methoxyethoxy)ethyl, or 2-[2-(2-methoxyethoxy)ethoxy]ethyl.
[0022] R 3 However, in embodiments representing polyester or polyoxyalkylene having 2 to 1000 repeating units, it may be a homopolymer or copolymer.
[0023] The linker L may be derived from an alcohol, in which case X' is the oxygen of the precursor alcohol; or it may be derived from an amine, in which case X' is the nitrogen of the precursor amine.
[0024] In the dimer or oligomer compound according to the present invention, m is 2 or more, preferably 3 to 20, and most preferably 3.
[0025] Linker L is ethylene, propylene, or C4-C 12 It may consist of any of the following: a polyester chain having 0 to 1000 repeating units, which is an alkylene, homopolymer, or copolymer; a polyoxyalkylene chain having 0 to about 1000 repeating units, which is a homopolymer or copolymer; triethanolamine; glycerol; or sugar.
[0026] According to a second aspect of the present invention, a fluorescent whitening agent or optical glossing agent of formula (II) having the following structure, [ka] In the formula, Y is either Z or X'L; Z is OH, OM, OR 3 , O(CH2) q SO3M, NH2, NHOH, NHR 4 , or NR 4 2, M represents an alkali metal or alkaline earth metal; R 3 This represents linear or branched alkyl, aryl, alkaryl, aralkyl, linear or branched alkyl alcohol, linear or branched alcohol polyol, hydroxyalkylamine, polyhydric alcohol, sugar, linear or branched alkyl ether, polyester having 2 to 1000 repeating units, or polyoxyalkylene chain having 2 to 1000 repeating units; q is between 1 and 5; R 4 These are independently methyl, ethyl, propyl, and C4-C 12Selected from alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propanyl, 1,3-dihydroxy-2-propanyl, 2,3-dihydroxypropyl, cyanomethyl, 2-aminoethyl, or dicarbamoylmethyl; or NR 4 2 represents a heterocyclic ring, such as morpholine; and R is H, CHR 5 R 6 , R 5 , R 6 , alkyl sulfonates, polyethers, CH2COZ or CH(COZ)((CH) n COZ) where each Z may be the same or different. R 5 and R 6 R independently represents hydrogen, alkyl (e.g., methyl, ethyl, propyl, isopropyl), vinyl, phenyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, aminomethyl, (dimethylamino)methyl, 5-aminopentyl, or cyano, optionally R 4 and R 5 They may be the same or different. n is either 1 or 2; In the equation, if Y is X'L; X' is O, S or NH; and A fluorescent whitening agent or optical glossing agent is provided, in which L represents a linker portion connecting m repeating units of a variant of formula II in which X' defined above is present instead of Y.
[0027] R 3 However, in embodiments representing linear or branched alkyl groups, R 3 The compound is preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or 2-ethylhexyl.
[0028] R 3 However, in embodiments representing alkyl alcohols, R 3The alcohol is preferably selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, dodecanol, or stearyl or oleyl alcohol.
[0029] R 3 However, in embodiments representing an arrow, R 3 is preferably phenyl, and R 3 In embodiments where R represents Alkaline, 3 The compound is preferably selected from benzyl or ethylphenyl.
[0030] R 3 However, in embodiments representing linear or branched alkyl alcohols, R 3 It is preferably selected from 4-hydroxybutyl.
[0031] R 3 However, in embodiments representing linear or branched alcohol polyols, R 3 is preferably a diol or triol. In the most preferred case, R 3 This can be selected from 2,3-dihydroxypropyl or 2-hydroxy-1-(hydroxymethyl)ethyl.
[0032] R 3 However, in embodiments representing hydroxyalkylamines, R 3 The is preferably selected from triethanolamine, N-methyldiethanolamine, or triisopropanolamine.
[0033] R 3 However, in embodiments representing polyhydric alcohols, R 3 It is preferably glycerol.
[0034] R 3 However, in the embodiment representing sugar, R 3 Preferably, it is selected from dextrose, fructose, galactose, glucose, lactose, maltose, or sucrose.
[0035] R 3 However, in embodiments representing linear or branched alkyl ethers, R 3 Preferably, the compound is selected from 2-(2-hydroxyethoxy)ethyl, 2-(2-hydroxy-1-methylethoxy)-1-methylethyl, 2-[2-(2-hydroxy-1-methylethoxy)-1-methylethoxy]-1-methylethyl, 3-(3-hydroxypropoxy)propyl, 3-[3-(3-hydroxypropoxy)propoxy]propyl, 4-(4-hydroxybutoxy)butyl, 4-[4-(4-hydroxybutoxy)butoxy]butyl, 2-(2-methoxyethoxy)ethyl, or 2-[2-(2-methoxyethoxy)ethoxy]ethyl.
[0036] R 3 However, in embodiments representing polyester or polyoxyalkylene chains having 2 to 1,000 repeating units, it may be a homopolymer or copolymer.
[0037] The linker L may be derived from an alcohol, in which case X' is the oxygen of the precursor alcohol; or it may be derived from an amine, in which case X' is the nitrogen of the precursor amine.
[0038] In the dimer or oligomer compound according to the present invention, m is 2 or more, preferably 3 to 20, and most preferably 3.
[0039] Linker L is ethylene, propylene, or C4-C 12 It may consist of any of the following: a polyester chain having 0 to 1000 repeating units, which is an alkylene, homopolymer, or copolymer; a polyoxyalkylene chain having 0 to about 1000 repeating units, which is a homopolymer or copolymer; triethanolamine; glycerol; or sugar.
[0040] The FWA and optical glossing agents of the present invention are preferably formulated for use as optical glossing agents or fluorescent whitening agents. Typically, such formulations include providing an active ingredient (FWA or optical glossing agent) together with at least one auxiliary compound that is typically present in fluorescent whitening or optical gloss formulations. Such auxiliary compounds may be selected from, for example, one or more detergents, bleaches, carrier compounds, stabilizers, and / or dispersants.
[0041] The present invention also provides the use of the above-mentioned compounds as fluorescent whitening agents or optical glossing agents.
[0042] The present invention also provides a fluorescent whitening or optical gloss formulation comprising the aforementioned fluorescent whitening agent or optical gloss agent and at least one detergent, bleach, carrier compound, stabilizer and / or dispersant.
[0043] Furthermore, the present invention provides a method for providing fluorescent whitening or optical gloss to a substrate, comprising contacting the substrate with one or more of the aforementioned compounds under conditions effective in enabling chemical and / or physical bonding of one or more compounds to or into the substrate. [Modes for carrying out the invention]
[0044] All current industry-standard fluorescent whitening agents or optical glossants, including DAS-1, DAS-2, DSPB, and FB28, absorb ultraviolet light in the 340–370 nm region and emit visible blue light in the 420–470 nm region. To achieve this effect, an elongated conjugated molecular system is required to provide the conjugated aromatic system with a sufficient number of π electrons to enable the appropriate energy transition to achieve emission at 420–470 nm upon de-excitation. As demonstrated by the chemical structures of current industry standards, this typically requires an elongated aromatic system based primarily on carbon and hydrogen, with a high molecular weight.
[0045] Pyridone and citradic acid derivatives are known to achieve similar π electron counts and also emit visible blue light in the 420–470 nm range. These derivatives, which have substantially lower molecular weights, achieve this by incorporating heteroatoms such as nitrogen and oxygen.
[0046] The excitation and deexcitation properties of the fluorescent whitening agent or optical glossing agent of the present invention can be mechanistically understood by referring to the prior art study SC Adv., 2015, 5, 34795, and attributing fluorescence in similar compounds in the 420-470 nm range to the same π*-π transition at the carbon-oxygen double bond, as seen in scaffolds based on pyridone and citradic acid. The carboxyl groups, particularly the carboxylic acid groups, present in the structures of formulas (I) and (II) of the present invention are thought to contribute to the required number of π electrons associated with fluorescence in the desired range.
[0047] As a result, the fluorescent whitening agent or optical gloss agent of the present invention is advantageous over current industry standards because it provides equivalent fluorescence using smaller compounds with smaller molecular weights. Furthermore, further functionalization of the structures of formulas (I) and (II) to adjust application performance can be easily achieved with little effect on the fluorescence behavior of the fluorescent whitening agent or optical gloss agent.
[0048] There are several further factors that govern the effectiveness of the FWA or optical glossing agent according to the present invention.
[0049] The FWA or optical glossing agent according to the present invention typically absorbs ultraviolet light in the region 340-370 nm and emits visible light in the region 420-470 nm. The quantum yield of these compounds in this regard is preferably at least about 30%, more preferably at least about 40%, even more preferably at least about 50%, and most preferably at least about 60%.
[0050] The FWA or optical glossing agents of the present invention exhibit significantly higher relative quantum yields than current industry standards. For example, only DSPB yields comparable values exceeding 70%. The FWA or optical glossing agents described in the present invention are advantageous over current standards because they can achieve similar fluorescence performance with much smaller molecular weights, thus reducing the load of the FWA or optical glossing agent in the end application. Lower loads can mitigate any potential adverse effects associated with the compound.
[0051] The FWA or optical glossing agent of the present invention typically exhibits good durability on cellulose-based fabrics, retaining at least about 30% of the load after a typical washing cycle.
[0052] The FWA or optical glossing agent according to the present invention can be sustainably produced from readily available starting materials using environmentally sustainable reagents. Accordingly, the present invention also provides fluorescent whitening agents or optical glossing agents derived from the condensation of dicarboxylic acids or polycarboxylic acids with amines, in particular from the condensation of dicarboxylic acids or polycarboxylic acids with amino acids or amino acid derivatives, in particular from the condensation of citric acid with amino acids or amino acid derivatives.
[0053] Current industry-standard FWAs and optical glossants, including DAS-1, DAS-2, DSPB, and FB28, possess high molecular weight conjugated aromatic systems, which have limited ability to be oxidized or hydrolyzed, resulting in low biodegradability. Consequently, current industry-standard FWAs are a growing environmental concern, as they are detected as pollutants not only in urban wastewater (Marine Pollution Bulletin, 2022, 178, 113559) but also in indoor environments (Environ.Sci.Technol., 2022, 56, 10131-10140). Recent studies have identified FWA as a source of urban wastewater pollution, adversely impacting aquatic ecosystems and water resources. Marine Pollution Bulletin, 2022, 178, 113559 identifies FWA as an emerging concern pollutant because it is present in wastewater at concentrations comparable to the top range of better-studied wastewater pollutants such as pharmaceuticals (approximately 10-1000 ng / L). Data from Sweden showed that DAS-2 was consistently detected in sample excretions at a high median concentration of approximately 1500 ng / L.
[0054] In comparison, the FWA and optical glossing agents according to the present invention have smaller fluorescent cores and are therefore more biodegradable, as they are more susceptible to biological attack, but still provide sufficient stability against oxidation and hydrolysis, making them useful for their intended applications.
[0055] The molecular weight of the FWA and optical gloss agent of the present invention is preferably less than about 1000, less than about 750, less than about 500, less than about 400, less than about 300, or less than about 200.
[0056] Estimating biodegradation based on chemical structure is complex due to variations in the physicochemical properties of organic compounds. Predictive methods for estimating biodegradation previously relied on metabolic pathways and microbial diversity. More recently, predictive methods utilize group contribution, QSAR, or machine learning techniques.
[0057] As described in Ecotoxicol.Environ.Saf.1989,18,252-267, a study conducted by 22 biodegradation experts constructed a hierarchy (ester=amide=anhydride > hydroxyl > carboxylic acid=epoxide=unsaturated site > benzene ring=methyl=methylene group) representing the approximate order in which various groups are considered to contribute to aerobic biodegradability. The general assumption was that already partially oxidized compounds are generally considered more susceptible to biological attack than partially unoxidized compounds, and all others equally, hydrolyzable chemicals are still considered to decompose more easily. The time required for final decomposition was generally estimated considering molecular weight, branching, halogenation, functional groups, solubility, and other factors.
[0058] Advantageously, the FWA and optical glossing agents according to the present invention are biodegradable. Preferably, they contain at least one functional group that is not oxidized or is partially oxidized, thereby being oxidizable or further oxidizable. Preferably, they contain at least one hydrolyzable group.
[0059] Accordingly, FWAs or optical brighteners containing at least one unstable group are also provided according to the present invention. Essentially biodegradable fluorescent whitening agents can be defined as being more than 20% but less than 60% biodegradable in water, as measured by the standard OECD 301A-F test. Easily biodegradable fluorescent whitening agents or optical brighteners may be characterized by the ability of the material to rapidly and completely biodegrade in water within a 10-day window of 28 days (either 70% or more dissolved organic carbon removal, 60% or more theoretical carbon dioxide removal, or 60% or more theoretical oxygen demand, depending on the standard OECD 301A-F test method).
[0060] The FWA and optical glossing agent according to the present invention are preferably stable at relatively high pH levels, which are typical conditions in laundry washing, such as about pH 7 to about pH 10 and pH 7.5 to about pH 9.5.
[0061] The FWA and optical glossing agent according to the present invention are preferably UV stable.
[0062] The FWA and optical glossing agent according to the present invention are preferably oxidatively stable in a conventional cleaning cycle. According to the present invention, preferred examples of fluorescent whitening agents and optical glossing agents are as follows: [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] [Table 1-7] [Table 1-8] [Table 1-9] [Table 1-10] [Table 1-11] [Table 1-12] [Table 1-13] [Table 1-14] [Table 1-15]
[0063] In certain embodiments of the present invention, the linker may be capable of supporting multiple fluorescent whitening cores, and examples of such linkers are shown below, which can be combined at each position with one of the common cores (I) and (II). [ka]
[0064] The fluorescent whitening agents or optical glossing agents according to the present invention have excellent chemical stability at relatively high pH, for example, the typical pH of laundry detergent formulations. They also have thermal stability that is very suitable for such applications and can be prepared by synthetic methods including temperatures up to 130°C (see below).
[0065] The fluorescent whitening agent or optical glossing agent according to the present invention can be used in a variety of applications, including but not limited to laundry, dishwashing, papermaking, personal care (cosmetics, hair care, etc.), inks, coatings, and adhesives. In these applications, the fluorescent whitening agent or optical glossing agent can make materials, such as cotton, appear whiter while simultaneously concealing yellowing due to aging.
[0066] Fluorescent whitening agents or optical glossing agents may be used in any type of formulation, such as liquids, powders, sheets, or bars, in different proportions and loads as needed.
[0067] synthesis Fluorescent whitening agents or optical glossing agents can be prepared from readily available starting materials such as citric acid or citradic acid. The preparation of the target compounds of the present invention (Scheme 1) can be advantageously more environmentally acceptable as a result of using common and renewable building blocks, such as citric acid, which are produced on a large scale by fermentation.
[0068] Each core structure can be readily synthesized by heating citric acid with a second amine building block in the presence of water, with water itself being the primary byproduct. Water-based synthesis is safer, cleaner, more environmentally friendly, and highly scalable.
[0069] Further functionalization of the core unit to modify and / or improve the persistence of the fluorescent whitening agent or optical gloss agent obtained in the desired application can be readily achieved by a second, easy reaction with either an alcohol or an amine.
[0070] Scheme 1: A typical synthesis route used for the optical gloss agent of the present invention (wherein Y is as defined in the first aspect of the present invention, X 1 ( is any suitable leaving group) [ka] In comparison, the preparation of existing optical glossants such as benchmark DAS 1, DAS 2, and FB28 (Scheme 2A) requires a complex synthesis method involving five synthesis steps, as well as the use of environmentally undesirable materials such as precious metal catalysts and hazardous materials such as cyanuryl chloride. Similarly, the preparation of optical glossant DSPB (Scheme 2B) requires complex synthesis steps involving environmentally undesirable and / or hazardous materials such as trimethylphosphite and dimethylformamide (DMF). Both molecular families (Scheme 2A or Scheme 2B) use petrochemical-derived raw materials.
[0071] Scheme 2A: Synthesis route used for current benchmark optical glosses such as DAS1, DAS2, and FB28 [ka]
[0072] Scheme 2B: Synthesis route used in the current benchmark optical gloss agent DSPB [ka]
[0073] General synthesis of the fluorescent whitening agent core unit (base of formula (I)) from citric acid A mixture of citric acid (1 equivalent) and the corresponding amine (1 equivalent) was dissolved in water (1 volume). The reaction mixture was heated to 100°C, and all the water was distilled. The reaction temperature was then raised to 140°C to melt the resulting residue, and the molten mixture was stirred for 16 hours, after which the reaction water was distilled. The resulting resin material was cooled to <100°C, and then fresh water (1 volume) was added. The mixture was then cooled to ambient temperature with vigorous stirring to disperse the product, and then filtered. The isolated solid was washed with fresh water (0.5 volume) and dried in a vacuum oven to obtain the final product.
[0074] Synthesis of fluorescent whitening agent core unit (1a) A mixture of citric acid (200 g, 1.05 mol) and cysteamine (80.3 g, 1.05 mol) was dissolved in water (300 ml). The reaction mixture was heated to 100°C, and all the water was distilled. The reaction temperature was then increased to 140°C, and the resulting residue was melted while stirring for 4 hours. The temperature was then increased to 160°C, and the molten mixture was stirred for 16 hours, after which the reaction water was distilled. After cooling the obtained resin material to <100°C, fresh water (300 ml) was added. The mixture was then cooled to ambient temperature while vigorously stirring to disperse the product, and then filtered. The isolated solid was washed with fresh water (150 ml), dried in a vacuum oven, and the final product was obtained as a yellow powder in a yield of 64.5% (131.4 g, 0.68 mol). Analytical data: HPLC purity: 99.7%; LC-MS (+ve ion): m / z 198.1
[0075] Synthesis of fluorescent whitening agent core unit (3a) A mixture of citric acid (200 g, 1.05 mol) and cysteine (127.2 g, 1.05 mol) was dissolved in water (325 ml). The reaction mixture was heated to 100°C, and all the water was distilled. The reaction temperature was then raised to 140°C to melt the resulting residue, and the molten mixture was stirred for 16 hours, after which the reaction water was distilled. After cooling the resulting resin material to <100°C, fresh water (325 ml) was added. The mixture was then cooled to ambient temperature while vigorously stirring to disperse the product, and then filtered. The isolated solid was washed with fresh water (150 ml) and dried in a vacuum oven to obtain the final product as a yellow powder in 61% yield (154.7 g, 0.64 mol).
[0076] Analytical data: HPLC purity: 99.8%; LC-MS (+ve ion): m / z 242.2; 1 H NMR(DMSO-d6,400=MHz,d):6.59(s,1H),6.52(s,1H),5.46(d,1H),3.92(t,1H),3.60ppm(d,1H); 13 C{ 1 H}NMR(DMSO-d6,75MHz,d):169.2,165.6,160.7,150.2,142.7,114.8,97.9,62.6 ppm.
[0077] Synthesis of fluorescent whitening agent core unit (4a) A mixture of citric acid (200 g, 1.05 mol) and benzylamine (127.2 g, 1.05 mol) was dissolved in water (325 ml). The reaction mixture was heated under reflux for 16 hours. The reaction mixture was then dried under vacuum and ground to obtain the final product as a yellow powder in nearly quantitative yield and good purity.
[0078] Esterification of the fluorescent whitening agent core unit (1a) with ethanol A mixture of FWA 1a (5 g, 0.026 mol) and p-toluenesulfonic acid (0.04 g, 0.002 mol) was suspended in 15 ml of industrial methylated spirit (IMS, also known as Industrial Denatured Alcohol, IDA), heated under reflux, and stirred for 24 hours. The reaction mixture was then boiled and dried to remove the reaction water. Fresh IMS (15 ml) was then added to the reaction mixture, and reflux was continued for another 24 hours. The reaction mixture was then cooled, and the solvent was removed under reduced pressure to obtain the target ester as a beige powder in near quantitative yield. Analytical data: HPLC purity: 95.8%; LC-MS (+ve ion): m / z 226.2
[0079] Esterification of fluorescent whitening agent core units with low-boiling point alcohols (<100°C) The prepared FWA core (1 equivalent) mixture was suspended in alcohol (3 volumes), heated under reflux, and stirred for 24 hours. The reaction mixture was then boiled dry to remove the reaction water. Fresh alcohol (3 volumes) was then added to the reaction mixture, and reflux was continued for another 24 hours. The reaction mixture was then cooled, and the solvent was removed under reduced pressure to obtain the target ester in near quantitative yield.
[0080] Esterification of fluorescent whitening agent core units with high-boiling point alcohols (>100°C) The prepared FWA core (1 equivalent) mixture was suspended in an alcohol (1.1 equivalents / carboxylic acid group) containing p-toluenesulfonic acid (0.08 equivalents). The resulting mixture was then heated to >100°C, with 130°C being the preferred reaction temperature, and the reaction water was distilled for 16 hours. The excess alcohol was then removed under reduced pressure or azeotropic distillation as needed. For alcohols with high boiling points, the desired ester was purified by either column chromatography or precipitation from acetone.
[0081] Amidation of the ethyl ester of FWA core 1a with ethylenediamine A prepared sample of the ethyl ester of FWA core 1a (2.25 g, 0.01 mol) was suspended in industrial methylated spirits (15 ml IMS), and ethylenediamine (1.17 g, 0.02 mol) was added to obtain an instantaneous orange color. The resulting mixture was heated under reflux and stirred for 16 hours. After the reaction was cooled, excess alcohol was removed under reduced pressure to obtain the desired amide as a beige powder in 82% yield (1.91 g, 0.008 mol). Analytical data: HPLC purity: 95.6%; LC-MS (+ve ion): m / z 240.2
[0082] Amidation of functionalized fluorescent whitening agents A prepared sample of the desired FWA core (1 equivalent) of ethyl ester was suspended in IMS (5 volumes), and the target amine (2 equivalents / carboxylic acid group) was added at room temperature. The resulting mixture was heated under reflux and stirred for 16 hours. After the reaction was cooled, the excess alcohol was removed under reduced pressure to obtain the desired amide.
[0083] Carrier In concentrated granular detergent compositions, the composition is typically provided to the end user for use as a diluent or dissolving solution. In such solutions, the pH to which the fluorescent whitening agent is exposed before use can be particularly high, potentially causing storage problems, especially with respect to storage stability. Therefore, there is a need for an improved delivery composition that is compatible with environmentally acceptable fluorescent whitening agents, particularly those defined according to the present invention.
[0084] Similarly, fluorescent whitening agents can be incorporated into fabric detergent compositions. However, simply incorporating them does not guarantee that the fluorescent whitening agents will be absorbed by the fabric during washing. One function of a detergent composition is to be absorbed and preferentially adhere to the surface of the fabric material so that oil and other residues are removed. Typically, this is achieved using surfactants. Surfactants can be classified as anionic, nonionic, and cationic. Therefore, a fabric detergent composition incorporating a fluorescent whitening agent is needed so that the fluorescent whitening agent may remain absorbed on the surface of the fabric material after the washing process, especially if a rinsing process follows the washing process. Thus, a fabric detergent composition is needed that can deliver an environmentally acceptable fluorescent whitening agent during the washing process and remain in place on the material after such a process.
[0085] In particular, there is a need for a delivery composition that enables an environmentally acceptable fluorescent whitening agent, specifically a structure as defined in this application, that provides delayed release of the fluorescent whitening agent at a specific point in the washing process. Specifically, this point in the washing process is when the probability of the fluorescent whitening agent adsorbing onto the fabric is highest. Alternatively, rapid release of the fluorescent whitening agent or optical glossing agent may also be advantageous in certain circumstances, as this allows the fluorescent whitening agent to adsorb onto a fabric before a significant concentration of surfactant is present, for example, in the washing method, thus competing with the fluorescent whitening agent for adsorption onto the fabric.
[0086] One embodiment of the present invention provides a fabric cleaning detergent composition. The fabric cleaning detergent composition may be in several different formats, such as compositions for hand washing, machine washing, uncolored clothing, and colored clothing.
[0087] Compositions providing oxidizing agents are widely used, and these can also cause stability issues for environmentally acceptable fluorescent whitening agents, such as the structures defined in this application. Therefore, there is a need for delivery compositions that mitigate or improve the problems caused by oxidizing agents present in fabric cleaning detergent compositions.
[0088] The aforementioned problems are particularly relevant to environmentally acceptable fluorescent whitening agents due to the chemical complexity of such molecules, the fact that these molecules exist in small amounts and therefore essentially have a high surface area-to-volume ratio in compositions, and the fact that compounds formulated to be environmentally acceptable often have unstable groups intended to be degraded in order to have improved biodegradability.
[0089] In particular, chemical groups designed to improve biodegradability are typically more unstable in the presence of oxidizing agents, under high pH conditions, or in combination thereof.
[0090] Furthermore, the fluorescent whitening agent used in the detergent composition is preferably present at a low level, for example, around 0.01%. Importantly, high concentrations, such as those caused by individual granules, are undesirable because they can result in a non-uniform distribution. This is particularly exacerbated, for example, by the sedimentation of the granular mixture during transport. Therefore, a delivery composition is needed that allows for a uniform distribution throughout the entire detergent composition, particularly the fabric detergent composition, and more specifically, along with any other relevant detergent components in the granular solid fabric detergent composition.
[0091] Accordingly, in another embodiment of the present invention, a solid carrier composition for a fluorescent whitening agent composition comprising a carrier and a fluorescent whitening agent is provided in accordance with the above.
[0092] In such embodiments, the fluorescent whitening agent or optical glossing agent may be absorbed into the structure of the carrier. Furthermore, the fluorescent whitening agent or optical glossing agent may be present in the carrier composition at a weight of less than 34%.
[0093] In another embodiment, a fluorescent whitening agent or optical glossing agent may be present in the carrier composition at a weight of 1% to 34%. In a preferred embodiment, the fluorescent whitening agent or optical glossing agent may be present at a weight of 15 to 30%. Advantageously, this appears to reduce any liquid dust generation and absorption from the granules, especially when the fluorescent whitening agent is provided as a liquid.
[0094] The fluorescent whitening agents according to the present invention may be provided in solid or liquid form. Fluorescent whitening agents may be particularly in liquid or low-melting-point form, which can make handling difficult, but can also be incorporated into products and exist as adjuvants. Examples of such products may include detergents, e.g., fabric detergents; cosmetics, e.g., sunscreens; papermaking, such as for paper finishing; and various other applications in which fluorescent whitening agents are incorporated. In these applications, the fluorescent whitening agent may be present in small amounts, typically less than 1% by weight, and sometimes as much as 0.01% by weight.
[0095] Therefore, handling and incorporating such materials is more difficult in these applications. Thus, to overcome this challenge, it is advantageous to increase the weight and volume of the fluorescent whitening agent by incorporating it into a carrier. However, it is crucial that the fabric whitening agent is completely incorporated into the carrier, especially if it is a liquid or a low-melting-point solid. In certain embodiments of the present invention, if such incorporation level is 34% by weight or less, the fluorescent whitening agent or optical glossing agent can be advantageously incorporated into the gaps of other porous structures.
[0096] In embodiments of the present invention, the carrier may be selected from one or more of the following: sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, cellulose, carboxymethylcellulose, polyvinyl alcohol with 100,000 or more repeating units, sodium silicate, polyvinylpyrrolidone with 50,000 or more repeating units, or zeolite. In particular, such materials are compatible with detergent compositions.
[0097] In preferred embodiments of the present invention, the carrier may be a water-soluble inorganic salt. These salts have been found to disperse fluorescent whitening agents more rapidly, particularly when incorporated into an aqueous medium.
[0098] In the present invention, the carrier composition may be prepared by drying the fluorescent whitening agent and the carrier from a solution, because this allows for the production of a homogeneous mixture before preparing the carrier composition in a solid form by drying.
[0099] In the present invention, drying of the composition is preferably achieved by spray drying. Spray drying has been found to enable the effective combination of fluorescent whitening agents, particularly those with relatively low solubility, with soluble components in the form of a carrier in a substantially homogeneous manner. This is especially useful when the fluorescent whitening agent is a liquid or a low-melting-point solid, because it can produce a homogeneous mixture with the solubilizing carrier for spray drying, resulting in a "dry" and low-dusting granule.
[0100] In the present invention, the carrier composition can be prepared by drying the composition in a fluidized bed. Advantageously, this method of drying is effective when the fluorescent whitening agent is sensitive to high drying temperatures. This is particularly important because the fluorescent whitening agent according to the present invention is readily biodegradable and often contains unstable groups such as esters, making it more temperature-sensitive compared to conventional fluorescent whitening agents.
[0101] In the present invention, when the carrier composition comprises an insoluble carrier and a low-solubility or solid fluorescent whitening agent, it can be prepared by co-forming granules of the carrier and fluorescent whitening agent with a binder. This process is advantageous in that it avoids high temperatures and is therefore advantageous in considering the aforementioned problems regarding the stability of the fluorescent whitening agent. The binder can be selected from sodium silicate or an organic polymer. In the most preferred embodiment, the binder may be an organic polymer, particularly polyvinyl alcohol or a polyvinyl alcohol copolymer. The polarity of these polymers is advantageous in that it provides a more homogeneous composition than polymers having low polarity or hydrophilicity.
[0102] Polycarboxylic acids can also be suitable binder materials, particularly when amine or amide functional groups are present in the fluorescent whitening agent, as they provide improved solubilization of the fluorescent whitening agent during the preparation of the carrier composition.
[0103] Clearly, there is a synergistic effect between proteolytic enzymes and fluorescent whitening agents, and therefore, in some further embodiments of the present invention, the carrier composition may further contain proteolytic enzymes. This is especially true when the fluorescent whitening agent contains an amide functional group. Furthermore, there is a synergistic effect between lipolytic enzymes and fluorescent whitening agents, and therefore, the carrier composition may further contain a lipolytic enzyme. This is especially true when the fluorescent whitening agent contains an ester functional group.
[0104] The fluorescent whitening agent or optical glossing agent may be a liquid at ambient temperature.
[0105] Fluorescent whitening agents or optical glossing agents may have a solubility in water of less than 1 g / liter at ambient temperature.
[0106] The carrier may be in the form of a polymer sheet that can form small bags or pouches for the detergent composition.
[0107] detergent A further aspect of the present invention provides a detergent composition comprising the aforementioned fluorescent whitening agent or optical glossing agent.
[0108] The detergent composition may contain detergent surfactants, such as anionic, cationic, zwitterionic, or nonionic surfactants.
[0109] In a preferred embodiment, the detergent composition includes a nonionic surfactant.
[0110] Advantageously, nonionic surfactants have been found to provide a preferred base detergent composition for the deposition of the fluorescent whitening agent or optical gloss agent of the present invention.
[0111] In embodiments of the present invention where the detergent surfactant is a nonionic surfactant, one or more rhamnolipids or sophorolipids may be selected. Examples of commercially available such surfactants include, but are not limited to, BioLoop 56L, BioLoop 56L-PG, BioLoop 68L, BioLoop 68L-PG, BioLoop 84L, and BioLoop 84L-PG.
[0112] In the present invention, the fluorescent whitening agent or optical glossing agent preferably has an amide functional group.
[0113] Such fluorescent whitening agents or optical glossing agents have been found to result in better adsorption on surfaces being cleaned by detergent compositions. While we do not wish to be bound by theory, it is understood that some positive charge on the amide can interact with negatively charged surfaces. This is conventionally understood to be the case when the articles are being cleaned.
[0114] The present invention has been found to provide improved deposition of FWA or optical gloss agents when used in related detergent compositions. The FWA or optical gloss agent is assumed to co-adsorb with cationic surfactants on the surface being cleaned.
[0115] In compositions utilizing positively charged surfactants such as cationic or zwitterionic surfactants, the FWA or optical glossing agent preferably has Y as OH or OM, and M is Na or K.
[0116] These FWAs or optical glossants have been found to provide improved deposition, possibly due to the combination of negatively charged FWAs or optical glossants and positively charged surfactants (which together provide improved surface adsorption). This is particularly beneficial for detergent compositions such as fabric softeners.
[0117] In the present invention, the pH of the detergent composition during use is preferably in the range of pH 8 to 10. This pH range is particularly beneficial for the adsorption of ionizable FWA or optical glossing agents.
[0118] In the present invention, the detergent composition is preferably a laundry detergent composition and includes, for example, fabric softeners, whitening agents, pretreatment agents, and conventional solid, liquid, gel, and pouch detergent compositions, as well as heavy-duty, light-duty "whites" and "coloreds" detergent compositions.
[0119] In the present invention, the detergent composition may preferably be a fabric washing detergent composition selected from one or more of the following: laundry detergent, fabric softener, bleach, or booster laundry aid (e.g., whitening agent).
[0120] In the present invention, the detergent composition preferably further comprises a proteolytic enzyme, and the FWA or optical glossing agent comprises an amide bond.
[0121] The detergent composition of the present invention may further contain a lipolytic enzyme, and in particular, in embodiments of FWA or optical glossing agents, it contains an ester bond.
[0122] The detergent composition of the present invention may be in the physical form of a powder (granules), liquid, gel, pouch, tablet, or solid sheet.
[0123] Preferably, the physical form is solid. This is especially true for FWAs or optical glossants where m is 3 or greater and L is a polymer. Such embodiments provide FWAs or optical glossants in solid form that are compatible with other solids and do not undergo hydrolysis in an undiluted state. When the solid is diluted during washing, for example, components of the detergent composition such as enzymes or pH agents induce hydrolysis, releasing the FWA or optical glossant into the washing composition.
[0124] The scope of the present invention includes detergent compositions selected from one or more of the following: laundry detergents, fabric softeners, bleaches, or booster laundry aids (e.g., whitening agents).
[0125] Accordingly, the present invention further provides a fluorescent whitening agent or optical gloss agent solid carrier composition comprising a carrier and a fluorescent whitening agent or optical gloss agent, in accordance with the above description.
[0126] The compounds according to the present invention may be capable of providing fluorescent whitening or optical gloss effects, and may be readily, finally, or essentially biodegradable. All compounds may have a common renewable building block, thereby making their production environmentally friendly. Furthermore, the compounds may have one or more of the following characteristics: adhesion to fabrics such as natural materials including cotton and cellulose; compatibility with synthetic fabric materials; providing peak fluorescence output in the blue portion (450 nm and 495 nm) or green portion (495 nm to 570 nm) of the visible spectrum; providing high fluorescence in solid form and in solution; providing high fluorescence when absorbed into fabrics and solutions; and / or providing higher absorption into cotton than 2,2'-stilbendisulfonic acid.
[0127] Other uses of the fluorescent whitening agent as defined in this invention: fabric The FWA or optical glossing agent of the present invention can be used in fabric manufacturing.
[0128] The FWA or optical glossing agent of the present invention can be used in the finishing process of cotton, preferably in the treatment of finished fabrics from woven (loom-bound) cloth.
[0129] The FWA or optical gloss agent of the present invention can be used when melt-spinning synthetic fibers.
[0130] paper The FWA or optical glossing agent of the present invention can be used in papermaking, preferably in a "wet" manufacturing process.
[0131] The FWA or optical glossing agent of the present invention can be used for paper finishing.
[0132] The FWA or optical glossing agent of the present invention can be used to treat cellulose fibers before papermaking.
[0133] cosmetics Cosmetic compositions can be provided by using the FWA or optical glossing agent of the present invention in combination with a skin emollient.
[0134] The FWA or optical gloss agent of the present invention can be used to manufacture sunscreen compositions.
[0135] The advantage of FWA or optical glossing agents in cosmetics is that they increase the apparent gloss, shine, or color intensity of cosmetics and do so in an environmentally acceptable manner. [Examples]
[0136] Example 1 - Evaluation of fluorescent whitening agents The fluorescent whitening agents and optical glossing agents of the present invention have been evaluated against commercially available benchmarks in terms of chemical and UV stability, quantum yield, fluorescence / whiteness effect, biodegradability, and persistence on cellulose.
[0137] Relative quantum yield A solution of FWA was prepared in 0.1 M sodium carbonate. The solution was diluted until a UV absorbance of 0.1 was measured (Agilent® Cary UV-vis), and then further diluted to obtain a range of UV absorbance readings. These solutions were then run and the fluorescence response was measured (Agilent® Cary Eclipse fluorescence spectrometer). The integrated area from the fluorescence measurements was plotted against the UV absorbance readings. The relative quantum yield was calculated by comparing this with the gradient measurements of quinine sulfate in 0.1 M sulfuric acid standard. The results are shown in Tables 1 and 2 below. [Table 2] [Table 3] It is readily apparent that the relative quantum yield of the compound according to the present invention is equivalent to or better than that of the standards of the prior art.
[0138] Fluorescence / whiteness effect measured with cellulose powder: Color measurements were performed using a Lovibond® LC100 spectrophotometer. The surface color of the powders was quantified using a series of values L*, a*, and b* from the color model CIELAB defined by the International Commission on Illumination (Commission Internationale de l'Eclairage). L* is a measure of the amount of white or black in the sample; higher L* values indicate brighter colored samples. The amount of red or green in the sample was determined by the "a*" value. The amount of blue or yellow in the sample was determined by the "b*" value; lower (more negative) b* values indicate more blue on the sample. Color can also be measured using a different model, CIE L*C*h*, where C* represents chroma and h* represents the hue angle. Powders from each persistence test were measured against blank washed cellulose to set the starting point for subsequent UV stability tests. The results are shown in Table 3 below. [Table 4] All compounds showed a substantial shift to a blue hue (h*=270) compared to the blank, demonstrating effectiveness in terms of both persistence and optical effect.
[0139] UV stability (i.e., light resistance) The cellulose powder prepared above was exposed to UV light for 3 months in a UV box under a 4W lamp (365nm). The samples were then visually inspected, photographed, and color-measured again to monitor for loss of whiteness and changes from blue to yellow or darker tones. The results are shown in Table 4 below. [Table 5]
[0140] The FWA of the present invention is stable under UV light under test conditions.
[0141] chemical stability FWA or optical glossing agent was weighed at 0.0100–0.0200 g into a 100 mL volumetric flask, and the volume was adjusted using deionized water. The solution was sonicated for 5 minutes to ensure a homogeneous dispersion was produced. The solution was divided into five 10 mL samples. Sample 1 was a blank with 0.2 mL of DI water added. Sample 2 was mixed with 0.1 mL of 1 M sodium hydroxide solution and 0.1 mL of DI water, Sample 3 with 0.1 mL of 1 M sodium bicarbonate solution and 0.1 mL of DI water, Sample 4 with 0.1 mL of 1 M sodium hydroxide solution and 0.1 mL of 0.75 M hydrogen peroxide, and Sample 5 with 0.1 mL of 1 M sodium carbonate solution and 0.1 mL of 0.75 M hydrogen peroxide. All samples were heated at 40°C for 48 hours and then analyzed by HPLC. The blank sample was used to determine the retention time and maximum response of the FWA or optical glossing agent. Any hydrolysis and oxidation of FWA or optical glossants result in new compounds appearing in the chromatogram at different retention times, along with a reduction in the response of the FWA or optical glossant. Other samples are reported as the % response of the FWA or optical glossant relative to the blank. Conditions 3 (carbonate) and 5 (carbonate and hydrogen peroxide) are most relevant to laundry applications (e.g., heavy-duty powder detergents). The results are shown in Table 5 below. [Table 6]
[0142] The monitoring of the chemical stability of FWA shown in Table 5 confirms the excellent stability of both the unfunctionalized and amine-functionalized structures under high pH and in the presence of oxidizing agents. These results demonstrate high suitability for laundry applications.
[0143] The fluorescent whitening agent of the present invention has been further evaluated for its biodegradability and persistence on cellulose compared to commercially available benchmarks.
[0144] Durability against cellulose: The buffer solution was prepared by weighing 0.10 g of SDS, 1.0 g of glycerol, 8.4 g of sodium carbonate, 1.7 g of sodium bicarbonate, and 0.4 g of ethylenediaminetetraacetic acid (EDTA) into a 50 mL beaker and transferring the contents to a 2000 mL beaker. The 50 mL beaker was rinsed with tap water into the 2000 mL beaker, and tap water was added while stirring until the contents were completely dissolved, bringing the total volume to approximately 1 L. This solution was then transferred to a 2 L volumetric flask, and tap water was added to adjust the volume.
[0145] FWA was weighed at a rate of 0.0100–0.0200 g into a 100 mL volumetric flask, and the volume was adjusted using a buffer solution. The solution was sonicated for 5 minutes to ensure that a uniform dispersion was produced.
[0146] 10 g of Thermo Scientific® microcrystalline cellulose 50 μm powder and 50 ± 1 g of FWA solution were added to a 250 mL beaker, and their exact weights were recorded. The cellulose / FWA slurry was stirred for 20 minutes and then filtered through a filtration unit equipped with a polypropylene filter cloth. The filtrate (mother liquor) was collected. The cellulose was rinsed three times with 50 mL of tap water, and the cellulose was re-slurred by brief stirring before filtration. The combined filtrates (mother liquor and rinses 1-3) were collected and weighed. The cellulose cake was removed from the filtration unit and dried in a vacuum oven at 35°C for further visual, fluorescence, and lightfastness testing.
[0147] To measure the amount of FWA retained on the cellulose, the initial sample and the combined filtrate were subjected to HPLC. The amount of FWA retained could be calculated using the FWA peak area and input / output weights. The results are shown in Tables 6 and 7 below.
[0148] Durability can be defined by the following criteria: poor (<25%), moderate (25-50%), good (50-85%), and excellent (>85%). [Table 7] [Table 8]
[0149] The compounds shown in Table 7 exhibit performance levels (in terms of persistence) that are comparable to the industry standards shown in Table 6, but are also non-toxic. Furthermore, these compounds are biodegradable, non-biobacterial, and can be produced from sustainable materials.
[0150] Durability of the fabric: 10 liters of tap water at 35°C was added to a top-loading washing machine (capacity 4.5 kg). A standard fabric sample (10 cm x 10 cm, supplied by CFT, Center for Testmaterials BV) was added to the water along with 20 g of ECE-2 dye transfer test detergent ISO 105 C-08 and 0.1 g of FWA. The washing machine was run for 9 minutes, and then completely drained.
[0151] Rinse the fabric with 5 liters of cold water, run the washing machine for 3 minutes, then drain, and then rinse the fabric a second time with 5 liters of cold water for 3 minutes. After rinsing, spin-dry the fabric sample for 3 minutes and then air dry completely.
[0152] The surface color of the sample was measured using two Lovibond® LC100 spectrophotometers. The average surface color is shown in Table 8 below. [Table 9]
[0153] All compounds showed a substantial shift to a blue hue (h*=270) compared to the blank, demonstrating effectiveness in terms of both persistence and optical effect.
[0154] Example 2 - Biodegradability evaluation using Biowin(trademark) The chemical structure of this invention is biodegradable. For the purposes of the present invention,
[0155] Essentially biodegradable fluorescent whitening agents are defined as having more than 20% but less than 60% biodegradability in water, as measured by the OECD 301A-F test.
[0156] A readily biodegradable fluorescent whitening agent is defined as having the ability to rapidly and completely biodegrade in water within a 10-day window of 28 days (removal of 70% or more dissolved organic carbon, 60% or more theoretical carbon dioxide, or 60% or more theoretical oxygen demand, according to the OECD 301A-F test method).
[0157] To provide a biodegradability prediction, Biowin® software was used. This biodegradability prediction method is available as part of the Estimation Program Interface (EPI) Suite® software provided by the U.S. Environmental Protection Agency (EPA). Environ.Sci.Technol.,1994,28,459-465 presents an example of a group contribution method for predicting the probability and rate of aerobic biodegradation. This is the type of method used by Biowin®.
[0158] The Biowin 3 and Biowin 5 models are particularly relevant to the present invention. The predicted biodegradability of several compounds according to the present invention was evaluated using these models. If the result of Biowin 3 (final survey model) is >=2.75 (i.e., "weeks" or faster) and the probability of Biowin 5 (MITI linear model) is >=0.5, the prediction is YES (easily biodegradable). If this condition is not met, the prediction is NO (not easily biodegradable). The results are shown in Tables 9 and 10 below. [Table 10-1] [Table 10-2] [Table 11-1] [Table 11-2]
[0159] Example 3 - Thermogravimetric analysis (TGA) Samples were analyzed using thermogravimetric analysis with a Mettler Toledo TGA\DSC3+ under airflow conditions and a temperature gradient from room temperature to 800°C. [Table 12] [Table 13]
[0160] Some of the low-temperature mass loss may be due to residual water loss. Nevertheless, most of the compounds of this invention can be considered stable up to 110°C. They also exhibit comparable mass loss at 150°C to the benchmark and therefore exhibit at least a similar degree of thermal stability.
[0161] The thermal stability of the fluorescent whitening agent and optical glossing agent of the present invention is important because, in the case of laundry powder detergents, the components can be introduced before the moisture removal step in a fluidized bed dryer where the temperature can reach 50 to 110°C.
[0162] Example 4 - Detergent properties Representative detergent compositions of the present invention are shown in Tables 13, 14, 15, and 16. [Table 14] [Table 15] [Table 16] [Table 17]
Claims
1. A fluorescent whitening agent or optical glossing agent of formula (I) having the following structure, 【Chemistry 1】 During the ceremony, A is CHR １ R ２ (CH ２ ) ｎ And R １ H, CH ２ It is either OH or COZ, R ２ is H or CH ２ It is OH, and n is 1 or 2, or A is an optionally substituted aromatic ring or heteroaromatic ring condensed with N and X, where N and X are each bonded to adjacent carbon atoms on the ring; X is O, S, or N-H; Y is either Z or X'L; Each said Z is independently OH, OM, OR ３ , O(CH ２ ), ｑ SO ３ M, NH ２ , NHOH, NHR ４ or NR ４ ２ wherein M is selected from alkali metals or alkaline earth metals; R ３ This represents linear or branched alkyl, aryl, alkaryl, aralkyl, linear or branched alkyl alcohol, linear or branched alkyl alcohol polyol, hydroxyalkylamine, polyhydric alcohol, sugar, linear or branched alkyl ether, polyester having 2 to 1000 repeating units, or polyoxyalkylene chain having 2 to 1000 repeating units; q is between 1 and 5; R ４ These are independently methyl, ethyl, propyl, and C ４ ~C １２ Selected from alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propanyl, 1,3-dihydroxy-2-propanyl, 2,3-dihydroxypropyl, cyanomethyl, 2-aminoethyl or dicarbamoylmethyl; or NR ４ ２ represents a heterocyclic ring (such as morpholine); and In the equation, if Y is X'L; X' is O, S or N-H; and A fluorescent whitening agent or optical glossing agent, where L represents a linker portion connecting m repeating units of formula I, which has X' as defined above, instead of Y.
2. A fluorescent whitening agent or optical glossing agent of formula (II) having the following structure, 【Chemistry 2】 In the formula, Y is either Z or X'L; Z is OH, OM, OR ３ , O(CH ２ ) ｑ SO ３ M, NH ２ , NHOH, NHR ４ Or NR ４ ２ And, M represents alkali metals or alkaline earth metals; R ３ This represents linear or branched alkyl, aryl, alkaryl, aralkyl, linear or branched alkyl alcohol, linear or branched alcohol polyol, hydroxyalkylamine, polyhydric alcohol, sugar, linear or branched alkyl ether, polyester having 2 to 1000 repeating units, or polyoxyalkylene chain having 2 to 1000 repeating units; q is between 1 and 5; R ４ These are independently methyl, ethyl, propyl, and C ４ ~C １２ Selected from alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propanyl, 1,3-dihydroxy-2-propanyl, 2,3-dihydroxypropyl, cyanomethyl, 2-aminoethyl or dicarbamoylmethyl; or NR ４ ２ represents a heterocyclic ring (such as morpholine); and R is H, CHR ５ R ６ , R ５ , R ６ , alkyl sulfonates, polyethers, CH ２ COZ or CH (COZ) ((CH) ｎ COZ) where each Z may be the same or different, R ５ and R ６ R independently represents hydrogen, alkyl (e.g., methyl, ethyl, propyl, isopropyl), vinyl, phenyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, aminomethyl, (dimethylamino)methyl, 5-aminopentyl, or cyano, optionally R ５ and R ６ They may be the same or different, and n is either 1 or 2; In the equation, if Y is X'L; X' is O, S or N-H; and L is a fluorescent whitening agent or optical glossing agent, representing a linker portion that connects m repeating units of a variant of formula II in which X', as defined above, is present instead of Y.
3. A fluorescent whitening agent or optical glossing agent according to claim 1 or claim 2, a. In the formula, R ３ R represents a linear or branched alkyl group. ３ The compound is preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or 2-ethylhexyl; b. In the formula, R ３ R represents an alkyl alcohol. ３ This is selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, dodecanol, or stearyl or oleyl alcohol; c. In the formula, R ３ represents aryl, R ３ It is phenyl; d. In the formula, R ３ represents Alkaline, R ３ This is selected from benzyl or ethylphenyl; e. In the formula, R ３ R represents a linear or branched alkyl alcohol. ３ It is selected from 4-hydroxybutyl; f. In the formula, R ３ R represents a linear or branched alcohol polyol. ３ is a diol or triol, optionally 2,3-dihydroxypropyl or 2-hydroxy-1-(hydroxymethyl)ethyl; g. In the formula, R ３ R represents a hydroxyalkylamine. ３ This is selected from triethanolamine, N-methyldiethanolamine, or triisopropanolamine; h. In the formula, R ３ represents a polyhydric alcohol, R ３ It is glycerol; i. In the formula, R ３ represents sugar, R ３ This is selected from dextrose, fructose, galactose, glucose, lactose, maltose, or sucrose; j. In the formula, R ３ R represents a linear or branched alkyl ether. ３ is selected from 2-(2-hydroxyethoxy)ethyl, 2-(2-hydroxy-1-methylethoxy)-1-methylethyl, 2-[2-(2-hydroxy-1-methylethoxy)-1-methylethoxy]-1-methylethyl, 3-(3-hydroxypropoxy)propyl, 3-[3-(3-hydroxypropoxy)propoxy]propyl, 4-(4-hydroxybutoxy)butyl, 4-[4-(4-hydroxybutoxy)butoxy]butyl, 2-(2-methoxyethoxy)ethyl, or 2-[2-(2-methoxyethoxy)ethoxy]ethyl; and / or k. In the formula, R ３ represents a polyester or polyoxyalkylene chain having 2 to 1,000 repeating units, wherein the chain is a homopolymer or copolymer, and is a fluorescent whitening agent or optical gloss agent.
4. a. Linker L is derived from an alcohol, and X' is the oxygen of the precursor alcohol; or b. Linker L is derived from an amine, and X' is the nitrogen of the precursor amine. The fluorescent whitening agent or optical glossing agent according to any one of claims 1 to 3.
5. A fluorescent whitening agent or optical glossing agent according to any one of claims 1 to 4, wherein m is 2 or more, optionally 3 to 20, and optionally 3, and is a dimer or oligomer compound.
6. Linker L is ethylene, propylene, or C ４ ~C １２ A fluorescent whitening agent or optical glossing agent according to any one of claims 1 to 5, comprising a polyester chain having 0 to 1,000 repeating units which is alkylene, homopolymer or copolymer, or a polyoxyalkylene chain having 0 to about 1,000 repeating units which is homopolymer or copolymer, triethanolamine, glycerol, or sugar.
7. A fluorescent whitening agent or optical glossing agent derived from the condensation of a dicarboxylic acid or polycarboxylic acid with an amine, optionally, from the condensation of a dicarboxylic acid or polycarboxylic acid with an amino acid or amino acid derivative, or optionally from the condensation of citric acid with an amino acid or amino acid derivative.
8. A fluorescent whitening agent or optical glossing agent according to any one of claims 1 to 7, which is formulated for use as a fluorescent whitening agent or optical glossing agent.
9. A fluorescent whitening agent or optical glossing agent according to claim 8, comprising a portion of a fluorescent whitening or optical glossing compound, wherein the compound further comprises at least one auxiliary compound optionally selected from one or more surfactants, detergents, bleaches, carrier compounds, stabilizers, and / or dispersants.
10. A fluorescent whitening or optical gloss compound comprising a fluorescent whitening agent or optical gloss agent according to any one of claims 1 to 8, and at least one detergent, bleach, carrier compound, stabilizer and / or dispersant.
11. Use of a compound of formula (I) or formula (II) according to any one of claims 1 to 8 as a fluorescent whitening agent or optical glossing agent.
12. A method for providing a substrate with fluorescent whitening or optical gloss, comprising contacting the substrate with a fluorescent whitening agent or optical gloss agent according to any one of claims 1 to 8 or a fluorescent whitening or optical gloss compound according to claim 10, under conditions effective in enabling chemical and / or physical bonding of the fluorescent whitening agent or optical gloss agent to or into the substrate.