Fluorescent whitening agent

Abstract

The present invention provides a fluorescent brightener or optical brightener of formula (I) or formula (II): Formula (I) or formula (II) has the structure: (I), (II) wherein Y is Z or X 'L; wherein: A is CR1R2 (CH2) n wherein R1 is H, CH2OH or COZ, R2 is H or CH2OH, and wherein n is 1 or 2, or wherein A is an optionally substituted aromatic or heteroaromatic ring fused to N and X wherein 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; z or each Z is independently OH, OM, OR3, O (CH2) qSO3M, NH2, NHOH, NHR4 or NR42, wherein M is selected from an alkali metal or an alkaline earth metal; r3 represents a linear or branched alkyl group, an aryl group, an alkaryl group, an aralkyl group, a linear or branched alkyl alcohol, a linear or branched alkyl alcohol polyol, a hydroxyalkylamine, a polyol, a sugar, a linear or branched alkyl ether, a polyester having 2 to 1000 repeating units or a polyoxyalkylene chain having 2 to 1000 repeating units; q is 1 to 5; r4 is independently selected from the group consisting of methyl, ethyl, propyl, C4 to C12 alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propionyl, 1, 3-dihydroxy-2-propionyl, 2, 3-dihydroxypropyl, cyanomethyl, 2-aminoethyl, or diamino formylmethyl, and R4 is independently selected from the group consisting of methyl, ethyl, propyl, C4 to C12 alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propionyl, 1, 3-dihydroxy-2-propionyl, 2, 3-dihydroxypropyl, cyanomethyl, 2-aminoethyl, or diamino formylmethyl; or NR42 represents a heterocyclic ring, such as morpholine; and wherein when Y is X 'L; x'is O, S or N-H; and L represents a linker moiety linking m repeating units of formula I or II, replacing Y with X'as defined above; r is H, CHR5R6, R5, R6, an alkyl sulfonate, a polyether, CH2COZ or CH (COZ) ((CH) nCOZ) wherein each Z may be the same or different, R5 and R6 independently represent 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 wherein R5 and R6 are the same or different, n is 1 or 2.

Description

Technical Field

[0001] This invention relates to fluorescent whitening agents (FWA), optical brighteners, and certain applications. Background Technology

[0002] The industry standards for fabric brighteners (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, along with other conventional FWAs or optical brighteners, have one or more of the following disadvantages:

[0003] 1. They are usually made from fossil fuels;

[0004] 2. They are non-biodegradable;

[0005] 3. They are poisonous in aquatic environments.

[0006] The object of the present invention is to provide an improved FWA or optical brightener in at least one of these aspects.

[0007] Existing technologies recognize that fluorophores can be synthesized from sustainable materials such as citric acid.

[0008] In this regard, RSCAdv.,2015,5,34795 discloses 4-oxo-1-thia-3a-aza-6-indencarboxylic acid and 5-oxo-2,3-dihydro-5H-[1,3]oxazolo[3,2-a]pyridine-7-carboxylic acid obtained by condensation of citric acid with an amino acid or a derivative thereof, but does not suggest any potential applications. The first-mentioned compound is also disclosed in CN108101929 and CN104530089 in the context of medical fluorescent imaging agents.

[0009] J. Mater. Chem. C, 2015, 3, 5976-5984 discloses 1,2,3,5-tetrahydro-5-oxo-imidazo[1,2-a]pyridine-7-carboxylic acid and 4-oxo-1-thia-3a-aza-6-indane ester, which are related to the production of fluorescent carbon nanoparticles by pyrolysis of citric acid and amines. The first of these compounds is also disclosed as a pharmaceutical intermediate in CN114507230.

[0010] Methyl-4-oxo-1-thia-3a-aza-3,6-indenecarboxylic acid, which is also associated with fluorescent carbon nanoparticles, is disclosed in RSCAdv.,2022,12,19,11640-11648 (Tables 1A-B).

[0011] CN109438479 discloses the potential applications of hexyl 4-oxo-1-thia-3a-aza-6-indanecarboxylate and certain other indanecarboxylate compounds in fluorescent whitening, but does not specify the specific application areas.

[0012] Dimeric and oligomeric indene carbamate compounds are widely disclosed in US2019 / 231909, but no application descriptions are provided.

[0013] Fluorescent imaging agents, 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 WO2016 / 164437.

[0014] The present invention seeks to provide FWA or optical brighteners that have functionality comparable to the aforementioned industry standards, but with fewer environmental drawbacks. Summary of the Invention

[0015] According to a first aspect of the present invention, a fluorescent whitening agent or optical brightening agent of formula (I) is provided, which has the following structure:

[0016]

[0017] in:

[0018] A is CR 1 R 2 (CH2) n , where R 1 For H, CH2OH or COZ, R 2 It is H or CH2OH, and n is 1 or 2, or A is an optionally substituted aromatic ring or heterocyclic ring fused with N and X, wherein N and X are bonded to adjacent carbon atoms on the ring, respectively;

[0019] X is O, S, or NH;

[0020] Y is either Z or X'L;

[0021] The Z, or each Z independently, is OH, OM, OR. 3 O(CH2) q SO3M, NH2, NHOH,

[0022] NHR 4 or NR 4 2, of which:

[0023] M is selected from alkali metals or alkaline earth metals;

[0024] R 3Represents straight-chain or branched alkyl, aryl, alkylaryl, aralkyl, straight-chain or branched alkyl alcohols, straight-chain or branched alkyl alcohol polyols, hydroxyalkylamines, polyols, sugars, straight-chain or branched alkyl ethers, polyesters having 2 to 1000 repeating units, or polyoxygenates having 2 to 1000 repeating units.

[0025] Alkenyl chain;

[0026] q ranges from 1 to 5;

[0027] The R 4 Or each R 4 Independently selected from methyl, ethyl, propyl, C4 to C 12 Alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propionyl, 1,3-dihydroxy-2-propionyl, 2,3-dihydroxypropyl, cyanomethyl, 2-aminoethyl or dicarboxymethyl; or, NR 4 2 represents a heterocycle, such as morpholine; and

[0028] Where Y is X'L;

[0029] X' is O, S, or NH; and

[0030] L represents the connecting body of m repeating units of the connecting type I, and Y is replaced by X' as defined above.

[0031] In embodiments where A is an optionally substituted aromatic heterocycle, A is preferably a pyridine ring.

[0032] In R 3 In embodiments representing straight-chain or branched alkyl groups, R 3 Preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or 2-ethylhexyl.

[0033] In R 3 In the embodiments representing alkyl alcohols, R 3 The preferred materials are methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, dodecanol, stearyl alcohol, or oleyl alcohol.

[0034] In R 3 In the implementation scheme representing aryl, R 3 Preferably phenyl, in R 3 In the embodiments representing alkylaryl groups, R 3 Preferably selected from benzyl or ethylphenyl.

[0035] In R 3 In embodiments representing straight-chain or branched alkyl alcohols, R 3 Preferably selected from 4-hydroxybutyl.

[0036] In R 3In embodiments representing straight-chain or branched-chain alcohol polyols, R 3 Preferably, it is a diol or triol. In the most preferred case, R 3 It can be selected from 2,3-dihydroxypropyl or 2-hydroxy-1-(hydroxymethyl)ethyl.

[0037] In R 3 In the embodiments representing hydroxyalkylamines, R 3 The preferred selection is from triethanolamine, N-methyldiethanolamine or triisopropanolamine.

[0038] In R 3 In the implementation scheme representing polyols, R 3 Glycerin is preferred.

[0039] In R 3 In the implementation scheme representing sugar, R 3 The preferred sugars are dextrose, fructose, galactose, glucose, lactose, maltose, or sucrose.

[0040] In R 3 In embodiments representing straight-chain or branched alkyl ethers, R 2 Preferably 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.

[0041] In R 3 In embodiments representing polyesters or polyoxyethylenes having 2 to 1000 repeating units, it can be a homopolymer or copolymer.

[0042] Linker L can be derived from an alcohol, in which case X' is the oxygen of the precursor alcohol; or it can be derived from an amine, in which case X' is the nitrogen of the precursor amine.

[0043] In the dimer or oligomer of the present invention, m is 2 or greater, preferably 3 to 20, and most preferably 3.

[0044] Linker L can be made of ethylene, propylene, or C4 to C4. 12 It comprises any one of the following: alkylene, a polyester chain having 0 to 1000 repeating units that are homopolymers or copolymers, or a polyoxyalkylene chain having 0 to 1000 repeating units that are homopolymers or copolymers, triethanolamine, glycerol, or sugar.

[0045] According to a second aspect of the present invention, a fluorescent whitening agent or optical brightening agent of formula (II) is provided, which has the following structure:

[0046]

[0047] Where Y is Z or X'L;

[0048] Z represents OH, OM, or OR. 3 O(CH2) q SO3M, NH2, NHOH, NHR 4 or NR 4 2,

[0049] M represents alkali metals or alkaline earth metals;

[0050] R 3 Represents straight-chain or branched alkyl, aryl, alkylaryl, aralkyl, straight-chain or branched alkyl alcohol, straight-chain or branched polyol, hydroxyalkylamine, polyol, sugar, straight-chain or branched alkyl ether, polyester having 2 to 1000 repeating units, or polyoxyalkylene chain having 2 to 1000 repeating units.

[0051] q ranges from 1 to 5;

[0052] R 4 Independently selected from methyl, ethyl, propyl, C4 to C 12 Alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propionyl, 1,3-dihydroxy-2-propionyl, 2,3-dihydroxypropyl, cyanomethyl, 2-aminoethyl or dicarboxymethyl; or, NR 4 2 represents a heterocycle, such as morpholine; and

[0053] R represents H, CHR 5 R 6 R 5 R 6 Alkyl sulfonates, polyethers, CH2COZ or CH(COZ)((CH) n COZ), where each Z can be the same or different.

[0054] R 5 and R 6 Independently representing hydrogen, alkyl (such as methyl, ethyl, propyl, isopropyl), vinyl, phenyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, aminomethyl, (dimethylamino)methyl, 5-aminopentyl or cyano, optionally wherein R 4 and R 5 Same or different, and

[0055] n is 1 or 2;

[0056] Where Y is X'L;

[0057] X' is O, S, or NH; and

[0058] L represents the connecting body portion of m repeating units of the connected type II variant, where X' exists as defined above in place of Y.

[0059] In R 3 In embodiments representing straight-chain or branched alkyl groups, R 3 Preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or 2-ethylhexyl.

[0060] In R 3 In the embodiments representing alkyl alcohols, R 3 The preferred materials are methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, dodecanol, stearyl alcohol, or oleyl alcohol.

[0061] In R 3 In the implementation scheme representing aryl, R 3 Preferably phenyl, in R 3 In the embodiments representing alkylaryl groups, R 3 Preferably selected from benzyl or ethylphenyl.

[0062] In R 3 In embodiments representing straight-chain or branched alkyl alcohols, R 3 Preferably selected from 4-hydroxybutyl.

[0063] In R 3 In embodiments representing straight-chain or branched-chain alcohol polyols, R 3 Preferably, it is a diol or triol. In the most preferred case, R 3 It can be selected from 2,3-dihydroxypropyl or 2-hydroxy-1-(hydroxymethyl)ethyl.

[0064] In R 3 In the embodiments representing hydroxyalkylamines, R 3 The preferred selection is from triethanolamine, N-methyldiethanolamine or triisopropanolamine.

[0065] In R 3 In the implementation scheme representing polyols, R 3 Glycerin is preferred.

[0066] In R 3 In the implementation scheme representing sugar, R 3 The preferred sugars are dextrose, fructose, galactose, glucose, lactose, maltose, or sucrose.

[0067] In R 3 In embodiments representing straight-chain or branched alkyl ethers, R 3Preferably 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.

[0068] In R 3 In embodiments representing polyester or polyoxyethylene chains having 2 to 1000 repeating units, it can be a homopolymer or copolymer.

[0069] Linker L can be derived from an alcohol, in which case X' is the oxygen of the precursor alcohol; or it can be derived from an amine, in which case X' is the nitrogen of the precursor amine.

[0070] In the dimer or oligomer of the present invention, m is 2 or greater, preferably 3 to 20, and most preferably 3.

[0071] Linker L can be made of ethylene, propylene, or C4 to C4. 12 It comprises any one of the following: alkylene, a polyester chain having 0 to 1000 repeating units that are homopolymers or copolymers, or a polyoxyalkylene chain having 0 to 1000 repeating units that are homopolymers or copolymers, triethanolamine, glycerol, or sugar.

[0072] The FWA and optical brightener of the present invention are preferably formulated as fluorescent whitening agents or optical brighteners, as appropriate. Typically, such formulation includes providing an active ingredient (FWA or optical brightener) and at least one auxiliary compound commonly found in fluorescent whitening or optical brightening formulations. Such auxiliary compounds may be selected from one or more of, for example, detergents, bleaching agents, carrier compounds, stabilizers, and / or dispersants.

[0073] The present invention also provides the use of the above-mentioned compounds as fluorescent whitening agents or optical brightening agents.

[0074] The present invention also provides a fluorescent whitening agent or an optical brightening agent, comprising the above-mentioned fluorescent whitening agent or optical brightening agent and at least one detergent, bleach, carrier compound, stabilizer and / or dispersant.

[0075] The present invention also provides a method for providing fluorescent whitening or optical brightening to a substrate, comprising contacting the substrate with one or more of the above-mentioned compounds under conditions that effectively bind one or more of the compounds to the substrate chemically and / or physically. Detailed Implementation

[0076] Current industry-standard fluorescent whitening agents or optical brighteners, including DAS-1, DAS-2, DSPB, and FB28, absorb ultraviolet light in the 340 nm to 370 nm range and emit visible blue light in the 420 nm to 470 nm range. To achieve this effect, elongated conjugated molecular systems are needed to provide an appropriate number of π-electrons within the conjugated aromatic system to enable appropriate energy transitions, thereby achieving emission in the 420 nm to 470 nm range upon de-excitation. As demonstrated by the current industry-standard chemical structures, this typically requires elongated aromatic systems primarily based on carbon and hydrogen, with high molecular weights.

[0077] Pyridones and citric acid derivatives are known to have similar π-electron counts and emit visible blue light in the 420 nm to 470 nm range. The significantly lower molecular weight of these derivatives is achieved through the introduction of heteroatoms (such as nitrogen and oxygen).

[0078] The excitation and deexcitation properties of the fluorescent brighteners or optical brighteners of the present invention can be understood mechanistically with reference to prior art study SCAdv., 2015, 5, 34795, which attributes the fluorescence of similar compounds in the 420 nm to 470 nm range to π*-π transitions in the same carbon-oxygen double bond, as found in pyridone- and citric acid-based scaffolds. The carboxyl groups, particularly carboxylic acid groups, present in the structures of formulas (I) and (II) of the present invention are believed to contribute to the desired number of π-electrons associated with fluorescence within the desired range.

[0079] Therefore, the fluorescent brighteners or optical brighteners of the present invention are more advantageous than current industry standards because they use smaller compounds with lower molecular weights, yet provide comparable fluorescence. Furthermore, the structures of formulas (I) and (II) can be readily functionalized to tune application performance with minimal impact on the fluorescence behavior of the fluorescent brighteners or optical brighteners.

[0080] According to the present invention, several other factors also affect the efficacy of FWA or optical brighteners.

[0081] The FWA or optical brighteners according to the invention typically absorb ultraviolet light in the range of 340 nm to 370 nm and emit visible light in the range of 420 nm to 470 nm. In this respect, the quantum yield of these compounds 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%.

[0082] The FWA or optical brighteners of this invention exhibit a much higher relative quantum yield than current industry standards. For example, only DSPB gives a comparable value greater than 70%. The FWA or optical brighteners described in this invention are superior to current standards because similar fluorescence performance can be achieved with a much smaller molecular weight, which in turn can lead to a lower loading of the FWA or optical brightener in the final application. The lower loading can mitigate any potential adverse effects associated with the compound.

[0083] The FWA or optical brightener of the present invention generally exhibits good directness to cellulosic fabrics, retaining at least about 30% load after a typical washing cycle.

[0084] The FWA or optical brightener according to the invention can be sustainably produced from readily available starting materials using environmentally sustainable reagents. Therefore, the invention also provides a fluorescent whitening agent or optical brightener derived from the condensation of dicarboxylic acids or polycarboxylic acids with amines, particularly the condensation between dicarboxylic acids or polycarboxylic acids and amino acids or amino acid derivatives, especially the condensation between citric acid and amino acids or amino acid derivatives.

[0085] Current industry-standard free radical ethers (FWAs) and optical brighteners, including DAS-1, DAS-2, DSPB, and FB28, all possess high molecular weight, highly conjugated aromatic systems with limited oxidative or hydrolytic capacity, resulting in poor biodegradability. Therefore, current industry-standard FWAs represent a growing environmental problem, as they are detected as pollutants not only in municipal wastewater (MarinePollution Bulletin, 2022, 178, 113559) but also in indoor environments (Environ. Sci. Technol., 2022, 56, 10131-10140). Recent studies have shown that FWAs are a source of pollution in municipal wastewater, negatively impacting aquatic ecosystems and water resources. MarinePollution Bulletin, 2022, 178, 113559 identifies FWAs as a newly emerging and concerning pollutant because their concentrations in wastewater are comparable to the highest concentration ranges of more well-studied wastewater pollutants (such as pharmaceuticals) (approximately 10 ng / L to 1000 ng / L). Swedish data show that DAS-2 is always detected in sample effluent at a high concentration of approximately 1500 ng / L.

[0086] In contrast, the FWA and optical brighteners according to the invention have smaller fluorescent cores and are therefore more readily biodegradable because they are more susceptible to biological attack, while still providing sufficient oxidative and hydrolytic stability for intended applications.

[0087] The molecular weight of the FWA and optical brightener 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.

[0088] Biodegradation estimation based on chemical structure is complex due to the varying physicochemical properties of organic compounds. Previous methods for estimating biodegradation relied on metabolic pathways and microbial diversity. Recently, prediction methods have employed population contributions, QSAR, or machine learning approaches.

[0089] See Ecotoxicol. Environ. Saf. 1989, 18, 252-267. Based on a survey of 22 biodegradation experts, a hierarchical structure was constructed to represent the approximate order in which various functional groups are considered to contribute to aerobic biodegradation: ester = amide = acid anhydride > hydroxyl > carboxylic acid = epoxide = unsaturated site > benzene ring = methyl = methylene. It is generally inferred that, all other things being equal, partially oxidized compounds are generally considered more susceptible to bioattack than those that are not partially oxidized, and hydrolyzable chemicals are considered more easily degraded. The time required for final degradation is usually inferred from considerations of molecular weight, branching, halogenation, functional groups, solubility, and other factors.

[0090] Advantageously, the FWA and optical brightener according to the invention are biodegradable. Preferably, they contain at least one unoxidized or only partially oxidized functional group, thus allowing them to be oxidized or further oxidized. Preferably, they contain at least one hydrolyzable group.

[0091] Therefore, the present invention also provides an FWA or optical brightener containing at least one unstable group. According to standard OECD 301A-F testing, an inherently biodegradable fluorescent whitening agent can be defined as having a biodegradability in water >20% but <60%. An easily biodegradable fluorescent whitening agent or optical brightener is characterized by its ability to rapidly and completely biodegrade in water within a 10-day window over 28 days (dissolved organic carbon removal ≥70%, theoretical carbon dioxide removal ≥60%, or theoretical oxygen demand ≥60%, depending on the standard OECD 301A-F testing method).

[0092] The FWA and optical brightener according to the invention are preferably stable at relatively high pH levels, such as from about pH 7 to about pH 10, and from pH 7.5 to about 9.5, which are typical conditions for laundry washing.

[0093] The FWA and optical brightener according to the present invention are preferably UV-stable.

[0094] The FWA and optical brightener according to the invention are preferably oxidically stable during normal washing cycles.

[0095] According to the present invention, preferred examples of fluorescent whitening agents and optical brightening agents are as follows:

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] In a specific embodiment of the invention, the linker is capable of carrying multiple fluorescent whitening nuclei, examples of which are given below, and can be coupled to one of the general nuclei (I) and (II) at each location.

[0113]

[0114] According to the present invention, fluorescent whitening agents or optical brighteners exhibit excellent chemical stability at relatively high pH levels, such as the typical pH of laundry detergent formulations. In these applications, they also possess very suitable thermal stability and can be prepared by synthetic methods at temperatures up to 130°C (see below).

[0115] The fluorescent whitening agents or optical brighteners according to the present invention can be used in a range 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 agents or optical brighteners can make materials (e.g., cotton) appear whiter while also masking yellowing due to aging.

[0116] Fluorescent brighteners or optical brighteners can be used in all types of formulations, such as liquids, powders, tablets, or rods, in appropriate proportions and loadings.

[0117] synthesis

[0118] Fluorescent brighteners or optical brighteners can be prepared from readily available starting materials (e.g., citric acid or citric acid). The preparation of the target compound of the present invention (Scheme 1) is more advantageously environmentally acceptable due to the use of common and renewable building blocks, such as citric acid produced on a large scale by fermentation.

[0119] Each core structure can be readily synthesized by heating citric acid and the second amine building blocks in the presence of water, with water itself being the main byproduct. Water-based synthesis is safer, cleaner, more environmentally friendly, and highly scalable.

[0120] Further functionalization of the core unit can be readily achieved through a second simple reaction with an alcohol or amine, in order to modify and / or improve the directness of the resulting fluorescent brightener or optical brightener in the desired application.

[0121] Scheme 1: A representative synthetic route for the optical brightening agent of the present invention, wherein Y is as defined in the first aspect of the present invention, X 1 For any suitable leaving group

[0122]

[0123] In contrast, the preparation of existing optical brighteners, such as the baselines DAS1, DAS2, and FB28 (Scheme 2A), requires complex synthetic methods, including five synthetic steps, and the use of environmentally unfriendly materials, such as noble metal catalysts and hazardous materials (e.g., cyanuric chloride). Similarly, the preparation of the fluorescent brightener DSPB (Scheme 2B) requires complex synthetic steps, including environmentally unfriendly and / or hazardous materials, such as trimethoxyphosphorus and dimethylformamide (DMF). Both molecular families (Scheme 2A or Scheme 2B) utilize petrochemical-derived raw materials.

[0124] Option 2A: Synthesis route for current benchmark optical brighteners such as DAS1, DAS2, and FB28

[0125]

[0126] Option 2B: Synthesis route of the current benchmark optical brightener DSPB

[0127]

[0128] General method for synthesizing the core unit (base of formula (I)) of fluorescent whitening agent from citric acid

[0129] A mixture of citric acid (equivalent) and the corresponding amine (1 equivalent) was dissolved in water (1 volume). The reaction mixture was heated to 100°C to distill off all the water. The reaction temperature was then raised to 140°C to melt the resulting residue, and the molten mixture was stirred for 16 hours, with the water from the reaction being distilled off. The resulting resin material was cooled to <100°C before adding fresh water (1 volume). The mixture was then cooled to ambient temperature with vigorous stirring to disperse the product before filtration. The separated solids were washed with fresh water (0.5 volume) and then dried in a vacuum oven to obtain the final product.

[0130] Synthesis of the fluorescent whitening agent core unit (1a)

[0131] A mixture of citric acid (200 g, 1.05 mol) and mercaptoethylamine (80.3 g, 1.05 mmol) was dissolved in water (300 mL). The reaction mixture was heated to 100 °C to distill off all the water. The reaction temperature was then raised to 140 °C and stirred for 4 hours to melt the resulting residue. The temperature was then raised to 160 °C, and the mixture was stirred and melted for 16 hours, with the water from the reaction being distilled off. The resulting resin material was cooled to <100 °C before adding fresh water (300 mL). The mixture was then cooled to ambient temperature with vigorous stirring to disperse the product before filtration. The separated solid was washed with fresh water (150 mL) and then dried in a vacuum oven to give a final product as a yellow powder in a yield of 64.5% (131.4 g, 0.68 mol).

[0132] Analytical data: HPLC purity: 99.7%; LCMS (+VE ions): m / z 198.1

[0133] Synthesis of the fluorescent whitening agent core unit (3a)

[0134] A mixture of citric acid (200 g, 1.05 mol) and L-cysteine ​​(127.2 g, 1.05 mL) was dissolved in water (325 mL). The reaction mixture was heated to 100 °C to distill off all the water. The reaction temperature was then raised to 140 °C to melt the resulting residue, and the molten mixture was stirred for 16 hours, with the water from the reaction being distilled off. The resulting resin material was cooled to <100 °C before adding fresh water (325 mL). The mixture was then cooled to ambient temperature with vigorous stirring to disperse the product before filtration. The separated solid was washed with fresh water (150 mL) and then dried in a vacuum oven to give a final product as a yellow powder in a yield of 61% (154.7 g, 0.64 mol).

[0135] Analytical data: HPLC purity: 99.8%; LCMS (+VE ions): m / z 242.2; 1 HNMR (DMSO-d6400=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, 62.6ppm.

[0136] Synthesis of the fluorescent whitening agent core unit (4a)

[0137] 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 give a final product as a yellow powder with near-quantitative yield and good purity.

[0138] Esterification reaction of fluorescent whitening agent core unit (1a) with ethanol

[0139] A mixture of FWA 1a (5 g, 0.026 mol) and p-toluenesulfonic acid (0.04 g, 0.002 mol) was suspended in industrial methylated ethanol (IMS, also known as industrial denatured ethanol, IDA, 15 mL), heated to reflux, and then stirred for 24 hours. The reaction mixture was then boiled to dryness to remove water from the reaction. 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 give the target ester as a beige powder in near-quantitative yield.

[0140] Analytical data: HPLC purity: 95.8%; LCMS (+VE ions): m / z 226.2

[0141] Esterification reaction of fluorescent whitening agent core units with low-boiling-point alcohols (<100℃)

[0142] The mixture of prepared FWA cores (1 equivalent) was suspended in alcohol (3 volumes), heated to reflux, and then stirred for 24 hours. The reactants were then boiled to dryness to remove water from the reaction mixture. Fresh alcohol (3 volumes) was then added to the reaction mixture, and reflux was continued for 24 hours. The reaction mixture was then cooled, and the solvent was removed under reduced pressure to give the target ester in near-quantitative yield.

[0143] Esterification reaction of fluorescent whitening agent core units with high-boiling-point alcohols (>100℃)

[0144] A mixture of the prepared FWA core (1 equivalent) and p-toluenesulfonic acid (0.08 equivalent) was suspended in an alcohol (1.1 equivalent per carboxylic acid group). The resulting mixture was then heated to >100°C, with 130°C being a preferred reaction temperature, and the reaction was carried out by water distillation for more than 16 hours. Excess alcohol was then removed under reduced pressure or azeotropic distillation, as appropriate. For high-boiling alcohols, the desired ester was purified by column chromatography or precipitation from acetone.

[0145] The amidation reaction of FWA nucleus 1a ethyl ester with ethylenediamine

[0146] The prepared FWA nucleus 1a ethyl ester sample (2.25 g, 0.01 mol) was suspended in industrial methylated ethanol (IMS, 15 mL), and then ethylenediamine (1.17 g, 0.02 mol) was added, immediately turning orange. The resulting mixture was heated under reflux and stirred for 16 hours. The reaction was then cooled, and excess alcohol was removed under reduced pressure to give the desired beige powdered amide in 82% yield (1.91 g, 0.008 mol).

[0147] Analytical data: HPLC purity: 95.6%; LCMS (+VE ions): m / z 240.2

[0148] Amide reaction of functionalized fluorescent whitening agents

[0149] The desired FWA nucleoethyl ester sample (1 equivalent) was suspended in IMS (5 volumes), and then the target amine (2 equivalents per carboxylic acid group) was added at room temperature. The resulting mixture was heated under reflux and stirred for 16 hours. The reaction was then cooled, and excess alcohol was removed under reduced pressure to obtain the desired amide.

[0150] carrier

[0151] In concentrated and granular detergent compositions, the composition is typically provided to the end user as a diluted or dissolved solution. In such solutions, the pH value to which the optical brightener comes into contact before use may be particularly high, which can lead to storage problems, especially in terms of storage stability. Therefore, there is a need for improved delivery compositions that are compatible with environmentally acceptable optical brighteners (particularly those defined according to the present invention).

[0152] Similarly, optical brighteners can be incorporated into fabric detergent compositions. However, mere incorporation does not guarantee that the optical brightener will adsorb onto the washed fabric. One of the functions of a detergent composition is to adsorb onto the surface of the fabric material and preferentially adhere to it, thereby removing oil and other residues. This is typically achieved using surfactants. Surfactants can be classified as anionic, nonionic, and cationic. Therefore, there is a need for a formulation of a fabric detergent composition incorporating optical brighteners that allows the optical brighteners to remain adsorbed onto the fabric material surface after the washing process, particularly when rinsing follows the washing process. Thus, there is a need for a fabric detergent composition that delivers an environmentally acceptable optical brightener during the washing process, and which remains in situ on the material afterward.

[0153] In particular, there is a need for delivery compositions of environmentally acceptable optical brighteners (especially those structures defined in this application) that provide delayed release of the optical brightener at specific points in the washing process. Specifically, these are the points in the washing process where the optical brightener is most likely to be adsorbed onto the fabric. Alternatively, in some cases, rapid release of the optical brightener or optical brightener can also be advantageous, as this would allow the optical brightener to be adsorbed onto a fabric (e.g., prior to the presence of a significant concentration of surfactant in the washing method), thus competing with the optical brightener for adsorption onto the fabric.

[0154] In one embodiment of the invention, a fabric washing detergent composition is provided. The fabric washing detergent composition can be in various different forms, such as compositions for hand washing, machine washing, colorless clothing, and colored clothing.

[0155] Compositions providing oxidants are widely used, but these compositions can also cause stability problems with environmentally acceptable fluorescent whitening agents (such as those structures defined in this application). Therefore, there is a need for delivery compositions that mitigate or improve the problems caused by oxidants present in fabric washing detergent compositions.

[0156] The aforementioned issues are particularly relevant to environmentally acceptable fluorescent whitening agents, due to the chemical complexity of these molecules, which are present in small amounts and thus inherently have a high surface area / volume ratio in the composition. Furthermore, compounds tailored for environmentally acceptable compositions often have unstable groups designed to degrade in order to achieve improved biodegradability.

[0157] It is worth noting that chemical groups designed to improve biodegradability are often more unstable in the presence of oxidants or under high pH conditions, or combinations thereof.

[0158] Furthermore, the optical brighteners used in the detergent composition are preferably present at low levels, for example, as low as 0.01%. Importantly, high concentrations, such as those caused by individual particles, are unfavorable because they lead to uneven distribution. This is particularly pronounced, for example, during transport due to the settling of the particle mixture. Therefore, there is a need for a delivery composition capable of uniform distribution throughout the entire composition, as well as any other related detergent components in the detergent composition, particularly for fabric washing detergent compositions, and even more particularly for particulate solid fabric washing detergent compositions.

[0159] Therefore, in another embodiment of the present invention, a solid carrier composition of a fluorescent whitening agent composition is provided according to the above, comprising a carrier and a fluorescent whitening agent.

[0160] In such an embodiment, the fluorescent whitening agent or optical brightening agent can be adsorbed into the structure of the carrier. Furthermore, the fluorescent whitening agent or optical brightening agent can be present in the carrier composition at less than 34% by weight.

[0161] In another embodiment, the optical brightener or fluorescent whitening agent may be present in the carrier composition at a concentration of 1% to 34% by weight. In a preferred embodiment, the optical brightener or fluorescent whitening agent may be present at a concentration of 15% to 30% by weight. Advantageously, this appears to result in less dust generation and less any liquid being wicked from the particles, particularly when the optical brightener is provided as a liquid.

[0162] The optical brighteners according to the invention can be provided in solid or liquid form. Optical brighteners are particularly suitable for liquid or low-melting-point forms, which makes them difficult to handle when incorporated into products as additives. Examples of such products include detergents, such as fabric detergents; cosmetics, such as sunscreens; papermaking, such as paper finishing; and various other applications in which optical brighteners are incorporated. In these applications, the optical brighteners may be present in small amounts, typically less than 1% by weight, sometimes as low as 0.01% by weight.

[0163] Therefore, handling and incorporating these materials is more difficult in these applications. To overcome this challenge, it is advantageous to increase the weight and volume of the carrier by incorporating the optical brightener. However, it is important, especially when the fabric brightener is a liquid or a low-melting-point solid, that it is completely incorporated into the carrier. In a particular embodiment of the invention, when such incorporation level is 34% by weight or less, the optical brightener or brightener can advantageously be incorporated into the gaps in the porous structure.

[0164] In embodiments of the present invention, the carrier may be selected from one or more of sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate cellulose, carboxymethyl cellulose, polyvinyl alcohol with 100,000 or more repeating units, sodium silicate, polyvinylpyrrolidone with 50,000 or more repeating units, or zeolite. In particular, these materials are compatible with detergent compositions.

[0165] In a preferred embodiment of the 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 aqueous media.

[0166] In this invention, the carrier composition can be prepared by drying the fluorescent whitening agent and the carrier from the solution, as this allows for the production of a homogeneous mixture before the carrier composition is prepared in solid form by drying.

[0167] In this invention, the drying of the composition is preferably achieved using spray drying. Spray drying has been found to enable the effective combination of fluorescent whitening agents, especially those with relatively low solubility, with the soluble components in carrier form in a substantially uniform manner. This is particularly useful when the fluorescent whitening agent is a liquid or a low-melting-point solid, as a homogeneous mixture with the dissolved carrier can be produced for spray drying, resulting in “dry” and low-dust particles.

[0168] In this invention, the carrier composition can be prepared by fluidized bed drying. Advantageously, this method of drying is effective where the fluorescent whitening agent is sensitive to high drying temperatures. This is particularly relevant because the fluorescent whitening agents according to the invention are readily biodegradable and typically contain unstable groups (e.g., esters), making them temperature-sensitive relative to conventional fluorescent whitening agents.

[0169] In this invention, the carrier composition comprises an insoluble carrier and a low-solubility or solid fluorescent whitening agent, which can be prepared by co-granulation of the carrier and the fluorescent whitening agent with a binder. This method avoids high temperatures, and is therefore advantageous considering the aforementioned issues regarding the stability of the fluorescent whitening agent. The binder can be selected from sodium silicate or organic polymers. In the most preferred embodiment, the binder can be an organic polymer, particularly polyvinyl alcohol or polyvinyl alcohol copolymers. The polar nature of these polymers advantageously provides a more homogeneous composition than polymers with low polarity or hydrophilicity.

[0170] Polycarboxylic acids can also be examples of suitable adhesive materials, especially in the presence of amine or amide functional groups in the fluorescent whitening agent, as they provide improved solubility of the fluorescent whitening agent during the preparation of the carrier composition.

[0171] Clearly, a synergistic effect exists between proteolytic enzymes and fluorescent whitening agents; therefore, in some further embodiments of the invention, the carrier composition may further comprise proteolytic enzymes. This is particularly true when the fluorescent whitening agent comprises an amide functional group. Furthermore, a synergistic effect exists between lipases and fluorescent whitening agents; therefore, the carrier composition may further comprise lipases. This is particularly true when the fluorescent whitening agent comprises an ester functional group.

[0172] Fluorescent brighteners or optical brighteners can be liquids at ambient temperature.

[0173] The solubility of fluorescent whitening agents or optical brightening agents in water at ambient temperature is less than 1 g / L.

[0174] The carrier can be in the form of a polymer sheet, which can be formed into a pouch or packet for use in detergent compositions.

[0175] Detergent

[0176] According to another aspect of the present invention, a detergent composition comprising the aforementioned fluorescent whitening agent or optical brightening agent is provided.

[0177] Detergent compositions may contain detergent surfactants, such as anionic surfactants, cationic surfactants, amphoteric surfactants, or nonionic surfactants.

[0178] In a preferred embodiment, the detergent composition comprises a nonionic surfactant.

[0179] Advantageously, nonionic surfactants have been found to provide a preferred base detergent composition for the deposition of the fluorescent whitening or optical brightening agents of the present invention.

[0180] In embodiments of the invention, the detergent surfactant is a nonionic surfactant, which may be selected from one or more of rhamnolipids or sophorolipids. Commercial examples of such surfactants include, but are not limited to, BioLoop 56L, BioLoop 56L-PG, BioLoop 68L, BioLoop 68L-PG, BioLoop 84L, and BioLoop 84L-PG.

[0181] In this invention, the fluorescent whitening agent or optical brightening agent preferably has an amide functional group.

[0182] It has been found that such fluorescent whitening agents, or optical brighteners, provide better adsorption on surfaces cleaned by detergent compositions. It is not desirable to be bound by theory, but it is understandable that a certain degree of positive charge on the amide can interact with a negatively charged service substance. This is generally believed to occur during the washing of items.

[0183] It has been found that, when used in relevant detergent compositions, the present invention can provide improved FWA or optical brightener deposition. This assumes that the FWA or optical brightener is co-adsorbed with the cationic surfactant on the surface being washed.

[0184] In compositions using positively charged surfactants (e.g., cationic or amphoteric surfactants), the FWA or optical brightener preferably has Y, where Y is OH or OM, and M is Na or K.

[0185] It has been found that these FWAs or optical brighteners provide improved deposition, likely because the combination of negatively charged FWAs or optical brighteners with positively charged surfactants collectively provides improved surface adsorption. This is particularly beneficial for detergent compositions, such as fabric softeners.

[0186] In this invention, the preferred pH for use of the detergent composition is between pH 8 and pH 10. pH values ​​within this range are particularly advantageous for the adsorption of ionizable FWA or optical brightening agents.

[0187] In this invention, the detergent composition is preferably a laundry detergent composition, such as a fabric softener, whitening agent, pretreatment agent, and conventional solid, liquid, gel, and packaged detergent compositions, as well as heavy-duty and light-duty "white" and "colored" detergent compositions.

[0188] In this invention, the detergent composition is preferably a fabric washing detergent composition selected from one or more of laundry detergents, fabric softeners, bleaching agents, or synergistic laundry additives (such as whitening agents).

[0189] In this invention, the detergent composition preferably further comprises a proteolytic enzyme, and the FWA or optical brightener comprises an amide bond.

[0190] The detergent compositions of the present invention may also contain lipases, particularly in embodiments where the FWA or optical brightener contains ester bonds.

[0191] The detergent composition of the present invention may be in the physical form of powder (granules), liquid, gel, packet, tablet or solid tablet.

[0192] Preferably, the physical form is a solid. This is particularly suitable for FWA or optical brighteners, where m is 3 or greater and L is a polymer. Such an embodiment provides a solid form of FWA or optical brightener that is compatible with other solids and does not hydrolyze in its undiluted state. When the solid is diluted, for example during washing, detergent composition components, such as enzymes or pH reagents, can initiate hydrolysis, releasing the FWA or optical brightener into the washing composition.

[0193] Included within the scope of this invention are detergent compositions selected from one or more of laundry detergents, laundry fabric softeners, bleaching agents, or synergistic laundry additives (such as whitening agents).

[0194] Therefore, the present invention further provides a fluorescent whitening agent or optical brightening agent solid carrier composition comprising a carrier and a fluorescent whitening agent or optical brightening agent according to the foregoing description.

[0195] The compounds according to the invention are capable of providing fluorescent whitening or optical brightening effects and are readily, eventually, or inherently biodegradable. These compounds may all share a common renewable building block, making their production environmentally friendly. Furthermore, these compounds may possess one or more of the following characteristics: direct affinity for fabrics (e.g., natural materials including cotton and cellulose); compatibility with synthetic fabric materials; providing peak fluorescence output in the blue (450 nm and 495 nm) or green (495 nm to 570 nm) portions of the visible spectrum; providing high fluorescence in both solid and solution forms; providing high fluorescence when adsorbed onto fabrics and solutions; and / or providing higher absorption on cotton than 2,2'-stilbene disulfonic acid.

[0196] Other applications of the fluorescent whitening agents defined in this invention:

[0197] fabric

[0198] The fluorescent whitening agent or optical brightening agent of the present invention can be used in fabric manufacturing.

[0199] The fluorescent whitening agent or optical brightening agent of the present invention can be used in the finishing process of cotton. Preferably, it is used in the process of processing greige (loom state) fabric into finished fabric.

[0200] The fluorescent whitening agent or optical brightening agent of the present invention can be used in melt-spun synthetic fibers.

[0201] Paper

[0202] The fluorescent whitening agent or optical brightening agent of the present invention can be used in papermaking. Preferably, it is used in a "wet" manufacturing process.

[0203] The fluorescent whitening agent or optical brightening agent of the present invention can be used in paper finishing.

[0204] The FWA or optical brightener of the present invention can be used to pretreat cellulose fibers before papermaking.

[0205] cosmetic

[0206] The fluorescent whitening agent or optical brightening agent of the present invention can be used in combination with emollients to provide cosmetic compositions.

[0207] The FWA or optical brightener of the present invention can be used to produce sunscreen compositions.

[0208] The advantage of FWA or optical brightener cosmetics is that they can increase the apparent gloss, shine, or color intensity of cosmetics in an environmentally acceptable manner.

[0209] Example

[0210] Example 1 - Evaluation of Fluorescent Whitening Agents

[0211] The fluorescent whitening agents and optical brightening agents of this invention have been evaluated in terms of chemical and UV stability, quantum yield, fluorescence / whitening effect, biodegradability, and direct affinity to cellulose compared to commercial benchmarks.

[0212] Relative quantum yield

[0213] An FWA solution was prepared in 0.1 M sodium carbonate. The solution was diluted to a measured UV absorbance of 0.1 (Agilent). TM CaryUV-vis was then further diluted to obtain a series of UV absorbance readings. These solutions were then manipulated to measure the fluorescence response (Agilent). TM (Cary Eclipse fluorescence spectrometer). The integrated area of ​​the fluorescence measurement was plotted against the UV absorbance reading. This was compared with the gradient measurement of quinine sulfate in 0.1 M sulfuric acid standard to calculate the relative quantum yield. The results are provided in Tables 1 and 2 below.

[0214] Table 1: Relative quantum yield of benchmark FWA or optical brightener

[0215]

[0216] Table 2: Relative quantum yield of FWA or optical brightener examples

[0217]

[0218] The relative quantum yield of the compounds according to the present invention can be readily seen to be comparable to or better than existing technical standards.

[0219] Fluorescence / whitening effect measured on cellulose powder:

[0220] use Color measurements were performed using an LC100 spectrochromic meter. The surface color of the powder was quantified using a series of values ​​L*, a*, and b* in the CIELAB color model defined by the International Commission on Illumination (ICI). L* measures the amount of white or black in the sample; a higher L* value indicates a lighter sample color. The a* value determines the amount of red or green in the sample. The b* value determines the amount of blue or yellow in the sample; a lower (more negative) b* value indicates more blue in the sample. Color can also be measured using a different model, CIE L*C*h*, where C* represents chromaticity and h* represents hue angle. Powders from each directness test were measured against a blank washed cellulose sample, setting a starting point for the next UV stability test. The results are shown in Table 3 below.

[0221] Table 3: Results of the compounds in the examples

[0222]

[0223]

[0224] Compared to the blank, all compounds showed a significant shift toward a blue hue (h* = 270), demonstrating their effectiveness in terms of directness and optical effects.

[0225] UV stability (i.e., lightfastness)

[0226] The cellulose powder prepared as described above was placed in a UV chamber and exposed to UV light under a 4W lamp (365nm) for 3 months. The samples were then visually inspected, photographed, and color measurements were performed again to monitor whiteness loss and changes from blue to yellow or darker shades. The results are shown in Table 4 below.

[0227] Table 4: Results of the example compounds after UV exposure

[0228]

[0229]

[0230] The FWA of this invention is stable under UV conditions under the test conditions.

[0231] Chemical stability

[0232] Weigh 0.0100 g to 0.0200 g of FWA or optical brightener into a 100 mL volumetric flask and dilute to volume with deionized water. Sonicate the solution for 5 minutes to ensure a homogeneous dispersion. Divide the solution into five 10 mL aliquots. Sample 1 serves as a blank; add 0.2 mL of deionized water. Add 0.1 mL of 1 M sodium hydroxide solution and 0.1 mL of deionized water to Sample 2; add 0.1 mL of 1 M sodium bicarbonate solution and 0.1 mL of deionized water to Sample 3; add 0.1 mL of 1 M sodium hydroxide solution and 0.1 mL of 0.75 M hydrogen peroxide to Sample 4; and add 0.1 mL of 1 M sodium carbonate solution and 0.1 mL of 0.75 M hydrogen peroxide to Sample 5. Heat all samples to 40 °C and maintain this temperature for 48 hours, then analyze by HPLC. The blank sample is used to determine the retention time and maximum response of the FWA or optical brightener. Any hydrolysis and oxidation of the FWA or optical brightener resulted in new compounds appearing on the chromatogram at different retention times, while simultaneously reducing the response of the FWA or optical brightener. Other samples reported the percentage response of the FWA or optical brightener relative to the blank. Conditions 3 (carbonate) and 5 (carbonate and hydrogen peroxide) were most relevant to laundry applications such as heavy-duty powder detergents. The results are shown in Table 5 below.

[0233] Table 5: Chemical stability of the compounds in the examples

[0234]

[0235] Table 5 shows the FWA chemical stability monitoring results, confirming the excellent stability of both the unfunctionalized and amine-functionalized structures at high pH and in the presence of oxidants. These results indicate high compatibility with laundry applications.

[0236] The biodegradability and direct affinity to cellulose of the fluorescent whitening agent of this invention have been further evaluated compared to commercial benchmarks.

[0237] Direct effect on cellulose:

[0238] To prepare a buffer solution, weigh 0.10 g SDS, 1.0 g glycerol, 8.4 g sodium carbonate, 1.7 g sodium bicarbonate, and 0.4 g EDTA into a 50 mL beaker, and then transfer the mixture to a 2000 mL beaker. Rinse the 50 mL beaker with tap water and then dilute to approximately 1 L with tap water while stirring until completely dissolved. Transfer the solution to a 2 L volumetric flask and bring it to a final volume with tap water.

[0239] Weigh 0.0100 g to 0.0200 g of FWA into a 100 mL volumetric flask and dilute to volume with buffer solution. Sonicate the solution for 5 minutes to ensure a homogeneous dispersion.

[0240] Add 10g of Thermo Scientific to a 250mL beaker TM 50 μm microcrystalline cellulose powder and 50 ± 1 g FWA solution were prepared, and their precise weights were recorded. The cellulose / FWA slurry was stirred for 20 minutes and then filtered through a polypropylene filter cloth in a filtration apparatus. The filtrate (mother liquor) was collected. The cellulose was rinsed three times with 50 mL of tap water, and the cellulose was re-slurryed by simple stirring before filtration. The combined filtrates (mother liquor and rinses 1 to 3) were collected and weighed. The cellulose cake was removed from the filtration apparatus and dried in a vacuum oven at 35 °C for further visual, fluorescence, and lightfastness tests.

[0241] To measure the amount of FWA retained on cellulose, the initial sample and combined filtrate were analyzed by HPLC. The retention amount of FWA was calculated using the peak area of ​​the FWA and the input-output weights. The results are shown in Tables 6 and 7 below.

[0242] Directness can be defined by the following criteria: poor (<25%), average (25% to 50%), good (50% to 85%), and excellent (>85%).

[0243] Table 6: Directness of the reference compound to cellulose

[0244]

[0245] Table 7: Direct effect of the compounds in the examples on cellulose

[0246]

[0247] The compounds shown in Table 7 demonstrate performance levels (in terms of directness) close to the industry standards shown in Table 6, while also being non-toxic. Furthermore, these compounds are biodegradable, non-bioaccumulative, and can be produced from sustainable materials.

[0248] The directness of fabrics:

[0249] At 35°C, add 10L of tap water to a top-loaded washing machine (4.5kg capacity). Add a standard sample of fabric (10cm×10cm, supplier: CFT, Test Material Center BV) along with 20g of ECE-2 dye transfer test detergent ISO105C-08 and 0.1g of FWA to the water. Run the washing machine for 9 minutes, then drain completely.

[0250] Add 5L of cold water to rinse the fabric. After running the washing machine for 3 minutes, drain the water and then rinse the fabric a second time with 5L of cold water within a 3-minute run. After rinsing, spin-dry the fabric sample for 3 minutes before it is completely air-dried.

[0251] use The surface color of the sample was measured using an LC100 spectrochromiste, in duplicate. The average surface color values ​​are shown in Table 8 below.

[0252] Table 8: Direct Effects of Compounds from Examples on Fabrics

[0253]

[0254]

[0255] Compared to the blank, all compounds showed a significant shift toward a blue hue (h* = 270), demonstrating their effectiveness in terms of directness and optical effects.

[0256] Example 2 - Using Biowin TM Conduct biodegradability assessment

[0257] The chemical structure of this invention is biodegradable.

[0258] For the purposes of this invention:

[0259] Inherently biodegradable fluorescent whitening agents are defined as having >20% but <60% biodegradability in water as measured by OECD 301A-F test.

[0260] A readily biodegradable fluorescent whitening agent is defined as having the ability to rapidly and completely biodegrade in water within a 10-day time window of 28 days (depending on the OECD 301A-F test method, with a dissolved organic carbon (DOC) removal rate ≥70%, theoretical carbon dioxide removal ≥60%, or theoretical oxygen demand ≥60%).

[0261] Biowin TM The software is used to predict biodegradability. This method for predicting biodegradability is based on the Software Evaluation Program Interface (EPI) Suite provided by the U.S. Environmental Protection Agency (EPA). TMPart of this paper, Environ. Sci. Technol, 1994, 28, 459-465, illustrates an example of a group contribution method for predicting the probability and rate of aerobic biodegradation. This is part of Biowin. TM The type of method used.

[0262] The Biowin 3 and Biowin 5 models are particularly relevant to this invention. These models were used to evaluate the predicted biodegradability of some compounds according to the invention. A prediction of yes (easily biodegradable) was made if the Biowin 3 (final investigation model) result was >= 2.75 (i.e., "weeks" or faster) and the Biowin 5 (MITI linear model) probability was >= 0.5. If this condition was not met, a prediction of no (not easily biodegradable) was made. The results are shown in Tables 9 and 10 below:

[0263] Table 9: Biodegradability scores of benchmark compounds predicted by Biowin

[0264]

[0265] Table 10: Biowin's predicted biodegradability scores of the structures in this invention

[0266]

[0267]

[0268] Example 3 - Thermogravimetric Analysis (TGA)

[0269] The temperature was raised from room temperature to 800°C under airflow, and the sample was analyzed using Mettler Toledo TGA / DSC3+ thermogravimetric analysis.

[0270] Table 11: Thermogravimetric analysis of reference compounds

[0271]

[0272]

[0273] Table 12: Thermogravimetric analysis of compounds in the examples

[0274]

[0275]

[0276] Some low-temperature mass loss can be attributed to the loss of residual moisture. Even so, most of the compounds of the present invention can be considered stable up to 110°C. They also show mass loss at 150°C comparable to the baseline, and therefore have at least a similar degree of thermal stability.

[0277] The thermal stability of the fluorescent whitening agent and optical brightening agent of the present invention is important because, in the case of laundry detergent, the components can be introduced before the dehydration stage in a fluidized bed dryer where the temperature can reach 50°C to 110°C.

[0278] Example 4 - Washing Power

[0279] Tables 13, 14, 15 and 16 describe detergent compositions representing the present invention.

[0280] Table 13: Representative laundry detergent compositions of conventional and dense compositions

[0281]

[0282]

[0283] Table 14: Representative Detergent Tablet Compositions of Zeolite-Based and Phosphate-Based Compositions

[0284]

[0285] Table 15: Representative laundry detergent compositions of homogeneous and structured compositions

[0286]

[0287] Table 16: Representative Fabric Bleach Detergent Compositions in Solid and Liquid Forms

[0288]

Claims

1. A fluorescent whitening agent or optical brightening agent of formula (I), wherein formula (I) has the following structure: in: A is CHR 1 R 2 (CH2) n , where R 1 For H, CH2OH or COZ, R 2 It is H or CH2OH, and n is 1 or 2, or A is an optionally substituted aromatic ring or heterocyclic ring fused with N and X, wherein N and X are bonded to adjacent carbon atoms on the ring, respectively; X is O, S, or NH; Y is either Z or X'L; The Z, or each Z independently, is OH, OM, OR. 3 O(CH2) q SO3M, NH2, NHOH, NHR 4 or NR 4 2, of which: M is selected from alkali metals or alkaline earth metals; R 3 Represents straight-chain or branched alkyl, aryl, alkylaryl, aralkyl, straight-chain or branched alkyl alcohol, straight-chain or branched alkyl alcohol polyol, hydroxyalkylamine, polyol, sugar, straight-chain or branched alkyl ether, polyester having 2 to 1000 repeating units, or polyoxyalkylene chain having 2 to 1000 repeating units. q ranges from 1 to 5; R 4 Independently selected from methyl, ethyl, propyl, C4 to C 12 Alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propionyl, 1,3-dihydroxy-2-propionyl, 2,3-dihydroxypropyl, cyanomethyl, 2-aminoethyl or dicarboxymethyl; or, NR 4 2 represents a heterocycle (e.g., morpholine); and Where Y is X'L; X' is O, S, or NH; and L represents the connecting body of m repeating units of the connecting type I, and Y is replaced by X' as defined above.

2. A fluorescent whitening agent or optical brightening agent of formula (II), wherein formula (II) has the following structure: Where Y is Z or X'L; Z represents OH, OM, or OR. 3 O(CH2) q SO3M, NH2, NHOH, NHR 4 or NR 4 2. M represents alkali metal or alkaline earth metal; R 3 Represents straight-chain or branched alkyl, aryl, alkylaryl, aralkyl, straight-chain or branched alkyl alcohol, straight-chain or branched polyol, hydroxyalkylamine, polyol, sugar, straight-chain or branched alkyl ether, polyester having 2 to 1000 repeating units, or polyoxyalkylene chain having 2 to 1000 repeating units. q ranges from 1 to 5; R 4 Independently selected from methyl, ethyl, propyl, C4 to C 12 Alkyl, benzyl, 2-hydroxyethyl, 1-hydroxy-2-propionyl, 1,3-dihydroxy-2-propionyl, 2,3-dihydroxypropyl, cyanomethyl, 2-aminoethyl or dicarboxymethyl; or, NR 4 2 represents a heterocycle (e.g., morpholine); and R represents H, CHR 5 R 6 、R 5 、R 6 Alkyl sulfonates, polyethers, CH2COZ or CH(COZ)((CH) n COZ), where each Z can be the same or different. R 5 and R 6 Independently representing hydrogen, alkyl (such as methyl, ethyl, propyl, isopropyl), vinyl, phenyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, aminomethyl, (dimethylamino)methyl, 5-aminopentyl or cyano, optionally wherein R 5 and R 6 Same or different, and n is 1 or 2; Where Y is X'L; X' is O, S, or NH; and L represents the connecting body portion of m repeating units of the connected type II variant, where X' exists as defined above in place of Y.

3. The fluorescent whitening agent or optical brightening agent according to claim 1 or 2, wherein: a. Where R 3 Represents straight-chain or branched alkyl groups, R 3 Preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or 2-ethylhexyl; b. Where R 3 Represents alkyl alcohols, R 3 Selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, dodecanol, stearyl alcohol, or oleyl alcohol; c. Where R 3 Represents aryl, R 3 It is phenyl; d. Where R 3 Represents alkylaryl, R 3 Selected from benzyl or ethylphenyl; e. Where R 3 Represents straight-chain or branched alkyl alcohols, R 3 Selected from 4-hydroxybutyl; f. Where R 3 Represents straight-chain or branched-chain alcohols and polyols, R 3 It is a diol or triol, optionally 2,3-dihydroxypropyl or 2-hydroxy-1-(hydroxymethyl)ethyl; g. Where R 3 Represents hydroxyalkylamine, R 3 Selected from triethanolamine, N-methyldiethanolamine, or triisopropanolamine; h. Where R 3 Represents polyols, R 3 It is glycerol; I. Among them, R 3 Represents sugar, R 3 Selected from dextrose, fructose, galactose, glucose, lactose, maltose, or sucrose; j. Where R 3 Represents straight-chain or branched alkyl ethers, R 3 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. Where R 3 It represents a polyester or polyoxyethylene chain with 2 to 1000 repeating units, the chain being a homopolymer or copolymer.

4. The fluorescent whitening agent or optical brightening agent according to any one of claims 1 to 3, wherein: a. Linker L is derived from an alcohol, and X' is the oxygen atom of the precursor alcohol; or b. Linker L is derived from an amine, and X' is the nitrogen of the precursor amine.

5. The fluorescent whitening agent or optical brightening agent according to any one of claims 1 to 4, wherein the fluorescent whitening agent or the optical brightening agent is a dimer or oligomer, wherein m is 2 or greater, optionally from 3 to 20, optionally 3.

6. The fluorescent whitening agent or optical brightening agent according to any one of claims 1 to 5, wherein the linker L is composed of ethylene, propylene, or C4 to C6. 12 It consists of any one of the following: alkylene, a polyester chain that is a homopolymer or copolymer having 0 to 1000 repeating units, or a polyoxyalkylene chain that is a homopolymer or copolymer having 0 to 1000 repeating units, triethanolamine, glycerol, or sugar.

7. A fluorescent whitening agent or optical brightening agent, said fluorescent whitening agent or optical brightening agent being derived from the condensation of a dicarboxylic acid or polycarboxylic acid with an amine, optionally derived from the condensation of a dicarboxylic acid or polycarboxylic acid with an amino acid or amino acid derivative, optionally derived from the condensation of citric acid with an amino acid or amino acid derivative.

8. The fluorescent whitening agent or optical brightening agent according to any one of claims 1 to 7, wherein the fluorescent whitening agent or the optical brightening agent is formulated for use as a fluorescent whitening agent or optical brightening agent.

9. The fluorescent whitening agent or optical brightening agent according to claim 8, wherein the fluorescent whitening agent or the optical brightening agent comprises a portion of a fluorescent whitening formulation or an optical brightening formulation, wherein the formulation further comprises at least one auxiliary compound, said auxiliary compound optionally selected from one or more of surfactants, detergents, bleaching agents, carrier compounds, stabilizers and / or dispersants.

10. A fluorescent whitening agent or optical brightening agent comprising, according to any one of claims 1 to 8, a fluorescent whitening agent or optical brightening agent and at least one detergent, bleach, carrier compound, stabilizer and / or dispersant.

11. Use of the compound of formula (I) or formula (II) according to any one of claims 1 to 8 as a fluorescent brightener or optical brightener.

12. A method of providing a substrate with fluorescent whitening or optical brightening, comprising contacting the substrate with a fluorescent whitening agent or optical brightening agent according to any one of claims 1 to 8, or a fluorescent whitening agent or optical brightening agent according to claim 10, under conditions that effectively bind the fluorescent whitening agent or optical brightening agent chemically and / or physically to or into the substrate.

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