TWI715878B - Leuco colorants and compositions - Google Patents

Abstract

A leuco composition comprises at least one leuco compound, the leuco compound comprising a leuco moiety and a polyalkyleneoxy moiety covalently bound to the leuco moiety. The polyalkyleneoxy moiety comprises at least one ethylene oxide group and at least one propylene oxide group. A laundry care composition comprises (a) at least one laundry care ingredient and (b) a leuco composition as described above. A method of treating a textile includes the steps of (a) providing such a laundry care composition; (b) adding the laundry care composition to a liquid medium; (c) placing textile articles in the liquid medium; (d) optionally, rinsing the textile; and (e) drying the textile articles.

Description

Leuco colorant and composition

Invention field

This application describes leuco compositions, laundry care compositions containing such leuco compositions, and the use of such compositions in textile washing. These types of compositions are provided in a stable, substantially colorless state and can then be transformed into a strong color state when exposed to certain physical or chemical changes, such as exposure to oxygen, ion addition, exposure to light and the like . The laundry care composition containing the leuco compound is designed to enhance the apparent or visually perceived whiteness of the textiles that have been washed or otherwise treated with the laundry care composition or to give them a desired hue.

Background of the invention

As the textile substrate ages, its color tends to fade or turn yellow due to exposure to light, air, dirt, and natural degradation of the fibers that make up the substrate. Therefore, in order to visually enhance these textile substrates and resist fading and yellowing, it is well known in the prior art to use polymeric colorants to dye consumer products. For example, it is well known to use whitening agents, namely optical brighteners or blue agents, in textile applications. However, due to harmful interactions with other formulation components (such as fragrances), traditional whitening agents lose their efficacy when stored. In addition, such whitening agents can suffer from poor deposition on the textile substrate. Therefore, formulators tend to increase the amount of whitening agent used in order to resist any loss of efficacy during storage and/or increase the amount of whitening agent that can be deposited on the textile substrate.

It is also known in the prior art that the leuco dye exhibits a change from a colorless or slightly colored state to a colored state when exposed to a specific chemical or physical trigger. The color change that occurs can usually be noticed by the human eye. Many of these compounds have some absorbance in the visible light region (400-750 nm), and therefore more or less have some color. In the present invention, if the dye does not present a significant color under its application concentration and conditions, but presents a significant color under its trigger form, it is regarded as a "leuco dye". When triggered, the color change is derived from the molar attenuation coefficient of the leuco dye molecules in the range of 400-750 nm, preferably in the range of 500-650 nm and best in the range of 530-620 nm (in some literature It is also referred to as the change in the molar extinction coefficient, the molar absorption coefficient and/or the molar absorption coefficient. Before and after triggering, the increase in the molar attenuation coefficient of the leuco dye should exceed 50%, more preferably more than 200% and most preferably more than 500%.

Leuco compounds can be used as whitening agents in laundry care compositions, such as laundry detergents. In such applications, adding a leuco compound, which is colorless or only slightly colored, will not significantly affect the aesthetics of the laundry care composition. Next, the leuco compound can be converted into a colored state, where it imparts the desired whitening benefits to the textile substrate.

One challenge of using tinting technology to deliver the benefits of whiteness is that consumers usually have clothes that are slightly colored (infused with light yellow), and the application of tinting, shading or bluing agents can damage the desired color of such clothes, causing consumers dissatisfied. There is still a need to develop a toning method, which is selectively deposited on aging consumer cotton clothing (clothes that are most likely to turn yellow over time, which require color correction) and are deposited on new clean cotton that does not require color correction Less deposits on clothing.

Although many leuco colorants show deposition shifts on consumer-sourced and aging cotton garments compared to new, clean cotton, we have found that propoxylate groups are used to replace certain ethoxy groups of TAM dyes. Chemical derivatives can cause improved excursions. These leuco colorants having EO and PO oxyalkylene groups show a larger deviation compared with leuco colorants having only EO oxyalkylene units. Therefore, the leuco colorant of the present invention can better deliver the benefits of whitening when needed, and avoid toning new and clean cotton clothing in which such toning is considered unnecessary.

Summary of the invention

In the first embodiment, the present invention provides a leuco composition comprising at least one leuco compound, the leuco compound comprising a leuco moiety and an alkyleneoxy moiety covalently bound to the leuco moiety, wherein The alkyleneoxy moiety contains at least one ethylene oxide group and at least one propylene oxide group.

In a second embodiment, the present invention provides a laundry care composition comprising (a) at least one laundry care ingredient and (b) the leuco composition as described above.

In a third embodiment, the present invention provides a method for treating textiles, which comprises the following steps: (a) providing a laundry care composition as described herein; (b) adding a laundry care composition to a liquid medium; c) Place the textile in a liquid medium; (d) Optionally rinse the textile; and (e) Dry the textile.

In a fourth embodiment, the present invention provides a laundry care composition comprising a laundry care ingredient and a leuco composition as described herein. In one aspect, the present invention provides a laundry care composition comprising: (i) 2 to 70% by weight of a surfactant; and (ii) 0.0001 to 20.0% by weight of a leuco composition as described herein Things.

In the fifth embodiment, the present invention provides a method for treating textiles, which comprises the following steps: (a) providing a laundry care composition comprising the leuco composition as described herein, (b) adding a liquid medium Add laundry care composition; (c) put the textile in a liquid medium; (d) optionally rinse the textile, and (e) dry the textile.

Detailed description of the preferred embodiment definition

As used herein, the term "alkoxy" is intended to include C ₁ -C ₈ alkoxy and alkoxy derivatives of polyhydric alcohols having repeating units, such as butylene oxide, oxyglycidol, ethylene oxide or Propylene oxide.

As used herein, the interchangeable terms "alkyleneoxy" and "oxyalkylene" and the interchangeable terms "polyalkyleneoxy" and "polyoxyalkylene" generally refer to containing The molecular structure of one or more of the following repeating units: -C ₂ H ₄ O-, -C ₃ H ₆ O-, -C ₄ H ₈ O- and any combination thereof. Non-limiting structures corresponding to these groups include, for example, -CH ₂ CH ₂ O-, -CH ₂ CH ₂ CH ₂ O-, -CH ₂ CH ₂ CH ₂ CH ₂ O-, -CH ₂ CH(CH ₃ )O- and -CH ₂ CH(CH ₂ CH ₃ )O-. In addition, the polyoxyalkylene component can be selected from the group consisting of: one or more monomers selected from C _2-20 alkyleneoxy and glycidyl or a mixture thereof.

In this article, the terms "ethylene oxide", "propylene oxide" and "butylene oxide" can be represented by their typical names "EO", "PO" and "BO" respectively.

As used herein, the terms "alkyl" and "alkyl terminated" are intended to mean any monovalent group formed by removing a hydrogen atom from a substituted or unsubstituted hydrocarbon. Non-limiting examples include branched or unbranched, substituted or unsubstituted hydrocarbyl moieties, including C ₁ -C ₁₈ alkyl, and in one aspect, C ₁ -C ₆ alkyl.

As used herein, unless stated otherwise, the term "aryl" is intended to include C ₃ -C ₁₂ aryl groups. The term "aryl" refers to carbocyclic and heterocyclic aryl groups.

As used herein, the term "alkaryl" refers to any alkyl substituted aryl substituent and aryl substituted alkyl substituent. More specifically, the term is intended to refer to aryl substituents substituted with C _7-16 alkyl groups and alkyl substituents substituted with C _7-16 aryl groups, which may or may not contain other substituents.

As used herein, the term "detergent composition" is a subset of laundry care compositions and includes cleaning compositions, including (but not limited to) products for washing fabrics. Such a composition may be a pretreatment composition for use before the washing step or may be a rinsing additive composition, and a cleaning aid, such as bleach additives and "dye binders" or pretreatment type.

As used herein, unless otherwise indicated, the term "laundry care composition" includes granular, powder, liquid, gel, slurry, unit dose, bar and/or tablet detergent and/or fabric treatment composition Products, including (but not limited to) products used for washing fabrics, fabric softening compositions, fabric reinforcing compositions, fabric refreshing compositions, and other products used to care and maintain fabrics and their combinations. Such a composition may be a pretreatment composition for use before the washing step or may be a rinsing additive composition, and a cleaning aid, such as a bleach additive and/or "dye binder" or a pretreatment composition or a substrate-loaded product , Such as a desiccant to add tablets.

As used herein, the term "leuco" (as used in reference to, for example, compounds, moieties, groups, dyes, monomers, fragments, or polymers) refers to an entity (for example, an organic compound or part thereof) that is exposed to When a specific chemical or physical triggering agent undergoes one or more chemical and/or physical changes, it causes a shift from the first color state (for example, uncolored or substantially colorless) to a second, higher color state. Suitable chemical or physical triggers include, but are not limited to, oxidation, changes in pH, changes in temperature, and changes in exposure to electromagnetic radiation (such as light). Suitable chemical or physical changes that occur in leuco entities include, but are not limited to, oxidative and non-oxidative changes, such as intramolecular cyclization. Therefore, in one aspect, a suitable leuco entity may be a reversibly reduced form of the chromophore. In one aspect, the leuco-colored portion preferably includes at least the first and second π-systems, which can be converted into a combined compound when exposed to one or more of the chemical and/or physical triggers described above The third combined π-system of the first and second π-systems.

As used herein, the term "leuco composition" or "leuco colorant composition" refers to a composition comprising at least two compounds with independently selected structures as described in further detail herein.

As used herein, the "average molecular weight" of the leuco colorant is reported as the weight average molecular weight, as determined by the molecular weight distribution: due to its manufacturing process, the leuco colorant disclosed herein may contain in its polymerized part Distribution of repeating units.

As used herein, the terms "maximum extinction coefficient" and "maximum molar extinction coefficient" are intended to describe the molarity at the maximum absorption wavelength (also referred to herein as the maximum wavelength) in the range of 400 nm to 750 nm Extinction coefficient.

As used herein, the term "first color" is used to refer to the color of the laundry care composition before triggering, and is intended to include any color, including colorless and substantially colorless.

As used herein, the term "second color" is used to refer to the color of the laundry care composition after triggering, and is intended to include any that can be distinguished from the first color of the laundry care composition (by visual inspection or using analytical techniques, Such as spectrophotometric analysis) color.

As used herein, the term "transforming agent" refers to any oxidizing agent other than molecular oxygen in any known form (single and triplet) known in the art.

As used herein, the term "trigger" refers to a reactant suitable for converting a leuco composition from a colorless or substantially colorless state to a colored state.

As used herein, the term "whitening agent" refers to a dye or a leuco colorant that can form a dye after being triggered. When it is on white cotton, the relative chromaticity is between 210 and 345, or even 240 to 320. Hue, or even relative chroma of 250 to 300 (e.g., 250 to 290), provides a hue to the knitted fabric.

As used herein, "cellulose matrix" is meant to include any matrix that contains at least a majority of the weight of cellulose. Cellulose can be found in wood, cotton, flax, jute and kapok. The cellulose matrix can be in the form of powder, fiber, slurry, and objects formed from powder, fiber, and slurry. Cellulose fibers include, but are not limited to, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (cellulose triacetate), and mixtures thereof. Objects formed from cellulose fibers include textiles, such as fabrics. The objects formed by the slurry include paper.

As used herein, articles such as "一" when used in a claim should be understood to mean one or more of the items claimed or described.

As used herein, the term "includes" means non-limiting.

As used herein, the term "solid" includes granular, powder, bar, and lozenge product forms.

As used herein, the term "fluid" includes liquid, gel, slurry, and gas product forms.

The test methods disclosed in the test method chapter of this application should be used to determine the respective values of the parameters of the applicant's invention.

Unless otherwise specified, all components or composition contents are related to the effective part of the component or composition, and do not include impurities such as residual solvents or by-products, which may be present in commercially available sources of such components or compositions .

Unless otherwise indicated, all percentages and ratios are by weight. Unless otherwise indicated, all percentages and ratios are calculated based on the total composition.

In one aspect, the molar extinction coefficient of the second color state at the maximum absorbance in the wavelength range of 200 to 1,000 nm (more preferably 400 to 750 nm) is preferably the first color state in the second color The molar extinction coefficient at the wavelength of the maximum absorbance of the state is at least five times, more preferably 10 times, even more preferably 25 times, and most preferably at least 50 times. Preferably, the molar extinction coefficient of the second color state at the maximum absorbance in the wavelength range of 200 to 1,000 nm (more preferably 400 to 750 nm) is preferably the first color state in the corresponding wavelength range The maximum molar extinction coefficient is at least five times, preferably 10 times, even more preferably 25 times, and most preferably at least 50 times. Those skilled in the art will recognize that these ratios can be much higher. For example, the maximum molar extinction coefficient of the first color state in the wavelength range of 400 to 750 nm can be as small as 10 M ^-1 cm ^-1 , and the second color state in the wavelength range of 400 to 750 nm The maximum molar extinction coefficient can be as high as 80,000 M ^-1 cm ^-1 or higher. In this case, the ratio of the extinction coefficient will be 8,000:1 or higher.

In one aspect, the maximum molar extinction coefficient of the first color state at a wavelength in the range of 400 to 750 nm is less than 1000 M ^-1 cm ^-1 , and the second first color is in the range of 400 to 750 nm The maximum molar extinction coefficient at the wavelength is greater than 5,000 M ^-1 cm ^-1 , preferably greater than 10,000, 25,000, 50,000 or even 100,000 M ^-1 cm ^-1 . Those familiar with this technology will recognize and understand that polymers containing more than one leuco moiety can have a significantly higher maximum molar extinction coefficient in the first color state (for example, due to the addition of a large number of leuco moieties) Or there are one or more leuco-colored parts that transform into a second color state).

The present invention relates to a leuco colorant that can be used in laundry care compositions, such as liquid laundry detergents, to provide a blue hue to the whitened textile substrate. Leuco colorants are compounds that are basically colorless or only slightly colored, but can produce strong colors when activated. One advantage of using leuco compounds in laundry care compositions is that such compounds (which are colorless before activation) allow the laundry care composition to exhibit its own color. Leuco colorants generally do not change the original color of laundry care compositions. Therefore, the manufacturers of such compositions can match consumers with the most attractive colors without worrying about the added ingredients (such as bluing agents) affecting the final color value of the composition.

The range of textiles encountered in consumers' homes is extremely large and usually includes garments constructed from a wide variety of natural and synthetic fibers and mixtures of these substances in the same washing load or even in the same apparel. The article can be constructed in a variety of ways and can contain any of a large number of finishes applied by the manufacturer. The amount of any such finishing agent remaining on the consumer's textiles depends on many factors, including the durability of the finishing agent under the specific washing conditions used by the consumer, the specific detergents and additives that the consumer may use, and the washing cycle of the article number. Depending on the history of each article, finishing agents may be present to varying degrees or substantially absent, and other materials present in the washing or rinsing cycle and contaminants encountered during wear may begin to accumulate on the article.

Those familiar with this technology should understand that any detergent formulation used by consumers will encounter textiles that represent a complete range of possibilities, and it is expected that not only the mode of action of various formulations on some textiles can (but in fact will) exist Significant difference. These differences can be found by routine experiments. For example, it has been found that the leuco colorant of the present invention can increase the whiteness of consumer aging garments and garments that have been applied with fabric enhancers, more than it increases the whiteness of new garments whose finishes have been removed by continuous washing . Therefore, formulations containing such leuco colorants may be superior to traditional formulations, and even formulations containing conventional toners, because newer clothing generally has less yellowing problems, and older consumer-oriented formulations Aging clothing is more prone to yellowing problems. The leuco colorant of the present invention has a tendency to increase the whiteness of aged clothing over clean new clothing, which is greater than that shown by many conventional toners.

As noted above, in the first embodiment, the present invention provides a leuco composition comprising at least one leuco compound, the leuco compound comprising a leuco moiety and an alkylene group covalently bound to the leuco moiety The oxy moiety, wherein the alkyleneoxy moiety contains at least one ethylene oxide group and at least one propylene oxide group.

The leuco compound may include any suitable leuco moiety as defined above. In one aspect, the leuco part is preferably selected from the group consisting of: diarylmethane leuco part, triarylmethane leuco part, 㗁𠯤 part, thiol part, hydroquinone part and arylamine基phenol moiety.

The diarylmethane leuco moieties suitable for use herein include, but are not limited to, monovalent or multivalent diarylmethylene moieties, which can form a second color state as described herein. Suitable examples include, but are not limited to, those derived from: Michler's methane, diarylmethylene substituted with -OH groups (such as Michler's dimer water molecules), and ethers and esters thereof , Diarylmethylene (bis(p-N,N-dimethyl)phenyl)acetonitrile) substituted with photocleavable groups (such as -CN groups), and similar such moieties.

； (I)

； (II)

； (III)

；及 (IV)

(V)； 其中式I-V與其氧化形式之比率為至少1:19、1:9或1:3，較佳為至少1:1，更佳為至少3:1，最佳為至少9:1或甚至19:1。In a more specific and preferred aspect, the leuco moiety is obtained by removing one or more hydrogen atoms from the structure of the following formula (I), (II), (III), (IV) or (V) Unit price or multi price part

; (I)

; (II)

; (III)

; And (IV)

(V); wherein the ratio of formula IV to its oxidized form is at least 1:19, 1:9 or 1:3, preferably at least 1:1, more preferably at least 3:1, most preferably at least 9:1 or Even 19:1.

In the structure of formula (I), where each individual R _o , R _m and R _p group on each of rings A, B and C is independently selected from the group consisting of: hydrogen, deuterium and R ⁵ ; each R ⁵ is independently selected from the group consisting of halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, ^{_{- (CH 2) n -OR 1}} , - (CH 2) n -NR 1 R 2, -C (O) R 1, -C (O) OR 1, -C (O) O -, -C (O )NR ¹ R ² , -OC(O)R ¹ , -OC(O)OR ¹ , -OC(O)NR ¹ R ² , -S(O) ₂ R ¹ , -S(O) ₂ OR ¹ , ^{_{-S (O) 2 O -,}} -S (O) 2 NR 1 R 2, -NR 1 C (O) R 2, -NR 1 C (O) OR 2, -NR 1 C (O) SR 2, ^{-NR 1 C (O) NR 2} R 3, -P (O) 2 R 1, -P (O) (OR 1) 2, -P (O) (OR 1) O - and -P (O) ( O ^-) _2; wherein the index n is an integer of 0-4, preferably 0-1, most preferably 0; wherein two different on the a, B and C ring R _o may be combined to form a five or A fused ring of multiple members; when the fused ring has six or more members, two R _o on different A, B and C rings can be combined to form an organic linkage optionally containing one or more heteroatoms In one embodiment, two R _o on different A, B and C rings are combined to form a heteroatom bridge selected from -O- and -S-, which produces a six-membered fused ring; on the same ring R _o and R _m or R _m and R _p on the same ring can be combined to form a fused aliphatic ring or a fused aromatic ring, any of which may contain heteroatoms; in the three rings A, B or C At least one of them, preferably at least two, more preferably at least three, most preferably all four R _o and R _m groups are hydrogen, preferably all of at least two of rings A, B and C The four R _o and R _m groups are hydrogen; in some embodiments, all R _o and R _m groups on rings A, B and C are hydrogen; preferably each R _p is independently selected from hydrogen,- OR ¹ and -NR ¹ R ² ; no more than two, preferably no more than one R _p is hydrogen, preferably no R _p is hydrogen; more preferably at least one, preferably two, most preferably all three R _p are -NR ¹ R ² ; In some embodiments, one or even both of rings A, B, and C can be independently selected C ₃ containing one or two heteroatoms independently selected from O, S and N -C ₉ heteroaryl ring replacement, the heteroaryl ring is optionally substituted with one or more independently selected R ⁵ groups; G is independently selected from the group consisting of hydrogen, deuterium, C ₁ -C ₁₆ Alkoxides, phenoxides, bisphenoxides, nitrous acid Salt, nitrile, alkylamine, imidazole, arylamine, polyalkylene oxide, halide, alkylsulfide, arylsulfide or phosphine oxide; in one aspect, for G, the fraction [(deuterium)/ (Deuterium + hydrogen)] is at least 0.20, preferably at least 0.40, even more preferably at least 0.50 and most preferably at least 0.60 or even at least 0.80; wherein any two of R ¹ , R ² and R ³ connected to the same heteroatom It can be combined to form a ring with five or more members, which optionally contains one or more other heteroatoms selected from the group consisting of -O-, -NR ¹⁵ -and -S-.

In the structure of formula (II)-(III), e and f are independently integers from 0 to 4; each of R ²⁰ and R ²¹ is independently selected from the group consisting of halogen, nitro, alkyl, and substituted The alkyl group, -NC(O)OR ¹ , -NC(O)SR ¹ , -OR ¹ and -NR ¹ R ² ; each R ²⁵ is independently selected from the group consisting of: monosaccharide part, disaccharide part , Oligosaccharide part and polysaccharide part, -C(O)R ¹ , -C(O)OR ¹ , -C(O)NR ¹ R ² ; and each R ²² and R ²³ is independently selected from the group consisting of : Hydrogen, alkyl and substituted alkyl.

In the structure of formula (IV), R ³⁰ is located at the ortho or para position of the bridged amine moiety and is selected from the group consisting of -OR ³⁸ and -NR ³⁶ R ³⁷ , each of R ³⁶ and R ³⁷ is independently Selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, acyl, R ⁴ , -C(O)OR ¹ , -C(O)R ¹ and- C(O)NR ¹ R ² ; R ³⁸ is selected from the group consisting of hydrogen, acyl group, -C(O)OR ¹ , -C(O)R ¹ and -C(O)NR ¹ R ² ; g and h are independently integers 0 to 4; each of R ³¹ and R ³² is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, Substituted alkylaryl, -(CH ₂ ) _n -OR ¹ , -(CH ₂ ) _n -NR ¹ R ² , -C(O)R ¹ , -C(O)OR ¹ , -C(O)O ^- , -C(O)NR ¹ R ² , -OC(O)R ¹ , -OC(O)OR ¹ , -OC(O)NR ¹ R ² , -S(O) ₂ R ¹ , -S( ^{_{O) 2 OR 1, -S (}} O) 2 O -, -S (O) 2 NR 1 R 2, -NR 1 C (O) R 2, -NR 1 C (O) OR 2, -NR 1 C (O)SR ² , -NR ¹ C(O)NR ² R ³ , -P(O) ₂ R ¹ , -P(O)(OR ¹ ) ₂ , -P(O)(OR ¹ )O ^- and ^{-P (O) (O -)} 2; wherein the index n is an integer of 0-4, preferably 0-1, most preferably 0; -NR ³⁴ R ³⁵ amine moiety in the ortho position or para position of bridging and R ³⁴ and R ³⁵ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and R ⁴ ; R ³³ Is independently selected from the group consisting of hydrogen, -S(O) ₂ R ¹ , -C(O)N(H)R ¹ , -C(O)OR ¹ and -C(O)R ¹ ; when When g is 2 to 4, any two adjacent R ³¹ groups may be combined to form a fused ring with five or more members, wherein no more than two atoms in the fused ring may be nitrogen atoms.

In the structure of formula (V), X ⁴⁰ is selected from the group consisting of oxygen atom, sulfur atom and NR ⁴⁵ ; R ⁴⁵ is independently selected from the group consisting of hydrogen, deuterium, alkyl, substituted alkyl group, an aryl group, the substituted aryl group, an alkaryl group, the alkyl substituted _{aryl, -S (O) 2 OH,} -S (O) 2 O -, -C (O) OR 1, -C (O)R ¹ and -C(O)NR ¹ R ² ; R ⁴⁰ and R ⁴¹ are independently selected from the group consisting of -(CH ₂ ) _n -OR ¹ , -(CH ₂ ) _n -NR ¹ R ² , where the index n is an integer from 0 to 4, preferably from 0 to 1, and most preferably 0; j and k are independently integers from 0 to 3; R ⁴² and R ⁴³ are independently selected from the group consisting of: Alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, -S(O) ₂ R ¹ , -C(O)NR ¹ R ² , -NC (O)OR ¹ , -NC(O)SR ¹ , -C(O)OR ¹ , -C(O)R ¹ , -(CH ₂ ) _n -OR ¹ , -(CH ₂ ) _n -NR ¹ R ² , where the index n is an integer of 0 to 4, preferably 0 to 1, and most preferably 0; R ⁴⁴ is -C(O)R ¹ , -C(O)NR ¹ R ² and -C(O)OR ¹ .

In the structures of formulas (I)-(V), any charge present in any of the aforementioned groups is balanced by suitable independently selected internal or external relative ions. Suitable independently selected external counter ions can be cationic or anionic. Examples of suitable cations include, but are not limited to, one or more metals preferably selected from Group I and Group II, most preferably these metals are Na, K, Mg and Ca, or organic cations such as ammonium, Ammonium and phosphonium. Examples of suitable anions include (but are not limited to): fluoride, chloride, bromide, iodide, perchlorate, hydrogensulfate, sulfate, aminosulfate, nitrate, dihydrogen phosphate, hydrogen phosphate Root, phosphate, bicarbonate, carbonate, methyl sulfate, ethanol sulfate, cyanate, thiocyanate, tetrachlorozincate, borate, tetrafluoroborate, acetate, chloroacetate, cyanide Glycolacetate, glycolate, aminoacetate, methylaminoacetate, dichloroacetate and trichloroacetate, 2-chloro-propionate, 2-hydroxypropionate, glycolate, thioglycolate, Thioacetate, phenoxyacetate, trimethylacetate, valerate, palmitate, acrylate, oxalate, malonate, crotonate, succinate, citrate, methylene-bis- Thioglycolate, ethylene-bis-iminoacetate, nitrotriacetate, fumarate, maleate, benzoate, methylbenzoate, chlorobenzoate, two Chlorobenzoate, hydroxybenzoate, aminobenzoate, phthalate, terephthalate, indole acetate, chlorobenzenesulfonate, benzenesulfonate, tosylate, biphenylsulfonate and Chlorotoluenesulfonate. Those who are generally familiar with this technique will fully understand that different relative ions can be used instead of the relative ions listed above.

As indicated above, in addition to the leuco moiety, the leuco compound also contains an alkyleneoxy moiety. In one aspect, the alkyleneoxy moiety includes at least one ethylene oxide group and at least one propylene oxide group. In another aspect, the alkyleneoxy moiety contains 1 to about 20 ethylene oxide groups and 1 to about 20 propylene oxide groups. In such alkyleneoxy moieties, different alkyleneoxy groups can be arranged in a block configuration or a random configuration. In one aspect, the alkyleneoxy groups of the alkyleneoxy moiety are arranged in a block configuration.

其中n、q、r及s係獨立地選自整數0至5，n及r之總和為2至10，且q及s之總和為2至10。在更特定態樣中，n及r之總和為2至5，且q及s之總和為2至5。The alkyleneoxy moiety can be covalently bonded to the leuco moiety via any suitable linking group. In one aspect, the alkyleneoxy moiety is covalently bonded to the leuco moiety via a linking group selected from the group consisting of oxygen atoms and nitrogen atoms. When the linking group is an oxygen atom, one valence position of the oxygen atom is occupied by the alkyleneoxy moiety and the second valence position of the oxygen atom is occupied by the rest of the leuco moiety. When the linking group is a nitrogen atom, one valence position of the nitrogen atom is occupied by the rest of the leuco moiety and one valence position of the nitrogen atom is occupied by the alkyleneoxy moiety. The remaining valence of the nitrogen atom can be occupied by any suitable group, such as a second alkyleneoxy moiety. In one aspect, the alkyleneoxy moiety is preferably covalently bonded to the leuco moiety via a nitrogen atom. In such embodiments, the nitrogen atom and the alkyleneoxy moiety together have the structure -NR ¹ (C ₂ H ₄ O) _n (C ₃ H ₆ O) _q H, where n and q are independently selected from integers 1 to 5, and R ¹ is selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and alkylene oxide Base part. In another aspect, the leuco compound contains two alkyleneoxy moieties, each alkyleneoxy moiety is covalently bonded to the leuco moiety via a nitrogen atom, the nitrogen atom and the alkyleneoxy moieties The parts have the following structure in common

Wherein n, q, r, and s are independently selected from integers 0 to 5, the sum of n and r is 2 to 10, and the sum of q and s is 2 to 10. In a more specific aspect, the sum of n and r is 2 to 5, and the sum of q and s is 2 to 5.

； (CI)

； (CII)

； (CIII)

；及 (CIV)

(CV)； 其中式CI-CV與其氧化形式之比率為至少1:19、1:9或1:3，較佳為至少1:1，更佳為至少3:1，最佳為至少9:1或甚至19:1。The leuco compound contained in the composition may have any suitable structure having the characteristics described above. In one aspect, the leuco compound has the same structure as the following formula (CI), (CII), (CIII), (CIV) or (CV)

; (CI)

; (CII)

; (CIII)

; And (CIV)

(CV); wherein the ratio of formula CI-CV to its oxidized form is at least 1:19, 1:9 or 1:3, preferably at least 1:1, more preferably at least 3:1, most preferably at least 9: 1 or even 19:1.

In the structure of formula (CI), each individual R _o , R _m and R _p group on each of rings A, B, and C is independently selected from the group consisting of hydrogen, deuterium and R ⁵ ; Each R ⁵ is independently selected from the group consisting of: halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,- ^{_{(CH 2) n -OR 1,}} - (CH 2) n -NR 1 R 2, -C (O) R 1, -C (O) OR 1, -C (O) O -, -C (O) NR ¹ R ² , -OC(O)R ¹ , -OC(O)OR ¹ , -OC(O)NR ¹ R ² , -S(O) ₂ R ¹ , -S(O) ₂ OR ¹ ,- ^{_{S (O) 2 O -,}} -S (O) 2 NR 1 R 2, -NR 1 C (O) R 2, -NR 1 C (O) OR 2, -NR 1 C (O) SR 2, - ^{NR 1 C (O) NR 2} R 3, -P (O) 2 R 1, -P (O) (OR 1) 2, -P (O) (OR 1) O - and -P (O) (O ^- ) ₂ ; wherein the index n is an integer of 0 to 4, preferably 0 to 1, and most preferably 0; wherein two R _o on different rings A, B and C can be combined to form five or more A fused ring of three members; when the fused ring has six or more members, two R _o on different A, B and C rings can be combined to form an organic linker optionally containing one or more heteroatoms In one embodiment, two R _o on different A, B and C rings are combined to form a heteroatom bridge selected from -O- and -S-, which produces a six-membered fused ring; R on the same ring _o and R _m or R _m and R _p on the same ring can be combined to form a fused aliphatic ring or a fused aromatic ring, any of which may contain heteroatoms; in the three rings A, B or C At least one of them, preferably at least two, more preferably at least three, most preferably all four R _o and R _m groups are hydrogen, preferably all four of at least two of rings A, B and C Each R _o and R _m group is hydrogen; in some embodiments, all R _o and R _m groups on rings A, B and C are hydrogen; preferably each R _p is independently selected from hydrogen, -OR ¹ and -NR ¹ R ² ; no more than two, preferably no more than one R _p is hydrogen, preferably no R _p is hydrogen; more preferably at least one, preferably two, most preferably all three R _{p are-} NR ¹ R ² ; In some embodiments, one or even both of rings A, B, and C can be independently selected C ₃ -containing one or two heteroatoms independently selected from O, S, and N C ₉ heteroaryl ring substitution, the heteroaryl ring is optionally substituted with one or more independently selected R ⁵ groups; G is independently selected from the group consisting of hydrogen, deuterium, C ₁ -C ₁₆ Alkoxide, phenoxide, bisphenoxide, nitrite , Nitrile, alkylamine, imidazole, arylamine, polyalkylene oxide, halide, alkyl sulfide, aryl sulfide or phosphine oxide; in one aspect, for G, the fraction [(deuterium)/( Deuterium + hydrogen)] is at least 0.20, preferably at least 0.40, even more preferably at least 0.50 and most preferably at least 0.60 or even at least 0.80; wherein any two of R ¹ , R ² and R ³ connected to the same heteroatom can be Combines to form a ring with five or more members, which optionally contains one or more other heteroatoms selected from the group consisting of -O-, -NR ¹⁵ -and -S-.

In the structures of formulas (CII) and (CIII), the variables e and f are independently integers 0 to 4; each of R ²⁰ and R ²¹ is independently selected from the group consisting of halogen, nitro, alkyl, and Substituted alkyl group, -NC(O)OR ¹ , -NC(O)SR ¹ , -OR ¹ and -NR ¹ R ² ; each R ²⁵ is independently selected from the group consisting of: monosaccharide part, disaccharide Part, oligosaccharide part and polysaccharide part, -C(O)R ¹ , -C(O)OR ¹ , -C(O)NR ¹ R ² ; and each of R ²² and R ²³ is independently selected from the following components Group: hydrogen, alkyl and substituted alkyl.

In the structure of formula (CIV), R ³⁰ is located at the ortho or para position of the bridged amine moiety and is selected from the group consisting of -OR ³⁸ and -NR ³⁶ R ³⁷ , each of R ³⁶ and R ³⁷ is independently Selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, acyl, R ⁴ , -C(O)OR ¹ , -C(O)R ¹ and- C(O)NR ¹ R ² ; R ³⁸ is selected from the group consisting of hydrogen, acyl group, -C(O)OR ¹ , -C(O)R ¹ and -C(O)NR ¹ R ² ; g and h are independently integers 0 to 4; each of R ³¹ and R ³² is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, Substituted alkylaryl, -(CH ₂ ) _n -OR ¹ , -(CH ₂ ) _n -NR ¹ R ² , -C(O)R ¹ , -C(O)OR ¹ , -C(O)O ^- , -C(O)NR ¹ R ² , -OC(O)R ¹ , -OC(O)OR ¹ , -OC(O)NR ¹ R ² , -S(O) ₂ R ¹ , -S( ^{_{O) 2 OR 1, -S (}} O) 2 O -, -S (O) 2 NR 1 R 2, -NR 1 C (O) R 2, -NR 1 C (O) OR 2, -NR 1 C (O)SR ² , -NR ¹ C(O)NR ² R ³ , -P(O) ₂ R ¹ , -P(O)(OR ¹ ) ₂ , -P(O)(OR ¹ )O ^- and ^{-P (O) (O -)} 2; wherein the index n is an integer of 0-4, preferably 0-1, most preferably 0; -NR ³⁴ R ³⁵ amine moiety in the ortho position or para position of bridging and R ³⁴ and R ³⁵ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and R ⁴ ; R ³³ Is independently selected from the group consisting of hydrogen, -S(O) ₂ R ¹ , -C(O)N(H)R ¹ , -C(O)OR ¹ and -C(O)R ¹ ; when When g is 2 to 4, any two adjacent R ³¹ groups may be combined to form a fused ring with five or more members, wherein no more than two atoms in the fused ring may be nitrogen atoms.

In the structure of formula (CV), X ⁴⁰ is selected from the group consisting of oxygen atom, sulfur atom and NR ⁴⁵ ; R ⁴⁵ is independently selected from the group consisting of hydrogen, deuterium, alkyl, substituted alkyl group, an aryl group, the substituted aryl group, an alkaryl group, the alkyl substituted _{aryl, -S (O) 2 OH,} -S (O) 2 O -, -C (O) OR 1, -C (O)R ¹ and -C(O)NR ¹ R ² ; R ⁴⁰ and R ⁴¹ are independently selected from the group consisting of -(CH ₂ ) _n -OR ¹ , -(CH ₂ ) _n -NR ¹ R ² , where the index n is an integer from 0 to 4, preferably from 0 to 1, and most preferably 0; j and k are independently integers from 0 to 3; R ⁴² and R ⁴³ are independently selected from the group consisting of: Alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, -S(O) ₂ R ¹ , -C(O)NR ¹ R ² , -NC (O)OR ¹ , -NC(O)SR ¹ , -C(O)OR ¹ , -C(O)R ¹ , -(CH ₂ ) _n -OR ¹ , -(CH ₂ ) _n -NR ¹ R ² , where the index n is an integer of 0 to 4, preferably 0 to 1, and most preferably 0; R ⁴⁴ is -C(O)R ¹ , -C(O)NR ¹ R ² and -C(O)OR ¹ .

In the structures of formula (I)-(V) and (CI)-(CV), R ¹ , R ² , R ³ and R ¹⁵ are independently selected from the group consisting of hydrogen, alkyl, and substituted Alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and R ⁴ ; wherein R ⁴ is an organic group composed of one or more organic monomers, and the molecular weight of these monomers In the range of 28 to 500, preferably 43 to 350, and even more preferably 43 to 250, the organic group can be partially substituted by one or more other leuco colorants of the structure of Formula IV. In one aspect, R ⁴ is selected from the group consisting of: alkyleneoxy (polyether), pendant alkyleneoxy (polyester), pendant alkyleneamine (polyamide), Epichlorohydrin, quaternary ammonium epichlorohydrin, alkyleneamine, hydroxyalkylene, oxyalkylene, carboxyalkylene, carboxyalkoxyalkylene and sugar. When any leuco colorant contains R ⁴ groups with three or more adjacent monomers, the leuco colorant is defined herein as a "polymeric leuco colorant." Those familiar with this technology will know that the characteristics of the compound in any of many characteristic properties (such as solubility, distribution, deposition, removal, dyeing, etc.) are consistent with the placement and placement of such adjacent monomers incorporated therein. Sex and number are related. Therefore, those skilled in the art can adjust the placement, consistency and number of such adjacent monomers, thereby changing any specific properties in a more or less predictable manner.

In the structure of formula (CI)-(CV), R ¹ , R ² and R ³ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl , Alkaryl, substituted alkaryl and R ⁴ . R ⁴ is an alkyleneoxy moiety as described above.

Furthermore, in the structures of formulas (CI)-(CV), any charge present in any of the aforementioned groups is balanced by suitable independently selected internal or external relative ions. Suitable independently selected external counter ions can be cationic or anionic. Examples of suitable cations include, but are not limited to, one or more metals preferably selected from Group I and Group II, most preferably these metals are Na, K, Mg and Ca, or organic cations such as ammonium, Ammonium and phosphonium. Examples of suitable anions include (but are not limited to): fluoride, chloride, bromide, iodide, perchlorate, hydrogensulfate, sulfate, aminosulfate, nitrate, dihydrogen phosphate, hydrogen phosphate Root, phosphate, bicarbonate, carbonate, methyl sulfate, ethanol sulfate, cyanate, thiocyanate, tetrachlorozincate, borate, tetrafluoroborate, acetate, chloroacetate, cyanide Glycolacetate, glycolate, aminoacetate, methylaminoacetate, dichloroacetate and trichloroacetate, 2-chloro-propionate, 2-hydroxypropionate, glycolate, thioglycolate, Thioacetate, phenoxyacetate, trimethylacetate, valerate, palmitate, acrylate, oxalate, malonate, crotonate, succinate, citrate, methylene-bis- Thioglycolate, ethylene-bis-iminoacetate, nitrotriacetate, fumarate, maleate, benzoate, methylbenzoate, chlorobenzoate, two Chlorobenzoate, hydroxybenzoate, aminobenzoate, phthalate, terephthalate, indole acetate, chlorobenzenesulfonate, benzenesulfonate, tosylate, biphenylsulfonate and Chlorotoluenesulfonate. Those who are generally familiar with this technique will fully understand that different relative ions can be used instead of the relative ions listed above.

； (CI) 其中，式(CI)與其氧化形式之比率為至少1:3；其中環A、B及C中之每一者上的每個個別R_o 、R_m 及R_p 基團係獨立地選自由以下組成之群：氫、氘及R⁵ ；其中各R⁵ 係獨立地選自由以下組成之群：鹵素、硝基、烷基、經取代之烷基、芳基、經取代之芳基、烷芳基、經取代之烷芳基、-(CH₂ )_n -O-R¹ 、-(CH₂ )_n -NR¹ R² 、-C(O)R¹ 、-C(O)OR¹ 、-C(O)O^- 、-C(O)NR¹ R² 、-OC(O)R¹ 、-OC(O)OR¹ 、-OC(O)NR¹ R² 、-S(O)₂ R¹ 、-S(O)₂ OR¹ 、-S(O)₂ O^- 、-S(O)₂ NR¹ R² 、-NR¹ C(O)R² 、-NR¹ C(O)OR² 、-NR¹ C(O)SR² 、-NR¹ C(O)NR² R³ 、-P(O)₂ R¹ 、-P(O)(OR¹ )₂ 、-P(O)(OR¹ )O^- 及-P(O)(O^- )₂ ；其中指數n為整數0至4，較佳為0至1，最佳為0；其中三個環A、B或C中之至少一者上的R_o 及R_m 基團中之至少一者為氫；各R_p 係獨立地選自氫、-OR¹ 及-NR¹ R² ；其中G係獨立地選自由以下組成之群：氫、氘、C₁ -C₁₆ 烷氧化物、苯氧化物、雙苯氧化物、亞硝酸鹽、腈、烷基胺、咪唑、芳基胺、聚環氧烷、鹵化物、烷基硫化物、芳基硫化物及膦氧化物；其中R¹ 、R² 及R³ 係獨立地選自由以下組成之群：氫、烷基、經取代之烷基、芳基、經取代之芳基、烷芳基、經取代之烷芳基及R⁴ ；R⁴ 為伸烷基氧基部分；且其中化合物中存在之任何電荷由適合的獨立選擇之內部或外部相對離子平衡。Therefore, in one aspect, the leuco compound is a triarylmethane leuco compound of formula (CI)

; (CI) where the ratio of formula (CI) to its oxidized form is at least 1:3; where each individual R _o , R _m and R _p group on each of rings A, B and C are independent Is selected from the group consisting of hydrogen, deuterium and R ⁵ ; wherein each R ⁵ is independently selected from the group consisting of halogen, nitro, alkyl, substituted alkyl, aryl, substituted aromatic Group, alkaryl group, substituted alkaryl group, -(CH ₂ ) _n -OR ¹ , -(CH ₂ ) _n -NR ¹ R ² , -C(O)R ¹ , -C(O)OR ^{1 , -C (O) O -,} -C (O) NR 1 R 2, -OC (O) R 1, -OC (O) OR 1, -OC (O) NR 1 R 2, -S (O) ^{_{2 R 1, -S (O)}} 2 OR 1, -S (O) 2 O -, -S (O) 2 NR 1 R 2, -NR 1 C (O) R 2, -NR 1 C (O) OR ² , -NR ¹ C(O)SR ² , -NR ¹ C(O)NR ² R ³ , -P(O) ₂ R ¹ , -P(O)(OR ¹ ) ₂ , -P(O) (oR ¹⁾ O ^- and ^{-P (O) (O -)} 2; wherein the index n is an integer of 0-4, preferably 0-1, most preferably 0; wherein the three rings A, B or C of At least one of the R _o and R _m groups on at least one is hydrogen; each R _p is independently selected from hydrogen, -OR ¹ and -NR ¹ R ² ; wherein G is independently selected from the following Group: hydrogen, deuterium, C ₁ -C ₁₆ alkoxide, phenoxide, bisphenoxide, nitrite, nitrile, alkylamine, imidazole, arylamine, polyalkylene oxide, halide, alkyl Sulfides, aryl sulfides and phosphine oxides; wherein R ¹ , R ² and R ³ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl , Alkaryl, substituted alkaryl and R ⁴ ; R ⁴ is an alkyleneoxy moiety; and any charge present in the compound is balanced by suitable independently selected internal or external relative ions.

(CVI) 其中各R⁴ 係獨立地選自由以下組成之群：H、甲基、乙基、((CH₂ CH₂ O)_a (C₃ H₆ O)_b )H及其混合物；較佳至少一個R⁴ 基團為((CH₂ CH₂ O)_a (C₃ H₆ O)_b )H；其中各指數a獨立地為整數1-100，各指數b獨立地為整數0-50，且其中所有R⁴ 基團中之所有獨立選擇之整數a之總和不超過100，且所有R⁴ 基團中之所有獨立選擇之整數b之總和不超過50。較佳至少兩個R⁴ 基團係選自甲基及乙基，最佳結構(CVI)中之至少一個N經兩個選自甲基及乙基，較佳甲基之R⁴ 基團取代。In one aspect, preferred leuco compounds include compounds conforming to the structure of formula (CVI),

(CVI) where each R ⁴ is independently selected from the group consisting of H, methyl, ethyl, ((CH ₂ CH ₂ O) _a (C ₃ H ₆ O) _b )H and mixtures thereof; preferably At least one R ⁴ group is ((CH ₂ CH ₂ O) _a (C ₃ H ₆ O) _b )H; wherein each index a is independently an integer 1-100, and each index b is independently an integer 0-50, and wherein the sum of all integers independently selected R ⁴ all of a group of not more than 100, b is an integer and the sum of all of all R ⁴ are independently selected groups of not more than 50. Preferably at least two R ⁴ groups are selected from methyl and ethyl, and at least one N in the best structure (CVI) is substituted with two R ⁴ groups selected from methyl and ethyl, preferably methyl .

(CVII) 其中各指數c獨立地為0、1或2，較佳各c為0或1，更佳c之兩個獨立選擇之值相同；各R⁴ 係獨立地選自由以下組成之群：H、Me、Et、((CH₂ CH₂ O)_a (C₃ H₆ O)_b )H及其混合物；較佳各R⁴ 為((CH₂ CH₂ O)_a (C₃ H₆ O)_b )H，其中各指數a獨立地為整數1-50，更佳為1-25，甚至更佳為1-20、1-15、1-10、1-5或甚至1-2；各指數b獨立地為整數0-25，更佳為0-15，甚至更佳為1-5或甚至1-3，且其中隱色著色劑中所有獨立選擇之整數a之總和不超過100，更佳不超過80，最佳不超過60、40、20、10或甚至不超過5，且隱色著色劑中所有獨立選擇之整數b之總和不超過50，更佳不超過40，最佳不超過30、20或甚至10。在尤其較佳態樣中，各指數c為1，各R⁴ 為((CH₂ CH₂ O)_a (C₃ H₆ O)_b )H，各指數a為整數1-5，各指數b為整數1-5，隱色化合物中所有獨立選擇之整數a之總和為4至10，且隱色著色劑中所有獨立選擇之整數b之總和為5至15。In another aspect, highly preferred leuco compounds include compounds conforming to the structure of formula (CVII),

(CVII) where each index c is independently 0, 1, or 2, preferably each c is 0 or 1, and more preferably the two independent choices of c have the same value; each R ⁴ is independently selected from the group consisting of: H, Me, Et, ((CH ₂ CH ₂ O) _a (C ₃ H ₆ O) _b )H and mixtures thereof; preferably each R ⁴ is ((CH ₂ CH ₂ O) _a (C ₃ H ₆ O ) _b ) H, wherein each index a is independently an integer of 1-50, more preferably 1-25, even more preferably 1-20, 1-15, 1-10, 1-5 or even 1-2; each The index b is independently an integer of 0-25, more preferably 0-15, even more preferably 1-5 or even 1-3, and the sum of all independently selected integers a in the leuco colorant does not exceed 100, and more Preferably not more than 80, best not more than 60, 40, 20, 10 or even not more than 5, and the sum of all independently selected integers b in the leuco colorant does not exceed 50, more preferably not more than 40, most preferably not more than 30, 20 or even 10. In a particularly preferred aspect, each index c is 1, each R ⁴ is ((CH ₂ CH ₂ O) _a (C ₃ H ₆ O) _b )H, each index a is an integer of 1-5, and each index b It is an integer of 1-5, the sum of all independently selected integers a in the leuco compound is 4 to 10, and the sum of all independently selected integers b in the leuco colorant is 5 to 15.

(CVIII)In another aspect, highly preferred leuco compounds include compounds conforming to the structure of formula (CVIII),

(CVIII)

Where R ⁸ is H or CH ₃ and the average value of each index b is independently about 1 to 2.

In one aspect, the surface tension value of the leuco colorant of the present invention exceeds 45 mN/m, more preferably exceeds 47.5 mN/m, and most preferably exceeds 50 mN/m. In another aspect, the surface tension value of the second color state of the leuco colorant exceeds 45 mN/m, more preferably exceeds 47.5 mN/m, and most preferably exceeds 50 mN/m. In another aspect of the present invention, the surface tension value of the leuco colorant and its corresponding second color state exceeds 45 mN/m, more preferably exceeds 47.5 mN/m, and most preferably exceeds 50 mN/m.

The leuco triarylmethane compound described herein can be prepared by any suitable synthetic method. For example, this type of compound can be through the acid between an aromatic aldehyde and an electron-rich aryl coupling agent (for example, in an amount of about 2 molar equivalents of aryl coupling agent and 1 molar equivalent of aromatic aldehyde). The catalyzed condensation reaction is produced. The aromatic aldehyde can be any suitable compound containing an aromatic moiety (for example, an aryl moiety, a substituted aryl moiety, a heteroaromatic moiety, or a substituted heteroaromatic moiety) which has a covalent attachment to it The aldehyde group. In one aspect, the aromatic aldehyde is preferably a substituted benzaldehyde, which contains (preferably at the para position of the aldehyde group) a group having the structure -OR ¹ or -NR ¹ R ² . In another aspect, the aromatic aldehyde is preferably a substituted benzaldehyde containing the group -NR ¹ R ² at the para position of the aldehyde group, wherein R ¹ and R ² are selected from the group consisting of hydrogen, Methyl or ethyl (more preferably methyl).

AC-I

AC II 其中指數a、b、c及d獨立地選自整數0至5；對於選自AC-I及AC-II之偶合劑，a及b之總和為2至10，且AC-II中c及d之總和為2至10。在更特定態樣中，對於選自AC-I及AC-II之偶合劑，a及b之總和為2至5，且AC-II中c及d之總和為2至5。在一個實施例中，AC-I中指數a及b之總和為2或3；AC至II中指數a及b之總和為2或3且AC-II中指數c及d之總和為1至5，較佳為2至4或甚至2至3。偶合劑AC-I及AC-II可以任何比例組合，限制條件為以產生隱色化合物之酸催化之縮合反應中使用的芳族醛之當量計，所使用之偶合劑之量足以提供至少兩莫耳當量。As noted above, in addition to aromatic aldehydes, condensation reactions also utilize aryl coupling agents. In order to produce leuco triarylmethane compounds, for every molar equivalent of aromatic aldehyde, the condensation reaction usually uses at least two molar equivalents of aryl coupling agent. In one aspect, a single aryl coupler compound can be used to provide two molar equivalents of aryl coupler utilized in the reaction. In another aspect, two molar equivalents of a mixture of two or more different aryl coupling agents may be used for the reaction. In such embodiments, the two or more different aryl coupling agents can be used in any combination or relative ratio, with the restriction that for every molar equivalent of aromatic aldehyde, the sum of the mixture is at least about two molar equivalents的aryl coupling agent. In such embodiments, the two or more different aryl coupling agents may differ in, for example, the number and/or nature of the substituents attached to the aryl moiety. In one aspect, the reaction may utilize a first aryl coupling agent, which includes a first oxyalkylene or polyoxyalkylene moiety having a first distribution of oxyalkylene, and a second aryl coupling agent, It contains a second oxyalkylene or polyoxyalkylene moiety having a second distribution of oxyalkylene that is different from the first distribution. For example, in one aspect, the first aryl coupling agent may include an oxyalkylene moiety composed of oxirane groups, such as the following AC-I, and the second aryl coupling agent may include The polyoxyalkylene part composed of oxyethylene group and propylene oxide group, such as the following AC-II,

AC-I

AC II where the indices a, b, c, and d are independently selected from integers 0 to 5; for the coupling agent selected from AC-I and AC-II, the sum of a and b is 2 to 10, and in AC-II, c The sum of d and d is 2-10. In a more specific aspect, for the coupling agent selected from AC-I and AC-II, the sum of a and b is 2 to 5, and the sum of c and d in AC-II is 2 to 5. In one embodiment, the sum of indices a and b in AC-I is 2 or 3; the sum of indices a and b in AC to II is 2 or 3 and the sum of indices c and d in AC-II is 1 to 5. , Preferably 2 to 4 or even 2 to 3. Coupling agents AC-I and AC-II can be combined in any ratio. The limitation is that the amount of coupling agent used is sufficient to provide at least two moles based on the equivalent of the aromatic aldehyde used in the acid-catalyzed condensation reaction to produce the leuco compound. Ear equivalent.

In one aspect, for example, one equivalent of p-N,N-dimethylbenzaldehyde is condensed with at least two molar equivalents of a mixture of the aryl coupling agents AC-I and AC-II shown above, wherein For the aryl coupling agent AC-I, the sum of the indices a and b is 2 or 3, preferably 2, and wherein preferably a and b are each 1; and for the aryl coupling agent AC-II, the indices a and The sum of b is 2 or 3, preferably 2, and wherein preferably a and b are each 1, and the average sum of indices c and d is about 2.5 to 3.0, and at least one of c or d is 1 .

Those skilled in the art will recognize that when two or more different aryl coupling agents are used to prepare the leuco compounds herein, it is expected that the products from such reactions will include the inclusion of incompatible coupling agents ( There are as many leuco compounds as different coupling agents used) and cross-coupling leuco compounds containing a mixture of aryl coupling agents used. For example, in a preparation method using two dissimilar aryl coupling agents A and B used in roughly equal molar amounts, excluding any disturbance caused by the difference in reactivity, the product distribution will contain about 25% containing two One part of the leuco compound of coupling agent A, 25% of the leuco compound containing two parts of coupling agent B, and 50% of the leuco compound containing one part A and one part B coupling agent.

The example leuco composition can be prepared according to the following description of the composition in which the aryl aldehyde is consistent with Ar-C(O)H, but can be prepared by a general method that can be easily adapted.

The four-neck flask is equipped with an overhead stirrer, condenser, temperature controller, heating mantle and nitrogen inlet. Next, add about 2 moles of aryl coupling agent or mixture of aryl coupling agents to the flask and heat to about 65-71°C. During heating, about 1 mol of Ar-C(O)H and a catalytic amount (about 0.4 mol) of urea dissolved in a small amount of water in advance are added. After mixing the above chemicals, add about 1.2 mol hydrochloric acid (in the form of crude Muriatic acid) dropwise to control the temperature below 90-100°C. After adding hydrochloric acid, the reaction was stirred at 95-100°C for about 7 hours.

Various methods can be used to extract the leuco colorant synthesized by the above method. One method is to neutralize the reaction product to about pH 9 and remove the water by rotary evaporation under reduced pressure. The resulting viscous substance is diluted with an organic solvent (such as isopropanol) and filtered to remove inorganic salts. The organic solvent is evaporated and the final product is obtained.

In another embodiment, the present invention provides a leuco composition obtained by the following steps: (i) providing one molar equivalent of aromatic aldehyde, (ii) providing about two molar equivalents of aryl coupling agent or aryl group A mixture of coupling agents, wherein at least one aryl coupling agent contains covalently bonded oxyalkylene or polyoxyalkylene moieties, wherein the oxyalkylene or polyoxyalkylene moieties contain at least one ethylene oxide group and At least one propylene oxide group, (iii) combine the aromatic aldehyde and aryl coupling agent in a suitable reaction vessel, (iv) add 0.01 to 0.5 equivalent of urea, (v) add crude hydrochloric acid to adjust the pH Between about 0 and 3, (vi) heat the mixture at 60 to 120°C for 2 to 12 hours, (vii) adjust the pH to at least about 7, and (viii) separate at least a portion from the liquid product to neutralize The leuco composition contains at least one leuco compound, the leuco compound contains a leuco moiety and an alkyleneoxy moiety covalently bound to the leuco moiety, wherein the leucochromic composition Contains at least one ethylene oxide group and at least one propylene oxide group. In one such embodiment, the leuco compound has a structure of formula (CVII) above, wherein at least one independently selected index b has a value of at least 1.

The amount of the leuco colorant used in the laundry care composition of the present invention can be any content suitable for achieving an increase in the whiteness index (WI CIE) of white fabrics or textiles. In one aspect, the laundry care composition comprises about 0.0001% to about 1.0% by weight, preferably 0.0005% to about 0.5% by weight, even more preferably about 0.0008% to about 0.2% by weight, most preferably 0.004% by weight The amount of leuco colorant to about 0.1% by weight.

In another aspect, the laundry care composition contains 0.0025 to 5.0 milliequivalents/kg, preferably 0.005 to 2.5 milliequivalents/kg, even more preferably 0.01 to 1.0 milliequivalents/kg, most preferably 0.05 to 0.50 milliequivalents/kg The amount of leuco colorant, where the unit milliequivalent/kg refers to the milliequivalent of the leuco color per kilogram of laundry composition. For a leuco colorant containing more than one leuco colorant, the milliequivalent value is related to the millimolar value of the leuco colorant by the following equation: (millimolar value of the leuco colorant)×(the leuco color part Milli-equivalent value / millimolar value of leuco colorant) = milli-equivalent value of leuco color. In the case where each leuco colorant has only a single leuco color part, and the value of milliequivalent/kg will be equal to the value of leuco colorant/kg of the laundry care composition.

(DI)

(DII)

(DIII)

(DIV)

(DV)。In addition to the leuco compounds, antioxidant compounds, and solvents discussed above, the leuco composition of the present invention may include other compounds. For example, the leuco composition may contain up to about 2% by weight of salts (such as sodium chloride or sodium sulfate), unreacted starting materials for the production of leuco compounds, and side reactions of the starting materials. Produced impurities and leuco compounds or degradation products of such impurities. Specific non-limiting examples of such substances include compounds of formula (DI)-(DV)

(DI)

(DII)

(DIII)

(DIV)

(DV).

(DVI)

(DVII)

(DVIII)

(DIX)。In the structures of formulas (DI)-(DV), R ¹⁰¹ and R ¹⁰² are independently selected from the group consisting of hydrogen, alkyl (such as methyl) and oxyalkylene. The oxyalkylene group may contain any suitable number of oxyalkylene repeating units (e.g., ethylene oxide and/or propylene oxide), such as the range disclosed above for the leuco compound present in the leuco composition. Such oxyalkylene groups of R ¹⁰¹ and R ¹⁰² may be independently terminated by a member selected from the group consisting of hydrogen, CH=CH ₂ , -CH ₂ -CH=CH ₂ , -CH=CH-CH ₃ , -CH ₂ -CHO, -CH(CH ₃ )-CHO, -CH ₂ -CO-CH ₃ , -CH ₂ -COOH, -CH(CH ₃ )-COOH, -CH ₂ -CH ₂ Cl, -CHCl -CH ₃ , -CH ₂ -CH ₂ -CH ₂ Cl, -CH ₂ -CHCl-CH ₃ and -CHCl-CH ₂ -CH ₃ . In addition, the groups R ¹⁰¹ and R ¹⁰² can be combined to form a group having the structure -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, which together with the nitrogen atom forms a pholine ring. Other compounds that may be present in the leuco composition include compounds of formula (DVI)-(DIX)

(DVI)

(DVII)

(DVIII)

(DIX).

(DX)

(DXI)Each aryl moiety of the compound of formula (DVI)-(DIX) may be independently unsubstituted or substituted with a nitro group or a group having the structure -NR ¹⁰¹ R ¹⁰² (usually in the para position), where R ¹⁰¹ and R ¹⁰² Are independently selected from the groups described above. Other compounds that may be present in the leuco composition include phenol and aminophenol, which usually contain a group having the structure -NR ¹⁰¹ R ¹⁰² at the para position of the hydroxyl group, wherein R ¹⁰¹ and R ¹⁰² are independently selected from the above Described group. The leuco composition may also contain compounds of formula (DX) and (DXI)

(DX)

(DXI)

(DXII)。In the structures of (DX) and (DXI), the aryl moiety and the cyclohexadienyl moiety can be unsubstituted or substituted with a nitro group or a group having the structure -NR ¹⁰¹ R ¹⁰² (usually in the para position), where R ¹⁰¹ and R ¹⁰² are independently selected from the groups described above. The leuco composition may also contain condensation products of some of the compounds described above (such as the compound of formula (DXII))

(DXII).

As noted above, the leuco composition may also contain the colored (eg, oxidized) form of the leuco compound present in the composition. In the case of the triarylmethane leuco colorant, the oxidized form of the triarylmethane leuco colorant (which contains a central carbocation) can be combined with the anion present in the leuco composition (such as the above as a leuco compound for A suitable charge balance forms an adduct together with the anion described by the ion.

The unreacted starting materials and impurities described above can be present in the leuco composition in any suitable amount. Preferably, these materials and impurities are present in the leuco composition in a relatively small amount, which will not adversely affect the performance of the leuco colorant to any significant degree. Excluding inorganic salts, unreacted starting materials and water, in a preferred embodiment, based on the active leuco compound, such impurities will be less than 10% by weight, preferably less than 5% by weight and more preferably less than 2% by weight exist.

The leuco composition may include any suitable number of leuco compounds as described above. In addition, in addition to the leuco compound, the leuco composition may contain any suitable solvent. In one aspect, the leuco composition includes a solvent selected from the group consisting of water, ethylene glycol, propylene glycol, glycerol, poly(ethylene glycol), poly(propylene glycol), ethylene oxide, and cyclic Copolymers and mixtures of oxypropane. In another aspect, the leuco composition includes a solvent selected from the group consisting of poly(ethylene glycol), poly(propylene glycol), a copolymer of ethylene oxide and propylene oxide, and non-volatile materials as disclosed below. Ionic surfactants and their mixtures. In a preferred embodiment, the leuco composition is dissolved in poly(ethylene glycol) (such as PEG200) before being incorporated into the laundry care composition.

In one aspect, in addition to the leuco compound and any suitable solvents that may be present, the leuco composition further includes an antioxidant compound. Antioxidant compounds can be used to stabilize the composition and reduce the amount of leuco compounds that prematurely convert to the second color state. In such compositions, any suitable antioxidant compound can be used. In one aspect, the antioxidant compound is selected from the group consisting of: hindered phenols (such as BHT, Irganox 1135, Irganox 1076, Irganox 1010, Irganox 1330 And Yancanox 1035), aromatic amines and their derivatives (such as Yangenox 5057), α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, ethoxyquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl hydroquinone, tert-butyl-hydroxyanisole, lignin sulfonic acid and its salts, 6-Hydroxy-2,5,7,8-tetra-methylchroman-2-carboxylic acid (Trolox™), 1,2-benzisothiazolin-3-one (Proxel GXL™), Benzofuran or benzopyran derivatives (such as Irganox® HP136 and AOX-1 commercially available from Milliken and Company, Spartanburg, USA), tocopherol sorbate, butylated hydroxybenzoic acid and its salts, gallic acid and Its alkyl esters, uric acid and its salts and alkyl esters, sorbic acid and its salts, dihydroxyfumaric acid and its salts, aromatic amines (such as Irganox® 5057) and mixtures thereof. In the case where the antioxidant is a liquid miscible with the leuco composition, the antioxidant may serve as a solvent or co-solvent.

The leuco composition of the present invention should be stored and transported in a closed container to prevent contamination from dust, moisture or other foreign objects. Preferably, the leuco composition is stored and transported in an airtight container. The shipping container can be made of a material with a low oxygen permeability coefficient P, where P = (of the permeate) (thickness of the film) / (surface area) (time) (pressure drop across the film), the unit is [cm ³ ×cm]/ [cm ² ×s×(cmHg)]. Suitable containers can be made of materials in which P×10 ^{10 is} less than 10 at 30°C, more preferably less than 5, and most preferably less than 2. This restricts the exposure of the material to oxygen and restricts the conversion of the leuco compound to the second color state during storage and shipping.

The container can be composed of any suitable size of tank truck, handbag, barrel, large glass bottle or main body load in cylinder. The best container is made of stainless steel or HDPE. The container can be an open head type or a sealed head type container. The stainless steel container may be unlined or optionally have any suitable coating lining, such as an epoxy or epoxy phenol coating. Some containers may contain at least one drain valve, and the containers are preferably sturdy, stackable, and DOT/UN approved. Suitable packages are available from multiple suppliers, such as General Steel, Mauser, Schütz, Cardinal Packaging or others. For non-limiting examples, suitable containers may be Ecobulk MX, Ecobulk MX-EX, Ecobulk MX-EV, Ecobulk MX, Cleancert, Ecobulk MX-EX-EV Cleancert, Ecobulk SX-EX, and Ecobulk MX impellers provided by Schuetz. , Such as Mauser® SM 6, Mauser® SM 13, Mauser® SM 15, Mauser® SM EX, Mauser® SM LP provided by Mauser. Optionally, HDPE containers may contain additives to protect the contents from UV and visible light, such as Mauser ^® SM LP* handbags or the like. In addition, HDPE containers can contain other protection provided by EVOH permeation barriers or Dualprotect systems (available from Schütz packaging systems).

As explained above, the leuco composition of the present invention is relatively stable and does not require specific shipping or filling requirements. For example, the material does not need to be packaged in an inert atmosphere or shipped under climate control to remain stable. However, the storage stability of the leuco composition can be improved by implementing certain measures. For example, it is better to ship and store this substance or other less stable substances in an oxygen-deficient atmosphere, cold temperature, or both. One way to create an oxygen-deficient atmosphere is to use inert gases such as nitrogen, argon or carbon dioxide. The container can be purged with inert gas for a period of time, or by evacuating and backfilling the container with inert gas. The purging time during purging should be at least three times longer than the time required to fill the head space of the container, and preferably at least five times longer. During purging or backfilling, the internal pressure should be similar to or slightly higher than atmospheric pressure. The preferred internal pressure range is 0.5 to 2 atm, more preferably 0.8 to 1.5 atm, and most preferably 0.95 to 1.2 atm. Those familiar with this technology will realize that the ideal pressure is the value under the conditions encountered during purging or backfilling and that the gas pressure will change when the temperature changes, roughly following the ideal gas law. In addition, the material itself can be purged with inert gas by bubbling inert gas through the product for a period of time before or after encapsulation.

For any container containing the leuco composition of the present invention or even a material with lower stability, the volume percentage of the container occupied by the material should be at least 50%, more preferably 80%, even more preferably 90% or even 95%, It also limits the volume that constitutes the headspace occupied by ambient air, inert gas or mixtures thereof. For materials that are sensitive to oxygen, limiting the amount of oxygen present in the container will slow the conversion of leuco compounds into a second color state. In addition, vessel designs that minimize the surface area of the interface between the material and the headspace are generally preferred. For this reason, shipping materials by restricting the movement of materials in the container can reduce the time-average surface area and increase the stability of the materials, especially materials containing less stable leuco compounds.

As stated above, the material of the present invention is stable enough to be stored and transported without climate control, where the temperature can be in the range of -40°C to 60°C depending on the climate and location. However, a lower temperature is preferred. The temperature range suitable for storage and transportation of chemical substances is -30°C to 60°C, more preferably -10°C to 50°C, and most preferably 0°C to 35°C.

Other products can be used for protection, such as oxygen scavengers in films, sachets, or directly incorporated into packaging materials to maintain the oxygen-deficient atmosphere in the container.

Any of the protective measures for minimizing the transformation of the leuco composition before being incorporated into the laundry care composition as described above can be similarly applied to the storage and storage of the laundry care composition containing the leuco composition Shipment.

It is believed that the leuco compounds and compositions described above are suitable for processing textile materials, such as in household washing processes. In particular, it is believed that due to the nature of the leuco compound, the leuco compound will be deposited on the fibers of the textile material. In addition, once deposited on the textile material, the leuco compound can be converted into a colored compound by applying a suitable chemical or physical trigger, which will convert the leuco compound into its colored form. For example, the leuco compound can be converted into its colored form when the leuco compound is oxidized to an oxidizing compound. By selecting an appropriate leuco component, the leuco compound can be designed to give the textile material a desired hue when the leuco compound is converted into its colored form. For example, leuco compounds that exhibit a blue hue when converted to a colored form can be used to resist the yellowing of textile materials that usually occurs due to the passage of time and/or repeated washing. Therefore, in other embodiments, the present invention provides a laundry care composition containing the above-mentioned leuco compound, and a household method for processing textile materials (for example, a method for washing clothes or clothing items).

Preferably, when converted into the second color state, the leuco compound has a relative chromaticity of 210 to 345, or even a relative chromaticity of 240 to 320, or even a relative chromaticity of 250 to 300 (for example, 250 to 290). Woven fabrics provide shades. The relative chromaticity can be determined by any suitable method known in the art. However, it can preferably be determined as described in further detail herein regarding the deposition of leuco entities on cotton for cotton without any leuco entities.

As indicated above, in the second embodiment, the present invention provides a laundry care composition, which includes a laundry care ingredient and a leuco composition as described herein. The laundry care composition may comprise any suitable leuco composition or combination of leuco composition as described herein. The laundry care composition may contain any suitable laundry care ingredients. The laundry care ingredients suitable for use in the present invention are described in detail below. Laundry care ingredients

The laundry care composition may contain other suitable adjuvants, which in some aspects may be fully or partially incorporated. The adjuvant can be selected according to the desired function of the laundry care composition. The first composition may include an adjuvant. In some aspects, in the case of a multi-compartment unit-dose article, the adjuvant may be a non-first (e.g., second, third, fourth, etc.) encapsulated in a compartment separated from the first composition. ) Part of the composition. The non-first composition can be any suitable composition. The non-first composition may be in the form of a solid, liquid, dispersion, gel, slurry, or a mixture thereof. When the unit dose contains multiple compartments, the leuco colorant may be added to or present in one, two, or even all compartments. In one embodiment, the leuco colorant is added to a larger compartment, resulting in a lower concentration, which can minimize any problems involving potential contact staining. On the other hand, the concentration of antioxidants and leuco colorants in a smaller volume compartment can result in higher local concentrations of antioxidants, which can provide enhanced stability. Therefore, those skilled in the art will understand that the dispenser can select the location and amount of the leuco colorant according to the required characteristics of the unit dose. Adjuvant

The laundry care composition may include a surfactant system. Based on the weight of the laundry care composition, the laundry care composition may comprise about 1% to about 80%, or 1% to about 60%, preferably about 5% to about 50%, more preferably about 8% to about 40% The surfactant system.

Surfactants : Suitable surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and amphoteric surfactants and mixtures thereof. Suitable surfactants can be linear or branched, substituted or unsubstituted, and can be derived from petrochemical or biological materials. The preferred surfactant system includes anionic and nonionic surfactants, preferably in a weight ratio of 90:1 to 1:90. In some cases, the weight ratio of the anionic and nonionic surfactants is preferably at least 1:1. However, the ratio may preferably be lower than 10:1. When present, the total surfactant content is preferably 0.1% to 60% by weight, 1% to 50% by weight or even 5% to 40% by weight of the composition of the present invention.

Anionic surfactants : Anionic surfactants include (but are not limited to) surface-active compounds that meet the following conditions: they contain an organic hydrophobic group, which usually contains 8 to 22 carbon atoms in its molecular structure or Usually 8 to 18 carbon atoms, and at least one water-soluble group, which is preferably selected from sulfonate, sulfate and carboxylate, in order to form a water-soluble compound. Typically, the hydrophobic group will contain a C ₈ -C ₂₂ alkyl group, or acyl group. Such surfactants are used in the form of water-soluble salts and the salt-forming cations are usually selected from sodium, potassium, ammonium, magnesium and mono-, wherein sodium cation is the commonly used cation selected.

The anionic surfactant and auxiliary anionic co-surfactant of the present invention may exist in acid form, and the acid form can be neutralized to form a surfactant that is desirably used in the detergent composition of the present invention salt. Typical agents used for neutralization include metal relative ionic bases, such as hydroxides, such as NaOH or KOH. More preferred reagents for neutralizing the anionic surfactants and auxiliary anionic surfactants or auxiliary surfactants of the present invention in acid form include ammonia, amines, oligoamines or alkanolamines. Preferably it is an alkanolamine. Suitable non-limiting examples include monoethanolamine, diethanolamine, triethanolamine and other linear or branched alkanolamines known in the art; for example, highly preferred alkanolamines include 2-amino-1-propanol Alcohol, 1-aminopropanol, monoisopropanolamine or 1-amino-3-propanol. Amine neutralization can be carried out to a complete or partial degree, for example, a part of the anionic surfactant mixture can be neutralized by sodium or potassium and a part of the anionic surfactant mixture can be neutralized by an amine or an alkanolamine.

Suitable sulfonate surfactants include methyl sulfonate, alpha olefin sulfonate, alkylbenzene sulfonate, especially alkylbenzene sulfonate, preferably C _10-13 alkyl benzene sulfonate. Suitable alkylbenzene sulfonates (LAS) can be obtained, preferably by sulfonating commercially available linear alkylbenzene (LAB). Suitable LABs include low-grade 2-phenyl LAB, such as those supplied by Sasol under the trademark Isochem® or LAB supplied by Petresa under the trademark Petrelab®. Other suitable LABs include high-grade 2-phenyl LAB, such as those supplied by Sasol under the trademark Hyblene ®Supplied LAB. Suitable anionic surfactants are alkylbenzene sulfonates, which are obtained by DETAL-catalyzed processes, but other synthetic routes such as HF are also suitable. In one aspect, the magnesium salt of LAS is used.

Suitable sulfate surfactants include alkyl sulfates, preferably C _8-18 alkyl sulfates, or mainly C ₁₂ alkyl sulfates.

Preferred sulfate surfactants are alkyl alkoxylated sulfates, preferably alkyl ethoxylated sulfates, preferably C _8-18 alkyl alkoxylated sulfates, preferably C _{8 -18} alkyl ethoxylated sulfates, preferably alkyl alkoxylated sulfates have an average degree of alkoxylation of 0.5 to 20, preferably 0.5 to 10, preferably alkyl alkoxylated sulfates It is a C _8-18 alkyl ethoxylated sulfate having an average degree of ethoxylation of 0.5 to 10, preferably 0.5 to 5, more preferably 0.5 to 3. The alkyl alkoxylated sulfate may have a broad alkoxy distribution or a peak alkoxy distribution.

Alkyl sulfates, alkyl alkoxylated sulfates, and alkylbenzene sulfonates can be linear or branched (including 2-fold alkyl substituted or medium chain branched types), substituted or unsubstituted, and It can be derived from petrochemical or biological materials. The branched group is preferably an alkyl group. Typically, the alkyl group is selected from methyl, ethyl, propyl, butyl, pentyl, cycloalkyl and mixtures thereof. Single or multiple alkyl branches may be present on the main hydrocarbyl chain of the starting alcohol used to produce the sulfated anionic surfactant used in the detergent of the present invention. The branched chain sulfated anionic surfactant is preferably selected from alkyl sulfates, alkyl ethoxy sulfates and mixtures thereof.

Alkyl sulfates and alkyl alkoxy sulfates are commercially available in a variety of chain lengths, ethoxylation and degree of branching. Commercially available sulfates include Neodol alcohol-based sulfates (such as Shell company), Lial-Isalchem and Safol (such as Sasol company), and natural alcohols (such as The Procter & Gamble Chemicals company).

Other suitable anionic surfactants include alkyl ether formates, including C10-C26 linear or branched chains, preferably C10-C20 linear, most preferably C16-C18 linear alkyl alcohols and 2 to 20, Preferably 7 to 13, more preferably 8 to 12, most preferably 9.5 to 10.5 ethoxylate. The acid form or the salt form can be used, such as sodium or ammonium salts, and the alkyl chain can contain one cis or trans double bond. Alkyl ether carboxylic acids are commercially available from Kao (Akypo®), Huntsman (Empicol®) and Clariant (Emulsogen®).

Nonionic surfactants : Suitable nonionic surfactants are selected from the group consisting of: C ₈ -C ₁₈ alkyl ethoxylates, such as NEODOL® nonionic surfactants from Shell; C ₆ -C ₁₂ alkyl phenol alkoxylates, wherein the preferred alkoxylate units are ethyleneoxy units, propyleneoxy units or mixtures thereof; C ₁₂ -C ₁₈ alcohols and C ₆ -C ₁₂ alkyl phenols and cyclic Condensates of oxyethane/propylene oxide block copolymers, such as Pluronic® from BASF; alkyl polysaccharides, preferably alkyl polyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether caps The poly(alkoxylated) alcohol surfactant; and mixtures thereof.

Suitable nonionic surfactants are alkyl polyglucoside and/or alkyl alkoxylated alcohol.

Suitable nonionic surfactants include alkyl alkoxylated alcohols, preferably C _8-18 alkyl alkoxylated alcohols, preferably C _8-18 alkyl ethoxylated alcohols, preferably alkyl The average degree of alkoxylation of the alkyl alkoxylated alcohol is 1 to 50, preferably 1 to 30, or 1 to 20, or 1 to 10, preferably the alkyl alkoxylated alcohol has 1 to 10, more Preferably 1 to 7, more preferably 1 to 5 and most preferably 3 to 7 C _8-18 alkyl ethoxylated alcohols with an average degree of ethoxylation. In one aspect, the alkyl alkoxylated alcohol is a C _12-15 alkyl ethoxylated alcohol having an average degree of ethoxylation of 7 to 10. Alkyl alkoxylated alcohols can be linear or branched, and substituted or unsubstituted. Suitable nonionic surfactants include the nonionic surfactants from BASF under the brand name Lutensol®.

Cationic surfactants : Suitable cationic surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary phosphonium compounds, and mixtures thereof.

Preferred cationic surfactant is a quaternary ammonium compound having the following general _{formula: (R) (R 1)} (R 2) (R 3) N + X - wherein, R is a straight-chain or branched, substituted or Unsubstituted C _6-18 alkyl or alkenyl moiety, R ₁ and R ₂ are independently selected from methyl or ethyl moieties, R ₃ is hydroxy, hydroxymethyl or hydroxyethyl moiety, X is an anion, It provides electrical neutrality, and preferred anions include: halide, preferably chloride; sulfate; and sulfonate.

Based on the weight of the composition, the fabric care composition of the present invention may contain up to about 30%, or about 0.01% to about 20%, or more or about 0.1% to about 20% of cationic surfactant. For the purposes of the present invention, cationic surfactants include cationic surfactants that can deliver fabric care advantages. Non-limiting examples of suitable cationic surfactants include: fatty amines, imidazoline quaternary materials and quaternary ammonium surfactants, preferably N,N-bis(octadecanoyl-oxy-ethyl) N,N-dimethylammonium chloride, N,N-bis(tallowyl-oxy-ethyl) N,N-dimethylammonium chloride, methylsulfate N,N-bis(octadecanoic acid) Base-oxy-ethyl) N-(2-hydroxyethyl) N-methylammonium; 1,2-bis(octadecanoyl-oxy)-3-trimethylammonium propane chloride; diethylene Alkyl dimethyl ammonium salts, such as di-canola dimethyl ammonium chloride, di(hard) tallow dimethyl ammonium chloride, di-canola dimethyl ammonium methyl sulfate; 1-methyl methyl sulfate -1-stearylaminoethyl-2-stearylimidazolinium; 1-tallowylaminoethyl-2-tallowimidazoline; N,N"-dialkyl two Ethylene triamine; N-(2-hydroxyethyl)-1,2-ethylenediamine or N-(2-hydroxyisopropyl)-1,2-ethylenediamine and glycolic acid reaction product, used Fatty acid esterification, where the fatty acids are (hydrogenated) tallow fatty acids, palm fatty acids, hydrogenated palm fatty acids, oleic acid, rapeseed fatty acids, hydrogenated rapeseed fatty acids; polyglycerol esters (PGE), oily sugar derivatives and wax emulsions and above A mixture of substances.

It should be understood that the combination of softener active agents disclosed above is suitable for use herein.

Amphoteric and zwitterionic surfactants : Suitable amphoteric or zwitterionic surfactants include amine oxide and/or betaine. The preferred amine oxide is alkyl dimethyl amine oxide or alkyl amide propyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide and especially cocoa dimethyl amine oxide . The amine oxide may have linear or moderately branched alkyl moieties. Typical linear amine oxides include water-soluble amine oxides that contain one R1 C8-18 alkyl moiety and two R2 and R3 moieties selected from the group consisting of C1-3 alkyl and C1-3 hydroxyalkyl. The preferred amine oxide is characterized by the formula R1-N(R2)(R3)O, wherein R1 is a C8-18 alkyl group and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl Group, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants may especially include linear C10-C18 alkyl dimethylamine oxide and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxide.

Other suitable surfactants include betaines, such as alkyl betaines, alkyl amido betaines, amidolithium azo betaines, sultaines (INCI Sultaines), and phosphobetaines. Leuco Colorant Thinner

Another component of the leuco colorant composition can be a diluent and/or a solvent. The purpose of diluents and/or solvents is usually (but not limited to) improving fluidity and/or reducing the viscosity of the leuco colorant. Although water is usually the preferred diluent and/or solvent due to its low cost and non-toxicity, other solvents can also be used. The preferred solvent is a solvent with low cost and low risk. Examples of suitable solvents include (but are not limited to) ethylene glycol, propylene glycol, glycerol, alkoxylated polymers (such as polyethylene glycol, polypropylene glycol), copolymers of ethylene oxide and propylene oxide, Tween 20®, Tween 40®, Tween 80® and the like, and combinations thereof. Among the polymers, copolymers of ethylene oxide and propylene oxide may be preferred. The characteristic of these polymers is usually the water cloud point, which can help separate the product and water to remove undesirable water-soluble impurities. Examples of ethylene oxide and propylene oxide copolymers include, but are not limited to, BASF's PLURONIC series polymers and Dow's TERGITOL™ series polymers. When the leuco colorant composition is incorporated into the laundry care composition, these polymers can also act as nonionic surfactants.

The laundry care composition described herein may also include one or more of the following non-limiting list of ingredients: fabric care benefits; cleaning enzymes; deposition aids; rheology modifiers; builders; chelating agents Bleaching agent; bleaching agent; bleaching agent precursor; bleaching auxiliary agent; bleaching catalyst; fragrance and/or fragrance microcapsules; zeolite loaded with fragrance; flavoring agent for starch encapsulation; polyglycerol ester; whitening agent; pearlescent agent; Enzyme stabilization system; scavengers, including fixatives for anionic dyes, complexing agents for anionic surfactants and their mixtures; optical brighteners or fluorescent agents; polymers, including (but not limited to) immune Contaminant polymers and/or soil suspension polymers; dispersants; defoamers; non-aqueous solvents; fatty acids; foam inhibitors, such as polysiloxane foam inhibitors; cationic starches; scum dispersants; substantial dyes; Colorants; opalizers; antioxidants; solubilizers, such as toluenesulfonate, cumenesulfonate, and naphthalenesulfonate; colored speckle; colored beads, balls or extrudates; clay softeners; Bacterial agent. Alternatively or in addition, the composition may include a surfactant, a quaternary ammonium compound, and/or a solvent system. The quaternary ammonium compound may be present in a fabric enhancer composition, such as a fabric softener, and contains a quaternary ammonium cation as a positively charged polyatomic ion of the structure NR ₄ ⁺ , wherein R is an alkyl group or an aryl group. Shading Dyes

The composition may contain other fabric sunscreens. Suitable fabric sunscreens include dyes, dye-clay combinations and pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of direct blue, direct red, direct violet, acid blue, acid red, acid violet, basic blue, basic violet and basic red. (CI) Classification of dyes or mixtures thereof. Preferred dyes include alkoxylated azothiophene, solvent violet 13, acid violet 50 and direct violet 9.

Aesthetic colorants. The composition may contain one or more aesthetic colorants. Suitable aesthetic colorants include dyes, dye-clay combinations, pigments, and Liquitint® polymeric colorants (Milliken & Company, Spartanburg, South Carolina, USA). In one aspect, suitable dyes and pigments include small molecule dyes and polymeric dyes. The aesthetic colorant may include at least one chromophore component selected from the group consisting of acridine, anthraquinone, anthraquinone, azo, benzodifuran, benzodifuranone, carotenoid, coumarin, flower Cyanine, diaza hemicyanine, diphenylmethane, formazan, hemicyanine, indigo, methane, methanesulfonate, naphthimide, naphthoquinone, nitrate, nitrous, cyanine, phenothidium, phthalocyanine ( Such as copper phthalocyanine), pyrazole, pyrazolone, quinolone, stilbene, styrene, triarylmethane (such as triphenylmethane), dibenzopyran and mixtures thereof.

In one aspect of the present invention, the aesthetic colorant includes Liquitint® Blue AH, Liquitint® Blue BB, Liquitint® Blue 275, Liquitint® Blue 297, Liquitint® Blue BB, Blue 15, Liquitint® Green 101, Liquitint® Orange 272 , Liquitint® Orange 255, Liquitint® Pink AM, Liquitint® Pink AMC, Liquitint® Pink ST, Liquitint® Purple 129, Liquitint® Purple LS, Liquitint® Purple 291, Liquitint® Yellow FT, Liquitint® Blue Buf, Liquitint® Pink AM , Liquitint® Pink PV, Acid Blue 80, Acid Blue 182, Acid Red 33, Acid Red 52, Acid Violet 48, Acid Violet 126, Acid Blue 9, Acid Blue 1 and their mixtures.

Encapsulation. The composition may include an encapsulation material. In one aspect, the encapsulant includes a core, a shell layer having an inner surface and an outer surface, and the shell layer encapsulates the core. The core can contain any laundry care adjuvant, but generally the core can contain a material selected from the group consisting of: fragrance; brightener; tinting dye; insect repellent; silicone; wax; flavor; vitamin; fabric softener ; In one aspect, skin care agents, paraffins; enzymes; antibacterial agents; bleaching agents; sensing agents; and mixtures thereof; and the shell layer may comprise a material selected from the group consisting of: polyethylene; polyamide Polyvinyl alcohol, optionally containing other co-monomers; polystyrene; polyisoprene; polycarbonate; polyester; polyacrylate; amino plastic, in one aspect, the amino plastic can Contains polyurea, polyurethane and/or polyureaurethane. In one aspect, the polyurea may contain polyoxymethylene urea and/or melamine formaldehyde; polyolefin; polysaccharide, In one aspect, the polysaccharide may include alginate and/or polyglucosamine; gelatin; shellac; epoxy resin; vinyl polymer; water-insoluble inorganic substance; polysiloxane; and mixtures thereof.

Preferably the encapsulant contains perfume. Preferably the encapsulant comprises a shell layer, which may comprise melamine formaldehyde and/or cross-linked melamine formaldehyde. Other preferred capsules contain a polyacrylate-based shell layer. A preferred encapsulant is disclosed, which comprises a core material and a shell layer, the shell layer at least partially surrounding the core material. At least 75%, 85%, or even 90% of these encapsulants can have a breaking strength of 0.2 MPa to 10 MPa, and 0% to 20%, or even less than 10% or 5% of the beneficial agent leakage, so that all the initial Encapsulated beneficial agent meter. Preferably, at least 75%, 85%, or even 90% of the encapsulants may have the following encapsulants (i) particle size of 1 to 80 microns, 5 to 60 microns, 10 to 50 Micrometers or even 15 micrometers to 40 micrometers, and/or (ii) at least 75%, 85%, or even 90% of the encapsulants have a particle wall thickness of 30 nm to 250 nm, 80 nm to 180 nm or even 100 nm to 160 nm. The formaldehyde scavenger can be used with the encapsulant, for example, in the capsule slurry and/or added to the composition before, during or after the encapsulant is added to such composition. Suitable capsules can be prepared according to the teachings of USPA 2008/0305982 A1; and/or USPA 2009/0247449 A1. Alternatively, suitable capsules can be purchased from Ppleton Papers Inc. of Appleton, Wisconsin USA.

In a preferred aspect, in addition to the encapsulant, the composition may include a deposition aid. Preferred deposition aids are selected from the group consisting of cationic and nonionic polymers. Suitable polymers include cationic starch, cationic hydroxyethyl cellulose, polyvinyl formal, locust bean gum, mannan, xyloglucan, tamarind gum, polyethylene terephthalate and containing methyl The polymer of dimethylaminoethyl acrylate optionally has one or more monomers selected from the group consisting of acrylic acid and acrylamide.

Perfume. The preferred composition of the present invention contains perfume. Generally, the composition contains perfume, which contains one or more perfume raw materials selected from the group as described in WO 08/87497. However, any fragrance suitable for use in laundry care compositions can be used. The preferred method of incorporating perfume into the composition of the present invention is through encapsulation of perfume particles, which contain water-soluble hydroxyl compounds or melamine-formaldehyde or modified polyvinyl alcohol. Deodorant material

The cleaning composition of the present invention may include deodorizing materials. Such materials can reduce or even eliminate the perception of one or more odors. These materials can be characterized by the calculated deodorization value ("MORV"), which is calculated according to the test method shown in WO 2016/049389.

As used in this article, "MORV" is the calculated deodorization value of the target material. The MORV of a material indicates the ability of such a material to reduce or even eliminate the perception of one or more odors.

Based on the weight of the composition, the cleaning composition of the present invention may comprise a total of about 0.00025% to about 0.5%, preferably about 0.0025% to about 0.1%, more preferably about 0.005% to about 0.075%, most preferably about 0.01% to About 0.05% of 1 or more deodorizing materials. The cleaning composition may include about 1 to about 20 deodorizing materials, more preferably 1 to about 15 deodorizing materials, and most preferably 1 to about 10 deodorizing materials.

The MORV of one, some or each deodorant material may be at least 0.5, preferably 0.5 to 10, more preferably 1 to 10, most preferably 1 to 5. One, some or each deodorant material may have a uniform MORV, defined as all MORV values> 0.5 for the odor tested as described herein. The blocking agent index of all deodorizing materials can be less than 3, more preferably less than about 2.5, even more preferably less than about 2, and more preferably less than about 1, and most preferably about 0. The average blocking agent index of all deodorizing materials can be about 3 to about 0.001.

In the cleaning composition of the present invention, the deodorizing material may have a fragrance fidelity index of less than 3, preferably less than 2, more preferably less than 1, and most preferably about 0, and/or a fragrance fidelity index of 3 to about 0.001 Average fragrance fidelity index. As the fragrance fidelity index decreases, the deodorizing material provides less and less odor impact while continuing to resist odor.

The cleansing composition of the present invention may contain perfume. The weight ratio of the deodorant composition part to the fragrance part may be about 1:20,000 to about 3000:1, preferably about 1:10,000 to about 1,000:1, more preferably about 5,000:1 to about 500:1, and Most preferably, it is about 1:15 to about 1:1. As the ratio of the deodorant composition to the fragrance part tightens, the deodorant material provides less and less odor impact while continuing to resist odor. Tannin

The cleansing composition of the present invention may contain tannic acid. Tannic acid is a secondary metabolite of polyphenols of higher plants, and it is tannin ester and its derivatives, wherein the tannin part or its derivatives is connected to a variety of polyol-, catechin- and triterpenoid cores ( Gallic tannins, ellagitannins and complex tannins), or oligomeric and polymeric proanthocyanidins (condensed tannins) that can have interflavan coupling and substitution modes. The cleansing composition of the present invention may contain tannin selected from the group consisting of tannins, ellagitannins, complex tannins, condensed tannins, and combinations thereof.

Polymer. The composition may contain one or more polymers. Examples are optionally modified carboxymethyl cellulose, poly(vinylpyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly (Vinylimidazole), polycarboxylate (such as polyacrylate), maleic acid/acrylic acid copolymer, and dodecyl methacrylate/acrylic acid copolymer.

The composition may include one or more amphoteric cleaning polymers. Such polymers have balanced hydrophilic and hydrophobic properties, allowing them to remove grease particles from fabrics and surfaces. Suitable amphoteric alkoxylated grease cleaning polymers include a core structure and a plurality of alkoxylate groups attached to the core structure. These cleaning polymers may comprise alkoxylated polyalkyleneimines, especially ethoxylated polyethyleneimine or polyethyleneimine having inner polyethylene oxide blocks and outer polypropylene oxide blocks. Generally, these cleaning polymers can be incorporated in the composition of the present invention in an amount of 0.005 to 10% by weight, usually 0.5 to 8% by weight.

The composition may include modified hexamethylene diamine. The modification of hexamethylene diamine includes: (1) One or two alkoxylation modification of each nitrogen atom of hexamethylene diamine. The alkoxylation modification consists of replacing the hydrogen atom on the nitrogen of hexamethylene diamine with a (poly) alkoxy chain having an average of about 1 to about 40 alkoxy moieties for each modification, wherein the alkoxy group The terminal alkoxy moiety of the chain is terminated by hydrogen, C1-C4 alkyl, sulfate, carbonate or a mixture thereof; (2) the substitution of a C1-C4 alkyl moiety for each nitrogen atom of hexamethylene diamine and One or two alkoxylation modification. Alkoxylation modification consists of replacing hydrogen atoms with (poly) alkoxy chain having an average of about 1 to about 40 alkoxy moieties for each modification, wherein the terminal alkoxy moiety of the alkoxy chain is End capped by hydrogen, C1-C4 alkyl or a mixture thereof; or (3) a combination thereof.

Alkoxylated polycarboxylates (such as alkoxylated polycarboxylates prepared from polyacrylates) are suitable for use herein to provide other grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815. Chemically, these materials contain polyacrylates with one ethoxy side chain per 7-8 acrylate units. The side chain has the formula -(CH2CH2O)m (CH2)nCH3, where m is 2-3 and n is 6-12. The side chains are esters connected to the "main chain" of the polyacrylate to provide a "combed" polymer structure. The molecular weight can vary, but is generally in the range of about 2000 to about 50,000. By weight, such alkoxylated polycarboxylates may comprise from about 0.05% to about 10% of the composition herein.

其中在式(I)中，R₀ 表示氫原子或CH₃ 基團，R表示CH₂ 基團、CH₂ CH₂ 基團或單鍵，X表示數值0-5，限制條件為當R為單鍵時，X表示數值1-5，且R₁ 為氫原子或C₁ 至C₂₀ 有機基團； 式(II)

其中在式(II)中，R₀ 表示氫原子或CH₃ 基團，R表示CH₂ 基團、CH₂ CH₂ 基團或單鍵，X表示數值0-5，且R₁ 為氫原子或C₁ 至C₂₀ 有機基團。Another suitable carboxylate polymer is a copolymer, which contains: (i) 50 to less than 98% by weight of structural units derived from one or more carboxyl-containing monomers; (ii) 1 to less than 49% by weight Structural units derived from one or more monomers containing sulfonate moieties; and (iii) 1 to 49% by weight derived from one or more types selected from formulas (I) and (II) containing ether bonds The structural unit of the monomer of the monomer: Formula (I):

Wherein in formula (I), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and X represents a value of 0-5. The restriction is that when R is a single When bonding, X represents a value of 1-5, and R ₁ is a hydrogen atom or a C ₁ to C ₂₀ organic group; formula (II)

Wherein in formula (II), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, X represents a value of 0-5, and R ₁ is a hydrogen atom or C ₁ to C ₂₀ organic group.

Preferably, the weight average molecular weight of the polymer is at least 50 kDa, or even at least 70 kDa.

Other suitable polymers include amphoteric graft copolymers. The preferred amphoteric graft copolymer comprises (i) a polyethylene glycol main chain; and (ii) and at least one pendant moiety selected from polyvinyl acetate, polyvinyl alcohol and mixtures thereof. The preferred amphoteric graft copolymer is Sokalan HP22 supplied by BASF. Other suitable polymers include random graft copolymers, preferably polyvinyl acetate grafted polyethylene oxide copolymers, which have a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyoxyethylene backbone is preferably about 6000 and the weight ratio of polyoxyethylene to polyvinyl acetate is about 40 to 60, and there is no more than 1 grafting point per 50 ethylene oxide units. Generally, these substances are incorporated into the composition of the present invention in an amount of 0.005 to 10% by weight, more usually 0.05 to 8% by weight.

The composition may include one or more stain-free polymers. Examples include antifouling polymers having a structure as defined by one of the following formulas (VI), (VII) or (VIII): (VI) -[(OCHR ¹ -CHR ² ) _a -O-OC- Ar-CO-] _d (VII) -[(OCHR ³ -CHR ⁴ ) _b -O-OC-sAr-CO-] _e (VIII) -[(OCHR ⁵ -CHR ⁶ ) _c -OR ⁷ ] _f where: a, b, and c are 1 to 200; d, e, and f are 1 to 50; Ar is 1,4-substituted phenylene; sAr is 1,3-substituted by SO ₃ Me at position 5 Substituted phenylene; Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, where the alkyl group is C ₁ -C ₁₈ alkyl or C ₂ -C ₁₀ hydroxyalkyl, or a mixture thereof; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from H or C ₁ -C ₁₈ N-alkyl or isoalkyl; and R ⁷ is linear or branched C ₁ -C ₁₈ alkyl, or linear or branched C ₂ -C ₃₀ alkenyl, or cycloalkane having 5 to 9 carbon atoms Group, or C ₈ -C ₃₀ aryl group, or C ₆ -C ₃₀ aryl alkyl group.

Suitable stain-free polymers are polyester stain-free polymers, such as Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6 supplied by Rhodia. Other suitable stain-free polymers include Texcare polymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325 supplied by Clariant. Other suitable stain-free polymers are Marloquest polymers, such as Marloquest SL supplied by Sasol.

The composition may also include one or more cellulose polymers, including cellulose polymers selected from alkyl cellulose, alkyl alkoxy alkyl cellulose, carboxy alkyl cellulose, and alkyl carboxy alkyl cellulose. Preferably, the cellulosic polymer is selected from the group comprising: carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof. In one aspect, the carboxymethyl cellulose has a carboxymethyl substitution degree of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.

Stain-free polymer : The composition may include a stain-free polymer. Suitable stain-free polymers have a structure as defined by one of the following structures (I), (II) or (III): (I) -[(OCHR ¹ -CHR ² ) _a -O-OC-Ar -CO-] _d (II) -[(OCHR ³ -CHR ⁴ ) _b -O-OC-sAr-CO-] _e (III) -[(OCHR ⁵ -CHR ⁶ ) _c -OR ⁷ ] _f where: a , B and c are 1 to 200; d, e and f are 1 to 50; Ar is 1,4-substituted phenylene; sAr is 1,3-substituted at position 5 by SO ₃ Me The phenylene; Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, where the alkyl group is C ₁ -C ₁₈ alkyl or C ₂ -C ₁₀ hydroxyalkyl, or a mixture thereof; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from H or C ₁ -C ₁₈ Alkyl or isoalkyl; and R ⁷ is a linear or branched C ₁ -C ₁₈ alkyl group, or a linear or branched C ₂ -C ₃₀ alkenyl group, or a cycloalkyl group having 5 to 9 carbon atoms , Or C ₈ -C ₃₀ aryl, or C ₆ -C ₃₀ aryl alkyl.

Suitable stain-free polymers are the TexCare® series of polymers sold by Clariant, such as TexCare® SRN240 and TexCare® SRA300. Other suitable stain-free polymers are the Repel-o-Tex® series of polymers sold by Solvay, such as Repel-o-Tex® SF2 and Repel-o-Tex® Crystal.

The detergent composition of the present invention can optionally use known polymeric stain-free agents, hereinafter referred to as "SRA". If used, SRA will usually account for 0.01% to 10.0% by weight of the composition, usually 0.1% to 5% by weight, preferably 0.2% to 3.0% by weight.

The preferred SRA usually has a hydrophilic section to have a hydrophilic effect on the surface of hydrophobic fibers (such as polyester and nylon), and a hydrophobic section to deposit on the hydrophobic fiber and remain adhered to it until the washing is completed And flushing cycle, thus acting as an anchor for the hydrophilic section. This can make it easier to clean dyeing that occurs after treatment with SRA in a subsequent washing procedure.

SRA may include, for example, a variety of charged (for example, anionic or even cationic (see US Patent No. 4,956,447)) and uncharged monomer units and the structure may be linear, branched, or even star-shaped. It may include end-capping portions, which are particularly effective in controlling molecular weight or changing physical or surface-active properties. The structure and charge distribution can be adjusted to suit different fiber or textile types and for different detergents or detergent additive products. Suitable stain-free polymers are polyester stain-free polymers, such as Repel-o-tex polymers, including Repel-o-tex, SF-2 and SRP6 supplied by Rhodia. Other suitable stain-free polymers include Texcare polymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325 supplied by Clariant. Other suitable stain-free polymers are Marloquest polymers, such as Marloquest SL supplied by Sasol. Examples of SRA are described in U.S. Patent Nos. 4,968,451; 4,711,730; 4,721,580; No. 4,702,857; No. 4,877,896; No. 3,959,230; No. 3,893,929; No. 4,000,093; No. 5,415,807; No. 4,201,824; No. 4,240,918 No. 4,525,524; No. 4,201,824; No. 4,579,681; and No. 4,787,989; European Patent Application 0 219 048; 279,134 A; 457,205 A; and DE 2,335,044.

Carboxylate polymer : The composition may include a carboxylate polymer, such as a maleate/acrylate random copolymer or a polyacrylate homopolymer. Suitable carboxylate polymers include: polyacrylate homopolymers with a molecular weight of 4,000 Da to 9,000 Da; maleate/acrylates with a molecular weight of 50,000 Da to 100,000 Da, or 60,000 Da to 80,000 Da Random copolymer.

Alternatively, these materials may comprise polyacrylates with one ethoxy side chain per 7-8 acrylate units. The side chain has the formula -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , where m is 2-3 and n is 6-12. The side chains are esters connected to the "main chain" of the polyacrylate to provide a "combed" polymer structure. The molecular weight can vary, but is generally in the range of about 2000 to about 50,000. By weight, such alkoxylated polycarboxylates may comprise from about 0.05% to about 10% of the composition herein.

其中在式(I)中，R₀ 表示氫原子或CH₃ 基團，R表示CH₂ 基團、CH₂ CH₂ 基團或單鍵，X表示數值0-5，限制條件為當R為單鍵時，X表示數值1-5，且R₁ 為氫原子或C₁ 至C₂₀ 有機基團； 式(II)

其中在式(II)中，R₀ 表示氫原子或CH₃ 基團，R表示CH₂ 基團、CH₂ CH₂ 基團或單鍵，X表示數值0-5，且R₁ 為氫原子或C₁ 至C₂₀ 有機基團。Another suitable carboxylate polymer is a copolymer, which contains: (i) 50 to less than 98% by weight of structural units derived from one or more carboxyl-containing monomers; (ii) 1 to less than 49% by weight Structural units derived from one or more monomers containing sulfonate moieties; and (iii) 1 to 49% by weight derived from one or more types selected from formulas (I) and (II) containing ether bonds The structural unit of the monomer of the monomer: Formula (I):

Wherein in formula (I), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and X represents a value of 0-5. The restriction is that when R is a single When bonding, X represents a value of 1-5, and R ₁ is a hydrogen atom or a C ₁ to C ₂₀ organic group; formula (II)

Wherein in formula (II), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, X represents a value of 0-5, and R ₁ is a hydrogen atom or C ₁ to C ₂₀ organic group.

Preferably, the weight average molecular weight of the polymer is at least 50 kDa, or even at least 70 kDa.

Such carboxylate-based polymers are preferably used in the composition herein at a content of about 0.1% to about 7% by weight. Suitable polymeric dispersants include carboxylate polymers, such as maleate/acrylate random copolymers or polyacrylate homopolymers. The preferred carboxylate polymer is a polyacrylate homopolymer having a molecular weight of 4,000 Daltons to 9,000 Daltons, or a maleate/acrylic acid having a molecular weight of 60,000 Daltons to 80,000 Daltons Ester copolymer. Polymeric polycarboxylates and polyethylene glycols can also be used. The polyalkylene glycol-based graft polymer can be prepared from polyalkylene glycol-based compounds and monomer materials, wherein the monomer materials include monomers containing carboxyl groups and optional other monomers. Optional other monomers that are not classified as monomers containing carboxyl groups include monomers containing sulfonic acid groups, monomers containing amine groups, allylamine monomers, quaternary ammonium allylamine monomers, and N vinyl monomers. Monomers, hydroxyl-containing monomers, vinyl aryl monomers, isobutylene monomers, vinyl acetate monomers, salts of any of these materials, derivatives of any of these materials, and mixtures thereof . Although not intending to be bound by theory, it is believed that when used in combination with other synergists (including low molecular weight polycarboxylates), polymeric dispersants enhance the overall structure by inhibiting crystal growth, particle-free peptization, and anti-redeposition Cleaner synergist performance. Examples of polymeric dispersants can be found in US Patent No. 3,308,067, European Patent Application No. 66915, EP 193,360 and EP 193,360.

Alkoxylated polyamine-based polymers : The composition may contain alkoxylated polyamine. Such materials include, but are not limited to, ethoxylated polyethylene diimine, ethoxylated hexamethylene diamine, and sulfated versions thereof. Also includes polypropoxylated derivatives. A variety of amines and polyalkyleneimines can be alkoxylated to various degrees, and optionally further modified to provide the aforementioned advantages. A suitable example is ethoxylation to a 600 g/mol polyethylene diimide core with 20 EO groups per NH and is available from BASF.

Suitable polymers based on alkoxylated polyamines include alkoxylated polyethyleneimine type, wherein the alkoxylated polyalkyleneimine has a polyalkyleneimine core and has one or more A side chain bonded to at least one nitrogen atom in the core of the polyalkyleneimine, wherein the alkoxylated polyalkyleneimine has the empirical formula (PEI) _a -(EO) _b -R ₁ ), where a is the average number average molecular weight (MW _PEI ) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine and is in the range of 100 to 100,000 Daltons, where b is the alkoxylation The average degree of ethoxylation of the one or more side chains of the polyalkyleneimine is in the range of 5 to 40, and wherein R ₁ is independently selected from the group consisting of hydrogen, C ₁ -C ₄ Alkyl groups and combinations thereof.

Other suitable alkoxylated polyalkyleneimines include alkoxylated polyalkyleneimines meeting the following conditions: wherein the alkoxylated polyalkyleneimine has a polyalkyleneimine core, The core has one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein the alkoxylated polyalkyleneimine has (PEI) _o -(EO) _m (PO ) _n -R ₂ or (PEI) _o -(PO) _n (EO) _m -R ₂ empirical formula (II), where o is the polyalkyleneimine core of alkoxylated polyalkyleneimine The average number average molecular weight (MW _PEI ) is in the range of 100 to 100,000 Daltons, where m is the average degree of ethoxylation of the one or more side chains of the alkoxylated polyalkyleneimine, which In the range of 10 to 50, where n is the average degree of propoxylation of the one or more side chains of the alkoxylated polyalkyleneimine, which is in the range of 1 to 50, and where R ₂ is independent The ground is selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl and combinations thereof.

Amphoteric graft copolymer : According to the present invention, amphoteric copolymers can also be used. Particularly suitable polymers include the following polymers (i) polyethylene glycol backbone; and (ii) and at least one side portion selected from polyvinyl acetate. Polyvinyl alcohol and mixtures thereof are also suitable for use in the present invention . Suitable polyethylene glycol polymers include random graft copolymers, which comprise: (i) a hydrophilic backbone comprising polyethylene glycol; and (ii) a hydrophobic side chain, which is selected from the group consisting of : C ₄ -C ₂₅ alkyl, polypropylene, polybutene, saturated vinyl ester of C ₁ -C ₆ monocarboxylic acid, C ₁ -C ₆ alkyl ester of acrylic acid or methacrylic acid and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone and have randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone can be in the range of 2,000 Da to 20,000 Da, or 4,000 Da to 8,000 Da. The molecular weight ratio of the main chain of polyethylene glycol to the side chain of polyvinyl acetate can be in the range of 1:1 to 1:5 or 1:1.2 to 1:2. The average number of grafting sites per ethylene oxide unit can be less than 1, or less than 0.8, and the average number of grafting sites per ethylene oxide unit can be in the range of 0.5 to 0.9. Or the average number of grafting sites per ethylene oxide unit can be in the range of 0.1 to 0.5 or 0.2 to 0.4. A suitable polyethylene glycol polymer is Sokalan HP22. Suitable polyethylene glycol polymers are described in WO 08/007320.

Cellulosic polymers : According to the present invention, cellulosic polymers can be used. Suitable cellulosic polymers are selected from alkyl cellulose, alkyl alkoxy alkyl cellulose, carboxy alkyl cellulose, alkyl carboxy alkyl cellulose, sulfo group, alkyl cellulose, more preferably From carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

Suitable carboxymethyl cellulose has a carboxymethyl substitution degree of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.

Suitable carboxymethyl cellulose has a degree of substitution greater than 0.65 and a degree of block effect greater than 0.45, as described in, for example, WO 09/154933.

The consumer product of the present invention may also include one or more cellulose polymers, including fibers selected from alkyl cellulose, alkyl alkoxy alkyl cellulose, carboxyalkyl cellulose, and alkyl carboxy alkyl cellulose素polymers. In one aspect, the cellulose polymer is selected from the group consisting of carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixtures thereof. In one aspect, the carboxymethyl cellulose has a carboxymethyl substitution degree of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da. Examples of carboxymethyl cellulose polymers are carboxymethyl cellulose commercially available as Finnfix ® GDA by CPKelko, and carboxymethyl cellulose that has been hydrophobically modified, such as carboxymethyl cellulose commercially available as Finnfix ® SH1 by CPKelco Alkyl ketene dimer derivatives of cellulose, or block carboxymethyl cellulose commercially available as Finnfix® V by CPKelco.

Cationic polymers : According to the present invention, cationic polymers can also be used. At the pH of the intended use of the composition, a suitable cationic polymer will have a cationic charge density of at least 0.5 meq/gm, in another embodiment, at least 0.9 meq/gm, in another embodiment, At least 1.2 meq/gm, in another embodiment, at least 1.5 meq/gm, but in one embodiment, it is also less than 7 meq/gm, which in another embodiment is less than 5 meq/gm, the pH value It will generally be in the range of pH 3 to pH 9, and in one embodiment, between pH 4 and pH 8. Herein, the "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. The average molecular weight of such suitable cationic polymers will generally be between 10,000 and 10 million, in one embodiment, between 50,000 and 5 million, and in another embodiment, between 100,000 and 300 million. Between ten thousand.

Cationic polymers suitable for the composition of the present invention contain cationic nitrogen-containing moieties such as quaternary ammonium or cationic protonated amine moieties. Any anionic counter ion can be used in combination with a cationic polymer, as long as the polymer remains soluble in water, the composition or the agglomeration phase of the composition, and as long as the counter ion is physically and chemically related to the basic composition of the composition. It is sufficient if it is compatible or does not improperly weaken product performance, stability or aesthetics in other ways. Non-limiting examples of such relative ions include halide (eg, chloride, fluoride, bromide, iodide), sulfate, and methylsulfate.

Non-limiting examples of such polymers are described in the CTFA Cosmetic Ingredient Dictionary edited by Estrin, Crosley, and Haynes, 3rd edition (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C. (1982)).

Particularly suitable cationic polymers that can be used according to the present invention include those in which the cationic polymer comprises a polymer selected from the group consisting of cationic cellulose, cationic guar gum, poly(acrylamide-co-chlorine Diallyl dimethyl ammonium), poly (acrylamide-co-diallyl dimethyl ammonium chloride-co-acrylic acid), poly (acrylamide dichloride-co-methacrylic acid) Aminopropyl-pentamethyl-1,3-propen-2-ol-ammonium), poly(acrylamide-co-N,N-dimethylaminoethyl acrylate) and its four grades Ammonium derivatives, poly(acrylamide-co-N,N-dimethylaminoethyl methacrylate) and its quaternary ammonium derivatives, poly(acrylamide-methacrylamide) Aminopropyltrimethylammonium chloride), poly(acrylamide-based acrylamidopropyltrimethylammonium chloride-co-acrylic acid), poly(diallyldimethyl chloride) Ammonium), poly(diallyldimethylammonium chloride-co-acrylic acid), poly(ethyl methacrylate-co-oleyl methacrylate-co-diethylaminoethyl methacrylate) ) And its quaternary ammonium derivatives, poly(ethyl methacrylate-co-dimethylaminoethyl methacrylate) and its quaternary ammonium derivatives, poly(hydroxypropyl acrylate-co-methacrylate) Propyl trimethyl ammonium chloride) and its quaternary ammonium derivatives, poly(hydroxyethyl acrylate-co-dimethylaminoethyl methacrylate) and its four Grade ammonium derivatives, poly(methacrylamide-co-dimethylaminoethyl acrylate) and its quaternary ammonium derivatives, poly(methacrylate-co-methacrylamide) Propyl trimethyl ammonium chloride), poly(vinylformamide-co-acrylic acid-co-diallyldimethylammonium chloride), poly(vinylformamide-co-dichloride Allyldimethylammonium), poly(vinylpyrrolidone-co-acrylamide-co-vinylimidazole) and its quaternary ammonium derivatives, poly(vinylpyrrolidone-co-methacrylic acid two Methylaminoethyl) and its quaternary ammonium derivatives, poly(vinylpyrrolidone-co-methacrylamide-co-vinylimidazole) and its quaternary ammonium derivatives, poly(vinylpyrrolidine) Ketone-co-vinylimidazole) and its quaternary ammonium derivatives, polyethylene diimine and including its quaternary ammonium derivatives, and mixtures thereof.

Other cationic polymers suitable for the composition include polysaccharide polymers; cationic guar gum derivatives; cellulose ethers containing quaternary nitrogen; synthetic polymers; copolymers of etherified cellulose, guar gum and starch. When used, the cationic polymer herein is soluble in the composition or soluble in the composition formed by the cationic polymer and anionic, amphoteric and/or zwitterionic surfactant components described above The composite reunion phase. The composite agglomerates of cationic polymers can also be formed from other charged materials in the composition.

Suitable cationic polymers are described in US Patent No. 3,962,418; No. 3,958,581; and US Publication No. 2007/0207109A1.

Dye transfer inhibitor (DTI). The composition may include one or more dye transfer inhibitors. In one embodiment of the present invention, the inventors unexpectedly discovered that in addition to the specified dye, a composition that also includes a polymeric dye transfer inhibitor can produce improved performance. The surprise is that these polymers prevent dye deposition. Suitable dye transfer inhibitors include (but are not limited to) polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyl azole Pyridone and polyvinylimidazole or mixtures thereof. Suitable examples include PVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and Chromabond S-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, Sokalan HP53, Sokalan HP59, Sokalan® HP from BASF 56K, Sokalan® HP 66. The dye control agent can be selected from (i) sulfonated phenol/formaldehyde polymers; (ii) urea derivatives; (iii) polymers of ethylenically unsaturated monomers, in which the polymers are molecularly imprinted by dyes; (iv) ) Fibers composed of water-insoluble polyamides, wherein the average diameter of the fibers does not exceed about 2 µm; (v) polymers obtainable from polymerizing benzophenone monomer compounds; and (vi) combinations thereof. Other suitable DTI systems are as described in WO2012/004134. When present in the target composition, the dye transfer inhibitor may be present in a content of about 0.0001% to about 10% by weight, about 0.01% to about 5% by weight, or even about 0.1% to about 3% by weight of the composition .

Other water-soluble polymers : Examples of water-soluble polymers include (but are not limited to) polyvinyl alcohol (PVA), modified PVA; polyvinylpyrrolidone; PVA copolymers, such as PVA/polyvinylpyrrolidone and PVA/polyvinylamine; partially hydrolyzed polyvinyl acetate; polyalkylene oxide, such as polyethylene oxide; polyethylene glycol; acrylamide; acrylic acid; cellulose, alkyl cellulose materials, such as methyl cellulose , Ethyl cellulose and propyl cellulose; cellulose ether; cellulose ester; cellulose amide; polyvinyl acetate; polycarboxylic acid and salt; polyamino acid or peptide; polyamide; polypropylene amide ; Maleic acid/acrylic acid copolymer; polysaccharides, including starch, modified starch; gelatin; alginate; xyloglucan, other hemicellulose polysaccharides, including xylan, glucuronic acid xylan, Arabinoxylan, mannan, glucomannan and galactoglucomannan; and natural gums, such as frangipane, xanthan gum and carrageenan, locus beans, acacia gum, tragacanth; and combination.

Non-limiting examples of amines include, but are not limited to, ether amines, cyclic amines, polyamines, oligomeric amines (e.g., triamines, diamines, pentamines, tetraamines), or combinations thereof. The composition described herein may include an amine selected from the group consisting of oligomeric amines, ether amines, cyclic amines, and combinations thereof. In some aspects, the amine is not an alkanolamine. In some aspects, the amine is not a polyalkyleneimine.

Examples of suitable oligomeric amines include tetraethylenepentamine, triethylenetetramine, diethylenetriamine and mixtures thereof.

Etheramine : The cleaning composition described herein may contain etheramine. The cleaning composition may contain about 0.1% to about 10%, or about 0.2% to about 5%, or about 0.5% to about 4% of ether amine based on the weight of the composition.

The weight average molecular weight of the ether amine of the present invention may be less than about 1000 g/mol, or about 100 to about 800 g/mol, or about 200 to about 450 g/mol, or about 290 to about 1000 g/mol , Or about 290 to about 900 grams/mole, or about 300 to about 700 grams/mole, or about 300 to about 450 grams/mole. The weight average molecular weight of the ether amine of the present invention may be about 150, or about 200, or about 350, or about 500 g/mol to about 1000, or about 900, or about 800 g/mol.

Alkoxylated phenol compound : The cleaning composition of the present invention may include an alkoxylated phenol compound. The alkoxylated phenol compound can be selected from the group consisting of: alkoxylated polyarylphenol compound, alkoxylated polyalkylphenol compound and mixtures thereof. The alkoxylated phenol compound may be an alkoxylated polyarylphenol compound. The alkoxylated phenol compound may be an alkoxylated polyalkylphenol compound.

Based on the weight of the cleaning composition, the alkoxylated phenol compound may be present in the cleaning composition in an amount of about 0.2% to about 10%, or about 0.5% to about 5%.

The weight average molecular weight of the alkoxylated phenol compound can be between 280 and 2,880.

Enzymes. Preferred compositions include one or more enzymes. Preferred enzymes provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include (but are not limited to) hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, mannan Enzymes, pectin lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligase, pullulanase, tanninase, pentosanase, malanase, β- Glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase and amylase, or mixtures thereof. A typical combination is an enzyme mixture that can include, for example, proteases and lipases and amylases. When present in the composition, the aforementioned other enzymes may be present at a content of about 0.00001% to about 2%, about 0.0001% to about 1%, or even about 0.001% to about 0.5% enzyme protein based on the weight of the composition.

Proteases. Preferred compositions include one or more proteases. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable proteases may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one aspect, the suitable protease may be serine protease, such as alkaline microbial protease or/and trypsin-type protease. Examples of suitable neutral or alkaline proteases include: (a) Subtilisin (EC 3.4.21.62), including those derived from Bacillus (such as US 6,312,936 B1, US 5,679,630, US 4,760,025, US 7,262,042 and WO09/021867 the Bacillus lentus (Bacillus lentus) are described, alkalophilic Bacillus (B.alkalophilus), Bacillus subtilis (B. subtilis), Bacillus amyloliquefaciens (B. amyloliquefaciens), Bacillus pumilus (Bacillus pumilus) and Giemsa Bacillus Bacillus ( Bacillus gibsonii ) protease. (b) Trypsin-type or chymotrypsin-type proteases, such as trypsin (for example, trypsin of porcine or bovine origin), including Fusarium protease described in WO 89/06270 and WO 05/052161 and WO The chymotrypsin derived from Cellumonas described in 05/052146 . (c) Metalloproteases, including those derived from Bacillus amyloliquefaciens described in WO 07/044993A2. Preferred proteases include proteases derived from Bacillus gibsonii or B. lentus.

Suitable commercially available proteases include the following: Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme by Novozymes A/S (Denmark) ®, Neutrase®, Everlase® and Esperase® proteases sold under the trademarks Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® by Genencor International And Purafect OXP® protease; sold by Solvay Enzymes under the trademarks Opticlean® and Optimase®; protease available from Henkel/Kemira, namely BLAP (US 5,352,604 of the sequence shown in Figure 29, and has the following mutation: S99D +S101 R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I) and BLAP F49 ( BLAP with S3T+V4I+A194P+V199M+V205I+L217D), all from Henkel/Kemira; and KAP from Kao ( Bacillus alkalophilus subtilisin with mutation A230V+S256G+S259N).

Amylase. A preferred composition may include amylase. Suitable alpha-amylases include alpha-amylases of bacterial or fungal origin. Including chemically or genetically modified mutants (variants). Preferably, the alkaline α-amylase is derived from strains of Bacillus, such as Bacillus licheniformis , Bacillus amyloliquefaciens , Bacillus stearothermophilus , Bacillus subtilis Or other Bacillus ( Bacillus sp. ), such as Bacillus NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818), DSM 12368, DSMZ No. 12649, KSM AP1378 (WO 97/00324), KSM K36 Or KSM K38 (EP 1,022,334). Preferred amylases include: (a) the variants described in WO 94/02597, WO 94/18314, WO 96/23874 and WO 97/43424, especially the enzymes listed as SEQ ID NO. 2 in WO 96/23874 Variants with substitutions at one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243 , 264, 304, 305, 391, 408, and 444. (b) The variants described in USP 5,856,164 and WO 99/23211, WO 96/23873, WO 00/60060 and WO 06/002643, especially compared with the AA560 enzyme listed as SEQ ID No. 12 in WO 06/002643 Variants with one or more substitutions at the following positions: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, and 484 are preferably variants that also contain deletions of D183* and G184*. (c) and in WO of SEQ ID No.4 06/002643 (from Bacillus SP722 of the wild-type enzyme) exhibits at least 90% identity of the variant, in particular a deletion variant of the body and at a position 183,184, and WO The variant described in 00/60060, which is incorporated herein by reference. (d) A variant showing at least 95% identity with the wild-type enzyme from Bacillus sp. 707 (SEQ ID NO: 7 in US 6,093,562), especially a variant containing one or more of the following mutations: M202, M208, S255, R172 and/or M261. Preferably, the amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and/or R172Q. Particularly preferred are amylases containing M202L or M202T mutations. (e) The variant described in WO 09/149130 is preferably the same as SEQ ID NO: 1 or SEQ ID NO: 2 in WO 09/149130 (from the wild-type enzyme of Geobacillus Stearophermophilus ) Or its truncated version) showing at least 90% consistency of the variant.

Suitable commercially available α-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S, Bagsvaerd, Denmark) , KEMZYM® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor International Inc., Palo Alto, California) and KAM ® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitable amylases include NATALASE®, STAINZYME® and STAINZYME PLUS® and mixtures thereof.

Lipases. Preferably, the present invention comprises one or more lipases, including "first cycle lipases", such as those described in US Patent 6,939,702 B1 and US PA 2009/0217464. The preferred lipase is the first wash lipase. In an embodiment of the present invention, the composition includes a first washing lipase. The first washing lipase includes a polypeptide type lipase, and has an amino acid sequence that meets the following conditions: (a) It has at least 90% identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109 (B) Compared with the wild-type lipase, the surface of the three-dimensional structure within 15A of E1 or Q249 with a positively charged amino acid contains a substitution of a neutral or negatively charged amino acid; and ( c) include peptide addition at the C-terminus; and/or (d) include peptide addition at the N-terminus and/or (e) meet the following restrictions: i) include a negative amino acid at position E210 of the wild-type lipase Ii) A negatively charged amino acid is included in the region corresponding to positions 90-101 of the wild-type lipase; and iii) a neutral or negative amino group is included in the position corresponding to N94 of the wild-type lipase The acid and/or have a negative or neutral net charge in the region corresponding to positions 90-101 of the wild-type lipase. Preferably, it is a variant of wild-type lipase from Thermomyces lanuginosus and contains one or more of the T231R and N233R mutations. Wild-type sequence of Swissprot Accession No. Swiss-Prot O59952 (woolly repellent derived from thermophilic lanuginosus (Humicola pubescent)) of 269 amino acids (amino acids 23-291). Preferred lipases would include the lipases sold under the trade names Lipex® and Lipolex® and Lipoclean®.

Endoglucanases. Other preferred enzymes include microbial-derived endoglucanases, and exhibit endo-β-1,4-glucanase activity (EC 3.2.1.4), including those against Bacillus The members are endogenous bacterial polypeptides and mixtures thereof, which have a sequence that is at least 90%, 94%, 97%, and even 99% identical to the amino acid sequence SEQ ID NO: 2 in US7,141,403 B2. Suitable endoglucanases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).

Pectin lyase. Other preferred enzymes include pectin lyase sold under the trade names Pectawash®, Pectaway®, Xpect® and Mannaway® (all from Novozymes A/S, Bagsvaerd, Denmark) and Purabrite® (Genencor Mannanase sold by International Inc., Palo Alto, California).

Nuclease. The composition may include nuclease. Nucleases are enzymes capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids. The nuclease herein is preferably deoxyribonuclease or ribonuclease or functional fragments thereof. The functional fragment or part means the part of the nuclease that can catalyze the cleavage of the phosphodiester bond in the DNA backbone and is therefore the region of the nuclease protein that maintains catalytic activity. Therefore, it includes truncated but functional versions of enzymes and/or variants and/or derivatives and/or homologues that retain functionality.

The nuclease is preferably deoxyribonuclease, preferably selected from any one of the following categories and mixtures thereof: EC 3.1.21.x, where x=1, 2, 3, 4, 5, 6, 7, 8 or 9; EC 3.1.22.y, where y=1, 2, 4, or 5; EC 3.1.30.z, where z=1 or 2; EC 3.1.31.1.

Bleaching agent. The composition may preferably contain one or more bleaching agents. Suitable bleaching agents other than bleach catalysts include photobleach, bleach activators, hydrogen peroxide, hydrogen peroxide sources, preformed peracids and mixtures thereof. Generally speaking, when a bleaching agent is used, the composition of the present invention may contain about 0.1% to about 50% or even about 0.1% to about 25% of the bleaching agent or mixture of bleaching agents based on the weight of the target composition. Examples of suitable bleaching agents include: (1) Photofading agents, such as sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanine, dibenzopyran dye, thioxanthone and mixtures thereof; (2) Preformed peracids: Suitable preformed peracids include (but are not limited to) compounds selected from the group consisting of: preformed peroxyacids or their salts, usually percarboxylic acids and salts, peroxy Carbonic acid and salt, perimidic acid and salt, peroxymonosulfuric acid and salt (such as Oxone®) and mixtures thereof. A particularly preferred peroxy acid is phthalimino-peroxy-alkanoic acid, especially ε-phthalimino peroxycaproic acid (PAP). Preferably, the melting point of peroxyacid or its salt is in the range of 30°C to 60°C. (3) The source of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts, such as perboric acid (usually monohydrate or tetrahydrate), percarbonic acid, persulfuric acid, perphosphoric acid, persilic acid Sodium salt and mixtures thereof. When used, the inorganic perhydrate salt is usually present in an amount of 0.05 to 40% by weight, or 1 to 30% by weight, of all fabrics and household care products, and it is usually incorporated into such fabrics and in the form of coatable crystalline solids. Home care products. Suitable coatings include inorganic salts, such as alkali metal silicates, carbonates or borates or mixtures thereof, or organic materials, such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and (4) A bleach activator with R-(C=O)-L, where R is an alkyl group, optionally a branched chain, and when the bleach activator is hydrophobic, it has 6 to 14 carbon atoms, or 8 Up to 12 carbon atoms, which when the bleach activator is hydrophilic, has less than 6 carbon atoms or even less than 4 carbon atoms; and L is a leaving group. Examples of suitable leaving groups are benzoic acid and its derivatives, especially benzene sulfonate. Suitable bleach activators include dodecanoyloxybenzene sulfonate, decanoyloxybenzene sulfonate, decanoyloxybenzoic acid or its salt, sulfonic acid 3,5,5-trimethylhexoxybenzene Benzene, tetraacetylethylenediamine (TAED) and nonyloxybenzene sulfonate (NOBS). (5) Bleaching catalyst. The composition of the present invention may also include one or more bleaching catalysts capable of accepting oxygen atoms from peroxyacid and/or its salts and transferring the oxygen atoms to an oxidizable substrate. Suitable bleaching catalysts include (but are not limited to): iminium cations and polyions; iminium zwitterions; modified amines; modified amine oxides; N-sulfonylimine; N-phosphonylimine Amine; N-Amino-ketone; Thiadiazole dioxide; Perfluoroimine; Cyclic sugar ketone and α-amino-ketone and mixtures thereof. A particularly preferred catalyst is the acylhydrazone type, such as 4-(2-(2-((2-hydroxyphenylmethyl)methylene)-hydrazino)-2-oxoethyl)-4- Methyl chloride. (6) The composition may preferably include a catalytic metal complex. A preferred type of metal-containing bleach catalyst is a catalyst system containing transition metal cations (such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations) with established bleach catalytic activity.

If necessary, the composition herein can be catalyzed by a manganese compound. Such compounds and amounts are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,576,282. In some embodiments, no other oxidant source is present in the composition, and molecular oxygen from the air provides the oxidation source.

Known cobalt bleach catalysts suitable for use herein are described in, for example, U.S. 5,597,936; U.S. 5,595,967.

When present, the source of hydrogen peroxide/peracid and/or bleach activator is usually from about 0.1 to about 60% by weight, from about 0.5 to about 40% by weight, or even from about 0.6 to about 10% by weight based on fabrics and household care products. The amount of weight% is present in the composition. One or more hydrophobic peracids or precursors thereof can be used in combination with one or more hydrophilic peracids or precursors thereof.

Generally, the source of hydrogen peroxide and the bleach activator will be combined. The source of hydrogen peroxide and the amount of peracid or bleach activator can be selected so that the molar ratio of available oxygen (from the peroxide source) to peracid is 1:1 to 35:1, or even 2:1 to 10 :1. If formulated as a liquid detergent, the peroxide source and activator can be formulated with a pH jumping system (such as borate/sorbitol) at low pH (usually 3-5).

The laundry care composition of the present invention can be particularly used in chlorinated water, such as the water commonly found in most household water supplies. Alternatively, leuco-containing systems can be used in combination with other bleaching sources (such as electrolysis) and can be used in automated application systems.

Synergists. The composition may preferably include one or more synergists or synergist systems. When a synergist is used, the composition of the present invention will usually contain at least 1%, 2% to 60% of the synergist. The composition may preferably include a small amount of phosphate and/or zeolite, for example, 1 to 10 or 5 wt%. The composition may even be substantially free of strong synergists; substantially free of strong synergists means "no intentional addition" of zeolite and/or phosphate. Typical zeolite synergists include zeolite A, zeolite P, and zeolite MAP. A typical phosphate synergist is sodium tripolyphosphate.

Chelating agent. The composition preferably contains a chelating agent and/or a crystal growth inhibitor. Suitable molecules include copper, iron and/or manganese chelating agents and mixtures thereof. Suitable molecules include hydroxamic acid, amino carboxylate, amino phosphate, succinate, salts and mixtures thereof. Non-limiting examples of chelating agents suitable for use herein include ethylenediaminetetraacetate, N-(hydroxyethyl)ethylenediaminetetraacetate, nitrotriacetate, ethylenediamine Tetrapropionate, Triethylenetetramine Caproate, Diethylenetriamine Valerate, Ethanol Diglycinate, Ethylene Diamine (Methylene Phosphonate), Diethylene Triamine penta (methylene phosphonic acid) (DTPMP), ethylenediamine disuccinate (EDDS), hydroxyethane dimethylene phosphoric acid (HEDP), methylglycine diacetic acid (MGDA), two Ethylenetriaminepentaacetic acid (DTPA), its salts and mixtures thereof. Other non-limiting examples of chelating agents used in the present invention can be found in US Patent Nos. 7445644, 7585376 and 2009/0176684A1. Other chelating agents suitable for use in this article are the commercially available DEQUEST series and chelating agents from Monsanto, DuPont, and Nalco, Inc. Other suitable chelating agents include the pyridyl N-oxide type.

Fluorescent brightener. The composition preferably contains one or more fluorescent brighteners. Commercially available optical brighteners suitable for use in the present invention can be divided into subgroups, which include (but are not limited to) stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine, dibenzothiophene- 5,5-Dioxides, azoles, derivatives of 5-membered and 6-membered heterocyclic rings, and other miscellaneous reagents. Especially preferred brighteners are selected from: 2-(4-styryl-3-sulfophenyl)-2H-naphthol [1,2-d]triazole sodium, 4,4'-bis{[ (4-Anilino-6-(N-methyl-N-2-hydroxyethyl)amino-1,3,5-tris-2-yl))amino)stilbene-2-2-disulfon Disodium acid, 4,4'-bis{[(4-anilino-6-(N-𠰌linyl)-l,3,5-tris-2-yl)]amino}stilbene-2-2 Disodium'-disulfonate and disodium 4,4'-bis(2-sulfostyryl)biphenyl. Other examples of such brightening agents are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific non-limiting examples of optical brighteners suitable for use in the composition of the present invention are the optical brighteners identified in US Patent No. 4,790,856 and US Patent No. 3,646,015.

The preferred brightener has the following structure:

Suitable fluorescent brightener content includes a lower limit content of about 0.01, about 0.05, about 0.1 or even about 0.2 wt% to an upper limit content of 0.5 or even 0.75% by weight.

In one aspect, the brightener can be loaded onto the clay to form particles.

Preferably, all or predominantly (usually at least 50% by weight, at least 75% by weight, at least 90% by weight, at least 99% by weight) of the brightener is in the α-crystalline form. The very preferred brightener includes CI fluorescent brightener 260, which preferably has the following structure:

This may be particularly applicable because it also dissolves in cold water, for example below 30°C or 25°C or even 20°C.

Enzyme stabilizer. The composition may preferably include an enzyme stabilizer. Any conventional enzyme stabilizer can be used, for example, by the presence of water-soluble sources of calcium and/or magnesium ions that can provide such ions to enzymes in finished fabrics and home care products. In the case of an aqueous composition containing a protease, a reversible protease inhibitor (such as a boron compound including borate, or preferably 4-methanylphenylboronic acid, phenylboronic acid and its derivatives) or a compound (such as Calcium formate, sodium formate and 1,2-propanediol) to further improve stability.

Solvent system. The solvent system in the composition of the present invention may be a solvent system containing only water or a mixture containing organic solvents (without or preferably with water). Organic solvents

The composition may optionally contain an organic solvent. Suitable organic solvents include C _4-14 ethers and diethers, glycols, alkoxylated glycols, C ₆ -C ₁₆ glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched chain alcohols , Alkoxylated aliphatic branched chain alcohols, alkoxylated linear C ₁ -C ₅ alcohols, linear C ₁ -C ₅ alcohols, amines, C ₈ -C ₁₄ alkyl and cycloalkyl hydrocarbons and halogenated Hydrocarbons, and mixtures thereof. Preferred organic solvents include 1,2-propanediol, 2,3-butanediol, ethanol, glycerin, ethoxylated glycerin, dipropylene glycol, methyl propylene glycol and mixtures thereof. Other lower alcohols, C ₁ -C ₄ alkanolamines such as monoethanolamine and triethanolamine can also be used. There may be no solvent system, such as the anhydrous solid embodiment of the present invention, but it is more typically about 0.1% to about 98% by weight of the liquid detergent composition of the organic solvent, preferably at least about 1% to about 50% by weight %, more usually about 5% to about 25% by weight, or about 1% to about 10% by weight. These organic solvents can be used in combination with water, or they can be used without water.

Structured liquid : In some embodiments of the invention, the composition is in the form of a structured liquid. Such structured liquids can be internally structured, whereby the structure is formed by the main components (such as surfactant materials) and/or by the use of secondary components (such as polymers, clay and/or silicate materials) Provides a three-dimensional matrix structure and is externally structured for use as, for example, a thickener. The composition may include a structurant, preferably 0.01% to 5% by weight, 0.1% to 2.0% by weight of structurant. Examples of suitable structurants are provided in US2006/0205631A1, US2005/0203213A1, US7294611, US6855680. The structurant is usually selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, cellulosic materials, microcellulose, hydrophobically modified alkali Metal swellable emulsions (such as Polygel W30 (3VSigma)), biopolymers, sanxian gum, gellan gum, hydrogenated castor oil, hydrogenated castor oil derivatives (such as non-ethoxylated derivatives and mixtures thereof, specific In other words, substances selected from the group of hydrogenated castor oil and hydrogenated castor oil derivatives), microcellulose, hydroxyl functional crystalline materials, long-chain fatty alcohols, 12-hydroxystearic acid, clay and mixtures thereof. A preferred structurant is described in US Patent No. 6,855,680, which defines in detail suitable hydroxyl functional crystalline materials. Preferably it is hydrogenated castor oil. Some structurants have a linear structure system and have a range of aspect ratios. Another preferred structurant is based on cellulose and can be derived from a variety of sources, including biomass, wood pulp, citrus fiber, and the like.

The composition of the present invention may contain high melting point fatty compounds. The high melting point fatty compound suitable for use herein has a melting point of 25°C or higher and is selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives and mixtures thereof. This section is not intended to include such low melting point compounds. Non-limiting examples of high melting point compounds can be found in the International Cosmetic Ingredient Dictionary, Fifth Edition, 1993 and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992. When present, the high melting point fatty compound is preferably included in the composition at a content of 0.1% to 40%, preferably 1% to 30%, more preferably 1.5% to 16%, based on the weight of the composition. Improved conditioning benefits (such as smoothness during application to wet hair, softness and moisturization on dry hair) can be 1.5% to 8%.

Cationic polymer. The composition of the present invention may contain a cationic polymer. The concentration of the cationic polymer in the composition is usually in the range of 0.05% to 3%, in another embodiment 0.075% to 2.0%, and in another embodiment 0.1% to 1.0%. At the pH of the intended use of the composition, a suitable cationic polymer will have a cationic charge density of at least 0.5 meq/gm, in another embodiment, at least 0.9 meq/gm, in another embodiment, At least 1.2 meq/gm, in another embodiment, at least 1.5 meq/gm, but in one embodiment, it is also less than 7 meq/gm, which in another embodiment is less than 5 meq/gm, the pH value It will generally be in the range of pH 3 to pH 9, and in one embodiment, between pH 4 and pH 8. Herein, the "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. The average molecular weight of such suitable cationic polymers will generally be between 10,000 and 10 million, in one embodiment, between 50,000 and 5 million, and in another embodiment, between 100,000 and 300 million. Between ten thousand.

Cationic polymers suitable for the composition of the present invention contain cationic nitrogen-containing moieties such as quaternary ammonium or cationic protonated amine moieties. Any anionic counter ion can be used in combination with a cationic polymer, as long as the polymer remains soluble in water, the composition or the agglomeration phase of the composition, and as long as the counter ion is physically and chemically related to the basic composition of the composition. It is sufficient if it is compatible or does not improperly weaken product performance, stability or aesthetics in other ways. Non-limiting examples of such relative ions include halide (eg, chloride, fluoride, bromide, iodide), sulfate, and methylsulfate.

Non-limiting examples of such polymers are described in the CTFA Cosmetic Ingredient Dictionary edited by Estrin, Crosley, and Haynes, 3rd edition (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C. (1982)).

Other cationic polymers suitable for the composition include polysaccharide polymers; cationic guar gum derivatives; cellulose ethers containing quaternary nitrogen; synthetic polymers; copolymers of etherified cellulose, guar gum and starch. When used, the cationic polymer herein is soluble in the composition or soluble in the composition formed by the cationic polymer and anionic, amphoteric and/or zwitterionic surfactant components described above The composite reunion phase. The composite agglomerates of cationic polymers can also be formed from other charged materials in the composition.

其中R⁹⁵ 係選自由H、甲基及其混合物組成之群。Suitable cationic polymers are described in US Patent No. 3,962,418; No. 3,958,581; and US Publication No. 2007/0207109A1. Nonionic polymer. The composition of the present invention may include a nonionic polymer as a modifier. Polyalkylene glycols having a molecular weight exceeding 1000 are suitable for use herein. Substances with the following general formula are applicable:

Wherein R ⁹⁵ is selected from the group consisting of H, methyl and mixtures thereof.

The composition may include modifiers, and specifically, silicones. The conditioning agent suitable for the composition of the present invention usually contains water-insoluble, water-dispersible, non-volatile liquid, which forms emulsified liquid particles. The modifiers suitable for the composition are modifiers usually characterized by the following: silicone (such as silicone oil, cationic silicone, polysilicone, high refractive index silicone and polysilicone resin), organic regulator Oils (such as hydrocarbon oils, polyolefins, and fatty esters) or combinations thereof, or otherwise form a liquid, dispersed particle regulator in the aqueous surfactant matrix herein. Such regulators should be physically and chemically compatible with the basic components of the composition, and they should not improperly reduce product stability, aesthetics or performance in other ways.

The concentration of the modifier in the composition should be sufficient to provide the desired modulating advantage. Such concentrations can vary with the modifier, the desired modifier performance, the average size of modifier particles, the types and concentrations of other components, and other similar factors.

The concentration of the silicone regulator is usually in the range of about 0.01% to about 10%. Non-limiting examples of suitable silicone regulators and optional suspending agents for silicone are described in U.S. Reissue Patent No. 34,584, U.S. Patent No. 5,104,646; No. 5,106,609; No. 4,152,416; No. 2,826,551; No. 3,964,500; No. 4,364,837; No. 6,607,717; No. 6,482,969; No. 5,807,956; No. 5,981,681; No. 6,207,782; No. 7,465,439; No. 7,041,767; No. 7,217,777; US Patent Application No. 2007 /0286837A1; 2005/0048549A1; 2007/0041929A1; British Patent No. 849,433; German Patent No. DE 10036533, all of which are incorporated herein by reference; Chemistry and Technology of Silicones, New York : Academic Press (1968); General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76; Silicon Compounds, Petrarch Systems, Inc. (1984); and Encyclopedia of Polymer Science and Engineering, Volume 15, Second edition, pages 204-308, in John Wiley & Sons, Inc. (1989).

Organic conditioning oil. The composition of the present invention may also contain about 0.05% to about 3% of at least one organic conditioning oil as a conditioning agent, alone or in combination with other conditioning agents such as silicones (described herein). Suitable conditioning oils include hydrocarbon oils, polyolefins and fatty esters. Hygiene. The composition of the present invention may also contain components for delivering hygiene and/or odor advantages, such as one or more of the following: zinc ricinoleate, revanol, quaternary ammonium salts (such as Bardac ®), polyethyleneimine (such as Lupasol® from BASF) and its zinc complexes, silver and silver compounds, especially designed to slowly release Ag+ compounds or nanosilver dispersions.

Probiotics. The composition may include probiotics, such as those described in WO2009/043709.

Foam accelerator. If a high degree of foaming is required, the composition may preferably contain a foam accelerator. Suitable examples are C ₁₀ -C ₁₆ alkanolamides or C ₁₀ -C ₁₄ alkyl sulfates, which are preferably incorporated in a content of 1%-10%. C ₁₀ -C ₁₄ monoethanol and diethanolamide illustrate typical types of such foam promoters. It is also advantageous to use such foam boosters and highly foaming adjuvant surfactants such as the above-mentioned amine oxides, betaine and sultaine. If necessary, water-soluble magnesium and/or calcium salts (such as MgCl ₂ , MgSO ₄ , CaCl ₂ , CaSO ₄ and the like) can be added typically at a content of 0.1%-2% to provide additional foam and enhance grease migration In addition to effectiveness.

Foam inhibitors. Compounds used to reduce or inhibit foam formation can be incorporated into the composition of the present invention. Suds suppression may be of particular importance in so-called "high concentration cleaning programs" and front-load washing machines as described in US Patent Nos. 4,489,455 and 4,489,574. Various materials can be used as foam inhibitors, and the foam inhibitors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples of foam inhibitors include monocarboxylic fatty acids and their soluble salts, high molecular weight hydrocarbons (such as paraffins), fatty acid esters (such as fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (such as Stearyl ketone), N-alkylated amino tris, waxy hydrocarbons (preferably with a melting point below about 100°C), silicone foam inhibitors and secondary alcohols. Particularly suitable silicone foam inhibitors are based on diphenyl-containing silicones.

By weight, the silicone foam inhibitor is usually used in an amount of up to 2.0% of the detergent composition, but higher amounts can also be used.

Pearlescent agent. The pearlescent agent as described in WO2011/163457 can be incorporated into the composition of the present invention.

The pearlescent agent can be a crystalline or glassy solid, transparent or translucent compound capable of reflecting and refracting light to produce a pearlescent effect. Typically, pearlescent agents are crystalline particles that are insoluble in the composition into which they are incorporated. Preferably the pearlescent agent has a thin plate or spherical shape. The particle size of the pearlescent agent is usually less than 200 microns, preferably less than 100 microns, more preferably less than 50 microns. Inorganic pearlescent agents include aluminosilicate and/or borosilicate. It is preferably aluminosilicate and/or borosilicate that has been processed to have a very high refractive index, preferably silicon dioxide, metal oxide, aluminosilicate and/or boron coated with oxychloride Silicate. A more preferred inorganic pearlescent agent is mica, and even more preferred is a mica treated with titanium dioxide, such as BASF Mearlin Superfine.

Based on the weight of the composition, the composition may contain 0.005% to 3.0% by weight, preferably 0.01% to 1% by weight of 100% active pearlescent agent. Pearlescent agents can be organic or inorganic. The composition may include organic and/or inorganic pearlescent agents.

Organic pearlescent agent: When the composition contains an organic pearlescent agent, based on the weight of the composition, it contains 100% active organic pearlescent agent at an active level of 0.05% to 2.0% by weight, preferably 0.1% to 1.0% by weight. Suitable organic pearlescent agents include mono- and/or diesters of alkylene glycol, such as ethylene glycol distearate.

Inorganic pearlescent agent: In another embodiment, the composition may also include an inorganic pearlescent agent. When the composition includes an inorganic pearlescent agent, it contains 100% active inorganic pearlescent agent at an active level of 0.005 wt% to 1.0 wt%, preferably 0.01 wt% to 0.2 wt% of the composition. Suspended particles

In one embodiment, the composition further includes a plurality of suspension particles in an amount of about 0.01% to about 5% by weight, or about 0.05% to about 4% by weight, or about 0.1% to about 3% by weight. Examples of suitable suspended particles are provided in US Patent No. 7,169,741 and US Patent Publication No. 2005/0203213, the disclosures of which are incorporated herein by reference. These suspended particles may comprise a liquid core or a solid core. The detailed description of these liquid core and solid core particles and the description of the preferred particle size, particle shape, particle density and particle burst strength are described in US Patent Application No. 12/370,714, the disclosure of which is incorporated herein by reference in.

In a preferred embodiment, the particles can be any discrete and visually distinguishable forms of substances, including (but not limited to) (deformable) beads, encapsulants, polymeric particulate plastics, metals (such as foil materials, Flakes, glitter), (interfering) pigments, minerals (salt, rock, gravel, lava, glass/silica particles, talc), plant materials (such as nuclei or seeds, plant fibers, stems, stems, leaves or Root), solid and liquid crystals and the like. There may be different particle shapes, ranging from spherical to plate.

In one embodiment, the suspension particles may be gas or bubbles. In this embodiment, the diameter of each bubble may be about 50 to about 2000 microns and may be about 0.01 to about 5 vol% of the composition, or about 0.05% to about 4 vol% of the composition, or about 0.1 of the composition. % To about 3% by volume. Sunscreen

In one embodiment, the composition may also include a sunscreen.

As the term is used herein, "sunscreens" are substances that are added to materials to make the resulting system opaque. In a preferred embodiment, the sunscreen is Acusol, which is commercially available from Dow Chemicals. Acusol sunscreen is provided in liquid form at a certain percentage of solids. When supplied, the pH of Acusol sunscreen is in the range of 2.0 to 5.0 and the particle size is in the range of 0.17 to 0.45 μm. In a preferred embodiment, Acusol OP303B and 301 can be used.

In another embodiment, the sunscreen may be an inorganic sunscreen. Preferably, the inorganic sunscreen can be TiO ₂ , ZnO, talc, CaCO ₃ and combinations thereof. The composite sunscreen-microsphere material can be easily formed with a pre-selected specific gravity, so that there is very little material separation tendency.

Solubilizer : The composition can optionally contain an effective amount of solubilizer, that is, about 0% to 15%, or about 1% to 10%, or about 3% to about 6%, so that the composition is in the water phase Content. Solubilizers suitable for use in this article include anionic solubilizers, specifically, sodium xylene sulfonate, potassium xylene sulfonate and ammonium xylene sulfonate, sodium toluene sulfonate, potassium toluene sulfonate and toluene sulfonic acid Ammonium, sodium cumene sulfonate, potassium cumene sulfonate and ammonium cumene sulfonate and mixtures thereof are as disclosed in US Patent 3,915,903.

Antioxidant: The composition may optionally contain an antioxidant, which is present in the composition at about 0.001 to about 2% by weight. Preferably, the antioxidant is present at a concentration in the range of 0.01 to 0.08% by weight. Mixtures of antioxidants can be used.

Antioxidants are substances as described in Kirk-Othmer (Volume 3, Page 424) and In Ullmann's Encyclopedia (Volume 3, Page 91).

其中R為C₁ -C₂₂ 直鏈或分支鏈烷基，較佳為甲基或分支鏈C₃ -C₆ 烷基、C₁ -C₆ 烷氧基，較佳為甲氧基；R₁ 為C₃ -C₆ 分支鏈烷基，較佳為第三丁基；x為1或2。位阻酚化合物為具有此式之烷基化酚之較佳類型。此類型之較佳位阻酚化合物為3,5-二-第三丁基-4-羥基甲苯(BHT)。An antioxidant used in the present invention is alkylated phenol, which has the following general formula:

Wherein R is C ₁ -C ₂₂ linear or branched chain alkyl, preferably methyl or branched C ₃ -C ₆ alkyl, C ₁ -C ₆ alkoxy, preferably methoxy; R ₁ It is a C ₃ -C ₆ branched chain alkyl group, preferably a tertiary butyl group; x is 1 or 2. The hindered phenol compound is a preferred type of alkylated phenol having this formula. The preferred hindered phenol compound of this type is 3,5-di-tert-butyl-4-hydroxytoluene (BHT).

In addition, the antioxidant used in the composition can be selected from the group consisting of: α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, ethoxyquin, 2,2,4-trimethyl -1,2-dihydroquinoline, 2,6-di-tertiary butyl hydroquinone, tertiary butyl hydroxyanisole, lignosulfonic acid and its salts, and mixtures thereof. It should be noted that ethoxyquin (1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline) is commercially available under the trade name Raluquin ^TM by the Raschig ^TM company.

Other types of antioxidants that can be used in the composition are 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox ^TM ) and 1,2-benzisothiazoline-3- Ketone (Proxel GXL ^TM ).

其中R₁ 及R₂ 各自獨立地為烷基或R₁ 及R₂ 可共同形成C₅ -C₆ 環狀烴基部分；B不存在或為CH₂ ；R₄ 為C₁ -C₆ 烷基；R₅ 為氫或-C(O)R₃ ，其中R₃ 為氫或C₁ -C₁₉ 烷基；R₆ 為C₁ -C₆ 烷基；R₇ 為氫或C₁ -C₆ 烷基；X為-CH₂ OH或-CH₂ A，其中A為包含氮之單元、苯基或經取代之苯基。較佳包含氮之A單元包括胺基、N-吡咯啶基、N-哌啶基、N-𠰌啉基、N-哌𠯤基及其混合物。Another antioxidant that can be used in the composition is benzofuran or benzopyran derivative, which has the following formula:

Wherein R ₁ and R ₂ are each independently an alkyl group or R ₁ and R ₂ can jointly form a C ₅ -C ₆ cyclic hydrocarbon group part; B does not exist or is CH ₂ ; R ₄ is a C ₁ -C ₆ alkyl group; R ₅ is hydrogen or -C(O)R ₃ , wherein R ₃ is hydrogen or C ₁ -C ₁₉ alkyl; R ₆ is C ₁ -C ₆ alkyl; R ₇ is hydrogen or C ₁ -C ₆ alkyl ; X is -CH ₂ OH or -CH ₂ A, where A is a nitrogen-containing unit, phenyl or substituted phenyl. Preferably, the nitrogen-containing A unit includes an amino group, N-pyrrolidinyl, N-piperidinyl, N-pyrolinyl, N-piperidinyl, and mixtures thereof.

Antioxidants can also be used, such as tocopherol sorbate, butylated hydroxybenzoic acid and its salts, gallic acid and its alkyl esters, uric acid and its salts, sorbic acid and its salts, and dihydroxyfumaric acid and its salts salt. In one aspect, the best type of antioxidant used in the composition is 3,5-di-tert-butyl-4-hydroxytoluene (BHT), α-tocopherol, β-tocopherol, γ- Tocopherol, delta-tocopherol, 1,2-benzisothiazolin-3-one (Proxel GXL ^TM ) and mixtures thereof.

The cleaning composition of the present invention may also contain an antibacterial agent. Cationic active ingredients may include (but are not limited to) n-alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, dialkyl dimethyl quaternary ammonium compounds (such as Didecyl dimethyl ammonium chloride), N,N-didecyl-N-methyl-poly(oxyethyl) ammonium propionate, dioctyl didecyl ammonium chloride, including quaternary substances (Such as benzethonium chloride and quaternary ammonium compounds with inorganic or organic counter ions (such as bromine)), carbonates or other moieties including dialkyl dimethyl ammonium carbonate, and antimicrobial amines, such as gluconic acid Chlorhexidine Gluconate, PHMB (polyhexaformin), salts of biguanides, substituted biguanide derivatives, organic salts of compounds containing quaternary ammonium or inorganic salts of compounds containing quaternary ammonium or mixture.

Packaging. Any conventional packaging can be used and the packaging can be completely or partially transparent so that consumers can see the color of the laundry care composition, which can be provided or contributed by the color of the dye of the present invention. Some or all packages may include UV absorbing compounds.

When in liquid form, the laundry care composition of the present invention can be aqueous (usually higher than 2% by weight or even higher than 5 or 10% by weight total water, up to 90 or up to 80% by weight or 70% by weight total water) or Non-aqueous (usually less than 2% by weight total water content). Typically, the composition of the present invention will be in the form of an aqueous solution or a uniform dispersion or suspension of surfactants, sunscreen dyes, and some optional other ingredients (some of which are usually in solid form). The surfactants , Shading dyes and optional other ingredients have been combined with the general liquid components of the composition (such as non-ionic liquid alcohol ethoxylates, aqueous liquid carriers and any other general liquid optional ingredients). Such solutions, dispersions or suspensions will be acceptably phase stable. When in liquid form, the laundry care composition of the present invention preferably has 1 to 1500 centipoise (1-1500 mPa×s) at 20s-1 and 21°C, more preferably 100 to 1000 centipoise (100-1000 mPa) ×s) and the best viscosity is 200 to 500 centipoise (200-500 mPa×s). The viscosity can be measured by conventional methods. The flat steel shaft can be used with a diameter of 40 mm and a gap of 500 µm, and the viscosity can be measured with the AR 550 rheometer from TA instruments. The high shear viscosity at 20s-1 and the low shear viscosity at 0.05-1 can be obtained by scanning the logarithmic shear rate from 0.1-1 to 25-1 at 21°C in 3 minutes. The better rheology described therein can be achieved using existing internal structures with detergent ingredients or using external rheology modifiers. More preferred laundry care compositions, such as detergent liquid compositions, have a high shear rate viscosity of about 100 to 1500 cps, more preferably 100 to 1000 cps. A unit dose laundry care composition, such as a detergent liquid composition, has a high shear rate viscosity of 400 to 1000 cp. Laundry care compositions, such as laundry softening compositions, generally have a high shear rate viscosity of 10 to 1000, more preferably 10 to 800 cp, and most preferably 10 to 500 cp. The hand wash composition has a high shear rate viscosity of 300 to 4000 cp, more preferably 300 to 1000 cp.

The liquid composition, preferably the laundry care composition herein, can be prepared by combining its components in any suitable order and mixing (e.g. stirring) the resulting combination of components to form a phase-stable liquid laundry care composition. In a method for preparing such compositions, the formation contains at least most or even substantially all of the liquid components (such as non-ionic surfactants, non-surface-active liquid carriers, and other optional liquid components) The liquid matrix in which the liquid components are fully blended into the liquid combination by shearing and stirring. For example, a mechanical stirrer can be effectively used for rapid stirring. While maintaining shear and stirring, substantially all anionic surfactants and solid form components can be added. Continue to stir the mixture and extend this time as needed to form a solution or a uniform dispersion of insoluble solid particles in the liquid phase. After adding some or all of the solid form material to this stirred mixture, incorporate any particles of enzyme material to be included (e.g., enzyme pellets). As a variation of the composition preparation procedure described above, one or more solid components can be added to the stirred mixture in the form of a solution or a particle slurry premixed with a smaller portion of one or more liquid components. After adding all the composition components, continue to stir the mixture for a period of time to form a composition with the desired viscosity and phase stability characteristics. Typically, this will involve agitation for a period of about 30 to 60 minutes.

It has been found that the leuco colorant of the present invention is suitable for liquid laundry care compositions with a wide pH range. For example, it has been found that the leuco colorant of the present invention is suitable for liquid laundry care compositions having a pH value greater than or equal to 10. It has also been found that the leuco colorant of the present invention is suitable for liquid laundry care compositions having a pH value of less than 10. Therefore, the leuco colorant is stable in a laundry care composition having a pH value greater than or equal to 10 and less than or equal to 10.

Pouch. In a preferred embodiment of the present invention, the composition is provided in unitized dosage form, in the form of a lozenge or preferably as a liquid contained in a water-soluble film called a bag or container. Solid (optionally granular)/gel/slurry form. The composition can be encapsulated in a single-compartment or multi-compartment bag. The multi-compartment bag is described in more detail in EP-A-2133410. When the composition is present in a multi-compartment bag, the composition of the present invention may be located in one or two or more compartments, so the dye may be present in one or more compartments, optionally in all compartments . Non-shading dyes or pigments or other aesthetic products can also be used in one or more compartments. In one embodiment, the composition is present in a single compartment of a multi-compartment bag.

The preferred film material is a polymeric material. As known in the art, film materials can be obtained, for example, by casting, blow molding, extrusion or blow extrusion of polymeric materials. Preferred polymers, copolymers or their derivatives suitable for use as bag materials are selected from polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxide, acrylamide, acrylic acid, cellulose, cellulose ether, and cellulose ester , Cellulose amide, polyvinyl acetate, polycarboxylic acid and salt, polyamino acid or peptide, polyamide, polypropylene amide, maleic acid/acrylic acid copolymer, polysaccharide (including starch and Gelatin), natural gums (such as xanthan gum and carragum). More preferably, the polymer is selected from polyacrylate and water-soluble acrylate copolymer, methyl cellulose, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose It is selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol copolymer, hydroxypropyl methyl cellulose (HPMC) and combinations thereof. Preferably, the polymer (such as PVA polymer) content in the bag material is at least 60%. The polymer may have any weight average molecular weight, preferably about 1000 to 1,000,000, more preferably about 10,000 to 300,000, and more preferably about 20,000 to 150,000. Mixtures of polymers can also be used as bag materials. Depending on the application of the compartment or bag and the required application, this can be beneficial for controlling the mechanical and/or dissolution characteristics of the compartment or bag. Suitable mixtures include, for example, mixtures in which the water solubility of one polymer is higher than that of the other polymer and/or the mechanical strength of one polymer is higher than that of the other polymer. Mixtures of polymers with different weight average molecular weights are also suitable, such as mixtures of PVA or copolymers thereof having a weight average molecular weight of about 10,000-40,000, preferably about 20,000, and a mixture of polymers having a weight average molecular weight of about 100,000 to 300,000, preferably about 150,000 The weight average molecular weight of PVA or its copolymer mixture. Herein, the polymer blend composition is also suitable, for example, including a hydrolytically degradable and water-soluble polymer blend such as polylactide and polyvinyl alcohol by mixing polylactide and polyethylene The alcohol is obtained and typically contains about 1% to 35% by weight of polylactide and about 65% to 99% by weight of polyvinyl alcohol. Here, it is preferable to use about 60% to about 98% hydrolyzed polymer, preferably about 80% to about 90% hydrolyzed polymer to improve the dissolution characteristics of the material.

Naturally, different film materials and/or films of different thicknesses can be used to make the compartment of the present invention. The benefit of choosing different films is that the resulting compartments can exhibit different solubility or release characteristics.

The best film materials are PVA films known as MonoSol product numbers M8630, M8900, and H8779, the film materials described in US 6 166 117 and US 6 787 512, and PVA films with corresponding solubility and deformability characteristics.

The film material herein may also contain one or more additive components. For example, it can be beneficial to add plasticizers such as glycerin, ethylene glycol, diethylene glycol, propylene glycol, sorbitol, and mixtures thereof. Other additives include functional detergent additives to be delivered to the clean water, such as organic polymeric dispersants.

Solid form. As mentioned previously, the laundry care composition may be in solid form. Suitable solid forms include lozenges and granular forms, such as granular particles, flakes or plates. Various techniques for forming detergent compositions in such solid forms are well known in the art and can be used herein. In one aspect, for example, when the composition is in the form of granular particles, the leuco colorant is provided in the form of particles, optionally including other but not all components of the laundry detergent composition. The colorant particles are combined with one or more other particles containing the remaining components of the laundry detergent composition. In addition, the colorant (optionally including other but not all components of the laundry care composition) may be provided in an encapsulated form, and the sunscreen dye encapsulant is combined with particles containing substantially the remaining components of the laundry care composition.

Method of use. The composition of the present invention prepared as described above can be used to form an aqueous cleaning/treatment solution for washing/treatment of fabrics. Generally, an effective amount of such a composition is added to water, such as in a conventional automatic fabric washing machine, to form such an aqueous washing solution. Next, the resulting aqueous cleaning solution is brought into contact with the fabric to be washed/treated with it (usually under stirring). The liquid detergent composition herein in an effective amount added to water to form an aqueous washing solution may comprise an amount sufficient to form about 500 to 7,000 ppm of the composition in the aqueous washing solution, or will provide about 1,000 to about 1,000 to 7,000 ppm in the aqueous washing solution. 3,000 ppm of the laundry care composition in this article.

Typically, the washing solution is formed by contacting the laundry care composition with clean water in such an amount, so that the concentration of the laundry care composition in the washing solution is higher than 0 g/l to 5 g/l, or from 1 g/l, which is to 4.5 g/l, or to 4.0 g/l, or to 3.5 g/l, or to 3.0 g/l, or to 2.5 g/l, or even to 2.0 g/l, or even to 1.5 g/l. The method of washing fabrics or textiles can be carried out in a top-loading or front-loading automatic washing machine, or can be used for hand washing laundry applications. In these applications, the formed cleaning solution and the concentration of the laundry detergent composition in the cleaning solution are the cleaning solution and concentration of the main cleaning cycle. When determining the volume of the cleaning solution, do not include any input water during any optional flushing step.

The cleaning fluid may contain 40 liters or less of water, or 30 liters or less, or 20 liters or less, or 10 liters or less, or 8 liters or less, or even 6 liters or less of water. The cleaning fluid may contain more than 0 to 15 liters, or from 2 liters and up to 12 liters, or even 8 liters of water. Usually, 0.01 kg to 2 kg of fabric per liter of washing liquid is added to the washing liquid. Generally, 0.01 kg, or 0.05 kg, or 0.07 kg, or 0.10 kg, or 0.15 kg, or 0.20 kg, or 0.25 kg of fabric per liter of cleaning solution is injected into the cleaning solution. Optionally make 50 g or less, or 45 g or less, or 40 g or less, or 35 g or less, or 30 g or less, or 25 g or less, or 20 g or more Little, or even 15 g or less, or even 10 g or less of the composition is contacted with water to form a cleaning liquid. Such compositions are usually used at a concentration of about 500 ppm to about 15,000 ppm in the solution. When the cleaning solvent is water, the water temperature is usually in the range of about 5°C to about 90°C and in the case of including fabrics, the water to fabric ratio is usually about 1:1 to about 30:1. Generally, the pH of the cleaning liquid containing the laundry care composition of the present invention is 3 to 11.5.

In one aspect, such a method is disclosed, which comprises the following steps: optionally washing and/or rinsing the surface or fabric, contacting the surface or fabric with any composition disclosed in this specification, and then optionally washing And/or rinse the surface or fabric, and optional drying step.

The drying of such surfaces or fabrics can be achieved by any of the common methods used in domestic or industrial situations. The fabric can include any fabric that can be washed under normal consumer or institutional conditions. The present invention is applicable to cellulosic substrates. In some aspects, it is also applicable to synthetic textiles (such as polyester and nylon) and Treatment of mixed fabrics and/or fibers including synthetic and cellulose fabrics and/or fibers. Examples of synthetic fabrics are polyester, nylon, and these materials can be present in the mixture together with cellulosic fibers (such as polyester cotton fabric). The pH of the solution is usually 7 to 11, more usually 8 to 10.5. The composition is usually used at a concentration of 500 to 5,000 ppm in the solution. The water temperature is usually in the range of about 5°C to about 90°C. The water to fabric ratio is usually about 1:1 to about 30:1.

Therefore, in the third embodiment, the present invention provides a method of processing textiles. The method preferably comprises the following steps (i) treating the textile with an aqueous solution containing the leuco composition as described herein, (ii) optionally washing the textile, and (iii) drying the textile. In one aspect, the present invention provides a method for treating textiles, which comprises the following steps: (i) treating the textiles with an aqueous solution containing a leuco composition as described herein, the aqueous solution containing 10 ppb to 5000 ppm At least one leuco compound and 0.0 g/L to 3 g/L of surfactant; (ii) optional washing; and (iii) drying textiles. The leuco composition used in this method can be any of the leuco composition described herein. In addition, the aqueous solution used in the method can be produced by directly adding the leuco composition to the aqueous medium or by adding the laundry care composition containing the leuco composition to the aqueous medium. Test Methods

The fabric sample used in the test method in this article is obtained from Testfabrics, Inc. West Pittston, PA, and is 100% cotton, type 403 (cut into 2”×2”) and/or type 464 (cut into 4 ''×6''), and unbrightened multi-fiber fabrics, especially type 41 (5 cm×10 cm).

All reflectance spectra and color measurements (including L*, a*, b*, K/S) and whiteness index (WI CIE) values on the dried fabric samples are obtained by using one of four spectrophotometers: (1 ) Konica-Minolta 3610d reflection spectrophotometer (Konica Minolta Sensing Americas, Inc., Ramsey, NJ, USA; D65 irradiation, 10° observer, excluding UV light), (2) LabScan XE reflection spectrophotometer (HunterLabs, Reston, VA; D65 irradiation, 10° observer, excluding UV light), (3) Color-Eye® 7000A (GretagMacbeth, New Windsor, NY, USA; D65 light, excluding UV), or (4) Color i7 Spectrophotometer (X-rite, Inc., Grand Rapids, MI, USA; D65 light, excluding UV).

Unless otherwise indicated, when the fabric is irradiated, the specified fabric after drying is equipped with Atlas Xenon Fade-OmeterCi3000+ (Atlas Material) equipped with S-type borosilicate internal (part number 20277300) and external (part number 20279600) filters. Testing Technology, Mount Prospect, Illinois, USA), exposed to simulated sunlight at a irradiance of 0.77 W/m ² at 420 nm, set to 37℃ maximum cabinet temperature, 57℃ maximum blackboard temperature (BPT blackboard geometry ) And 35% RH (relative humidity). Unless otherwise indicated, radiation continues for the duration stated. I. Method for measuring the efficiency of the leuco composition of the cleaning solution

Before use, the cotton sample (type 464) was stripped by washing twice with a heavy-duty liquid laundry detergent (1.55 g/L in an aqueous solution) without brightener at 49°C. Prepare concentrated stock solutions of each leuco composition to be tested in a solvent selected from ethanol or 50:50 ethanol: water, preferably ethanol.

Using Konica-Minolta 3610d reflection spectrophotometer, measure all L*, a*, b* and whiteness index (WI CIE) values of cotton fabric on the dry sample.

The substrate cleaning solution was prepared by dissolving AATCC Heavy Duty Liquid Laundry Cleaner (5.23 g/1.0 L) without brightener in deionized water. Four samples of stripped cotton were weighed together and placed in a 250 mL Erlenmeyer flask with two pieces of 10 mm glass marble. For each washing solution to be tested, a total of three such flasks were prepared. Add the leuco-conjugate raw material to the substrate washing solution to obtain a leuco-conjugate cleaning solution with the required cleaning concentration of 2.00×10 ^-6 equivalents/liter.

An aliquot of this washing solution sufficient to provide a 10.0:1.0 liquid:fabric (w/w) ratio was placed in each of three 250 mL Erlenmeyer flasks. Add 1000 gpg of raw material hardness solution to each flask to obtain a final clean hardness of 6 gpg (3:1 Ca:Mg).

Place the flask in a Model 75 manual shaker (Burrell Scientific, Inc., Pittsburg, PA) and stir for 12 minutes at the maximum setting, then remove the cleaning solution by suction, and add the cleaning solution equivalent to the one used The volume of the volume of the solution (0 gpg). Add 1000 gpg raw material hardness solution to each flask to obtain a final rinse hardness of 6 gpg (3:1 Ca:Mg), and then stir for 4 minutes. The rinsing solution was removed by suction. The fabric sample was spin-dried (Mini Countertop Rotary Dryer, The Laundry Alternative Inc., Nashua, NH) for 1 minute, and then placed in a food dehydrator set at 135°F in the dark Dry for 2 hours. After the drying process, the samples can be stored in the dark or exposed to light for different amounts of time, and then the properties of the fabric can be measured.

Because the habits of consumers all over the world vary greatly, the method used must realize the possibility of measuring the advantages of leuco compounds across various conditions. One such condition is exposure to light after drying. Some leuco compounds show less benefit under dark storage than under light storage, so each leuco compound must be tested under two sets of conditions to determine the best benefit. Therefore, Method I includes exposing the drying fabric to simulated sunlight for various incremental times, then obtaining a measurement value, and setting the LCE value to the maximum value obtained from the exposure time set described below. A. Dark conditions after drying

After drying, the fabric was stored in the dark at room temperature between each measurement time point. After the end of the two-hour drying cycle, the cotton fabric L*, a*, b* and whiteness index (WI CIE) values were measured at time t=0, 6, 24, and 48 hours. At each time point t, obtain the average value of 12 samples (three flasks, each flask has four samples) produced by each leuco colorant to achieve the L*, a*, b* and WI CIE Sample value.

In order to obtain the L*, a*, b* and whiteness index (WI CIE) values of the control treatment, repeat the above procedure as described with the following exceptions: (1) Use AATCC weight without brightener in deionized water Load the liquid laundry detergent (5.23 g/1.0 L) to prepare a reference substrate cleaning solution, and (2) obtain the average value of 12 samples of the reference substance measured after the drying cycle to reach L*, a* The sample values of, b* and WI CIE, and the control value at t=0 is also used as the control value at t=6, 24, and 48 hours.

Use the following formula to calculate the leuco colorant efficiency (LCE) of the leuco colorant in the laundry care formulation based on the data collected at each time point t: LCE _t = DE* = ((L* _c -L* _s ) ² + (a* _c -a* _s ) ² + (b* _c -b* _s ) ² ) ^1/2 where the subscripts c and s respectively refer to the control substance, that is, the AATCC heavy-duty liquid without brightener Fabrics and samples washed in laundry detergents, that is, fabrics washed in laundry care formulations containing leuco colorants, where the value used to calculate LCE _t is the corresponding time point t (0, 6, 24 or 48 hours) The value of time.

Obtain the average value of the WI CIE value of 12 samples (three flasks, each flask has four samples) produced by each washing solution, and use the following formula to calculate the change in whiteness index after washing: ΔWI = WI CIE (after washing)-WI CIE (before washing)

There will be independent values for laundry care formulations (ΔWI _sample ) and AATCC HDL (ΔWI _control ) without brightener. The whiteness change between the two formulations is given by: δΔWI= ΔWI _sample -ΔWI _control B. Light condition after drying

After drying, the designated cotton fabric is exposed to simulated sunlight for 15 minutes, 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 120 minutes and 240 minutes. After each exposure period, measure the L*, a*, b* and whiteness index (WI CIE) values of the cotton fabric on the sample. The calculation of the LCE and ΔWI values at each exposure time point is as described in Method IA above, and the LCE and ΔWI values of the sample and the comparative laundry care formulation are set to the maximum obtained from the set of exposure times listed value. II. A method for determining the relative chrominance (AATCC compared with the control) of

The relative chromaticity transferred from the leuco colorant to the cotton fabric treated according to Method I described above is determined as follows. a) Obtain the average value of a* and b* of 12 samples from each solution. Use the following formula to determine Δa* and Δb*: Δa* = a* _s -a* _c and Δb* = b* _s -b * _c where the subscripts c and s refer to fabrics washed in AATCC Heavy Duty Liquid Cleaner (control) without brighteners and fabrics washed in laundry care formulations (samples) containing leuco colorants, respectively . b) If the absolute values of Δa* and Δb* are both <0.25, relative chromaticity (RHA) is not calculated. If any one of the absolute values of Δa* or Δb* > 0.25, use one of the following formulas to determine RHA: RHA = ATAN2(Δa*,Δb*), for Δb* > 0 RHA = 360 + ATAN2( Δa*,Δb*), for Δb* ＜ 0

The relative chromaticity at each time point can be calculated, and the data is collected in the dark after drying or light after drying. Any of these points can be used to satisfy the claimed requirements. III. Method for measuring the surface tension value of leuco colorant and its oxidized form

The material to be tested is the leuco colorant according to the present invention, or a dye representing the second colored state of the leuco colorant (for example, triarylmethane dye). A total of 250-255 mg of the material to be tested is weighed into a 4 ounce glass bottle and 50.0 mL of deionized water (Barnstead B-Pure System, approximately 17.27 ohm) and a magnetic stir bar are added. Cover the glass bottle, place it on a magnetic stirring plate and stir the mixture at 22.0°C for one hour. Subsequently, the stirring was stopped and the mixture was left undisturbed for one hour. At the end of this time, 10.0 mL of the solution was aspirated into the syringe, and the syringe was then equipped with a glass fiber Acrodisc® filter which filters the aliquot into a 20 mL scintillation vial. A VWR LabMax pipette was used to pipette 45.0 microliters of the filtered solution into each of the eight independent wells of the 96-well plate. The solution was tested with a Kibron Delta 8 surface tensiometer at about 22.0°C and the average value of eight measured copies was reported as the surface tension value (mN/m). Example 1

A measurement of the tendency of leuco colorants to increase the whiteness of aging garments compared to clean new garments.

Leuco Colorants 1 and 2 were used for testing to determine the extent to which leuco compounds provide improved whiteness to consumer-sourced aging cotton fabrics and clean, stripped new cotton fabrics. The structure of the tested leuco colorant is shown below.

Leuco Colorant 1 (a+b=0) and Leuco Colorant 2 (a+b=2.8; the sum of all a+b=5.6)

For the stripped cotton fabric, the test was performed according to method IA as disclosed herein, with pattern 403 instead of pattern 464. Next, use a sample of aged white T-shirt fabric cut from consumer sources (St. Vincent DePaul 4”×6” T-shirt sample, heavily contaminated; purchased from J&R Coordinating Services, Cincinnati, OH, USA). The stripped cotton was subjected to the test procedure again, in which the sample of the T-shirt had the L*, a*, b* and WI CIE values as indicated in Table 1 below before washing. When testing aged white T-shirts from consumer sources, only two copies were placed in each cleaning bottle. Table 1. Average values of aging cotton T-shirts from consumers before washing

For the calculation in each case, use the WI CIE value measured at 2, 24 and 48 hours after drying, and calculate the stripped cotton fabric and consumers washed in the composition according to Method IA according to the equation provided in the method The source of the whiteness index change (ΔWI) of the aged white T-shirt fabric.

^a 100%棉花，型式403，Test Fabrics, Inc.，經剝離。^b 消費者來源之100%棉花白色T恤。The whiteness change caused by the leuco colorant contained in the cleaning solution is the same in the two cleaning agent formulations (control (without leuco colorant) and sample (with leuco colorant)). The whiteness index of the fabric is changed, and it is calculated by the equation provided in the method. The results of the cleaning test are shown in Table 2 below. Table 2. The bleaching rate of aging consumer cotton apparel compared to clean cotton

^a 100% cotton, type 403, Test Fabrics, Inc., stripped. ^b 100% cotton white T-shirt from consumers.

隱色著色劑J (平均值a+b ≈ 2.5；所有a + b之總和 ≈ 5.0)The data in Table 2 shows that the leuco colorant containing EO and PO oxyalkylene moieties provides whiteness deviation from new, clean cotton to aging consumer cotton, which is always greater than self-contained only with EO oxygen. The offset obtained by the leuco colorant part of the alkylene unit. This means that the use of this type of leuco colorant (for example, 2 ) will provide aging cotton with the same whiteness benefits as leuco compounds with only EO-based alkylene groups (for example, 1 ) without compromising the color of new cotton garments Completeness. Therefore, the inventive leuco colorant of the present invention provides consumers with obvious advantages, effectively depositing it in places where it is needed (easy to show yellowed aging cotton) while avoiding unnecessary or no color adjustment in new, clean Deposited on the fabric. Example 2

Leuco Colorant J (average a+b ≈ 2.5; the sum of all a + b ≈ 5.0)

Divide a variety of different cotton fabrics (Testfabrics, Inc. West Pittston, PA; 100% cotton, cut into 4"×6") into two equivalent sets and test them as they are, except that the additional stripping is described below The second set of the sample type number 403 (CW120 cotton, cut into 4”×4”; a different batch number from the first set) and added to the test set. Wash one set in a heavy-duty liquid cleaner without leuco colorant (formulation A) and wash the other set in the same cleaner with leuco colorant J (formulation B). Use a 5,300 ppm heavy-duty liquid detergent formulation, at a ratio of 12:1 liquid to fabric, in city water (approximately 6 gpg, 3:1 Ca:Mg) for each wash for 12 minutes, the liquid detergent formulation The composition of the material is provided in Table 3 below. At a ratio of 12:1 liquid to fabric, rinse with city water for four minutes. Then, the fabric was air-dried in the dark at room temperature for 48 hours. Table 3. Heavy-duty liquid detergent formulations A and B

Using a CM3610d spectrophotometer (Konica Minolta, Ramsey, NJ; D65 irradiation, 10° observer, excluding UV light), before washing and 48 hours after washing, measure the L*, a of the cotton fabric on a dry sample *, b* and whiteness index (WI CIE) value. Obtain the average value of the WI CIE value of the duplicate samples produced by each laundry care formulation and use the following formula to calculate the whiteness index change after washing: ΔWI = WI CIE (after washing)-WI CIE (before washing)

The whiteness change caused by the leuco coloring agent J contained in the cleaning solution is obtained by comparing the whiteness index changes of the same type number fabrics cleaned in the two detergent formulations A and B, and is obtained by the following formula Calculation: δΔWI _CIE = ΔWI (cleaning agent B)-ΔWI (cleaning agent A)

The results of the fabric are listed below, and the value of δΔWI _CIE obtained is used for numerical organization. The consistency and results of the tested fabrics are provided in Table 4 below. Table 4. Values of δΔWI _CIE obtained for various standard cotton fabrics

It should be noted that when washed in two detergents, the whiteness value varies widely depending on the specific type of cotton fabric used in the test. This is also true for the same cotton type number that meets the following conditions: one of which has been washed with AATCC heavy duty liquid laundry detergent (1.55 g/L in an aqueous solution) at 49°C without brightener before use It was peeled twice (produced δΔWI CIE value of 1.93), and the other was not peeled (produced δΔWI CIE value of 0.72). This indicates that the established detergent formulations used by consumers will encounter textiles that represent multiple possibilities, and the way the formulations act on some textiles will generally be significantly different from other textiles. These differences can be found by routine experiments, as shown by the above data. Example 3

The fully oxidized forms of leuco colorants 1 and J from Examples 1 and 2, respectively, were deposited via a cleaning cycle on a Type 403 cotton sample. The oxidized form of the leuco colorant J was also deposited through the washing cycle on the aged white T-shirt fabric of consumer origin as described above. The fabric samples are made in Atlas Xenon Fade-OmeterCi3000+ (Atlas Material Testing Technology, Mount Prospect, Illinois, USA) equipped with S-type borosilicate internal (part number 20277300) and external (part number 20279600) filters Exposure to simulated sunlight with 0.77 W/m ² irradiance at 420 nm to test the degree of photofading of fabric samples, set at 37℃ maximum cabinet temperature, 57℃ maximum blackboard temperature (BPT blackboard geometry) and 35% RH (relative humidity). The exposure of the Type 403 fabric lasts for 30 minutes and 120 minutes; the exposure of the aged white T-shirt from consumers lasts for 120 minutes. After 30 and 120 minutes of irradiation, the fading of leuco colorant J was less than that of leuco colorant 1 . After 120 minutes, the fading of the leuco colorant J on the clean fabric and the aged white T-shirt from the consumer was similar. Example 4

。 將12.45公克4-乙醯胺基苯甲醛及苯胺-2,4(用平均2個EO及4個PO烷氧基化之苯胺)添加至配備有加熱套、攪拌器、冷凝器及氮氣入口之三頸圓底燒瓶中。接著，使2.71公克脲溶解於18公克水中，且向反應物中添加該溶液。在混合之後，向反應混合物中緩慢添加23.74公克濃HCl (37%)，同時保持溫度低於90℃。在氮氣下，在90℃下攪拌反應混合物6小時。在反應完成之後，將燒瓶之內含物添加至過量的碳酸氫鈉溶液(30 g於600 mL水中)中。使用乙酸乙酯自所得混合物萃取產物且用去離子水洗滌。使用旋轉式蒸發器移除乙酸乙酯，且經由真空烘箱乾燥所得產物。調配物實例 This example illustrates the preparation method of the compound having the following structure according to the present invention

. Add 12.45 grams of 4-acetamidobenzaldehyde and aniline-2,4 (aniline alkoxylated with an average of 2 EO and 4 PO) to the heating jacket, stirrer, condenser and nitrogen inlet Three-necked round bottom flask. Next, 2.71 g of urea was dissolved in 18 g of water, and this solution was added to the reactant. After mixing, 23.74 grams of concentrated HCl (37%) was slowly added to the reaction mixture while keeping the temperature below 90°C. Under nitrogen, the reaction mixture was stirred at 90°C for 6 hours. After the reaction was completed, the contents of the flask were added to an excess of sodium bicarbonate solution (30 g in 600 mL water). The product was extracted from the resulting mixture using ethyl acetate and washed with deionized water. A rotary evaporator was used to remove ethyl acetate, and the resulting product was dried via a vacuum oven. Examples of formulations

The following are illustrative examples of the cleaning composition of the present invention and are not intended to be limiting.

基於總清潔及/或處理組成物重量。酶含量係以原料報導。Example 3-9: Heavy-duty liquid laundry detergent composition

Based on total cleaning and/or treatment composition weight. Enzyme content is reported as raw material.

Examples 10 to 20: Unit dose composition

基於總清潔及/或處理組成物重量。酶含量係以原料報導。These examples provide various formulations of unit-dose laundry detergents. Compositions 8 to 12 contain a single unit dose compartment. The film using the encapsulation composition is a polyvinyl alcohol-based film.

Based on total cleaning and/or treatment composition weight. Enzyme content is reported as raw material.

基於總清潔及/或處理組成物重量，酶含量係以原料報導。In the following examples, the unit dose has three compartments, but similar compositions with two, four or five compartments can be prepared. The film used to encapsulate the compartment is polyvinyl alcohol.

Based on the weight of the total cleaning and/or treatment composition, the enzyme content is reported as raw material.

AE1.8S is C _12-15 alkyl ethoxy (1.8) sulfate AE3S is C _12-15 alkyl ethoxy (3) sulfate AE7 is C _12-13 alcohol ethoxylate, average ethoxy The degree of conversion is 7 AE8 is C _12-13 alcohol ethoxylate, the average degree of ethoxylation is 8 AE9 is C _12-13 alcohol ethoxylate, the average degree of ethoxylation is 9 Amylase 1 is Stainzyme® , 15 mg active substance/g, supplied by Novozymes amylase 2 is Natalase®, 29 mg active substance/g, supplied by Novozymes, xyloglucanase is Whitezyme®, 20 mg active substance/g, supplied by Novozymes chelating agent 1 Is diethylene triamine pentaacetic acid chelating agent 2 is 1-hydroxyethane 1,1-diphosphonic acid dispersin B is glycoside hydroxylase, with 1000 mg active substance/g reported that DTI is poly(4-vinylpyridine) -1-oxide) (such as Chromabond S-403E®) or poly(1-vinylpyrrolidone-co-1-vinylimidazole) (such as SokalanHP56®) Dye control agent The dye control agent according to the present invention, such as Suparex ® O.IN (M1), Nylofixan® P (M2), Nylofixan® PM (M3) or Nylofixan® HF (M4) HSAS is a moderately branched chain alkyl sulfate, as disclosed in US 6,020,303 and US 6,060,443 LAS is Linear alkyl benzene sulfonate with average aliphatic carbon chain length C ₉ -C ₁₅ (HLAS is in acid form) Leuco colorant Any suitable leuco colorant or mixture thereof according to the present invention is Lipex® , 18 mg active substance/g, supplied by Novozymes Liquitint ^® V200 is a thiophene azo dye supplied by Milliken Mannaway®, 25 mg active substance/g, supplied by Novozymes, nuclease is phosphodiesterase SEQ ID NO 1, reported that the optical brightener 1 is 4,4'-bis{[4-anilino-6-(N-𠰌lineyl)-s-tri𠯤-2-yl] at 1000 mg active substance/g -Amino}-2,2'-stilbene disulfonic acid disodium optical brightener 2 is 4,4'-bis-(2-sulfostyryl)biphenyl disodium (sodium salt) optical brightener 3 is the Optiblanc SPL10® fragrance encapsulant from 3V Sigma, the core-shell melamine formaldehyde fragrance microcapsule polishing enzyme is p-nitrobenzyl esterase, and the reported polymer 1 is double ((C) at 1000 mg active substance/g ₂ H ₅ O)(C ₂ H ₄ O)n)(CH ₃ )-N ⁺ -C _x H _2x -N ⁺ -(CH ₃ )-Bis((C ₂ H ₅ O)(C ₂ H ₄ O)n), where n=20-30, x=3 to 8, or polymerization of its sulfated or sulfonated variants Substance 2 is ethoxylated (EO ₁₅ ) tetraethylenepentamine polymer 3 is ethoxylated polyethyleneimine polymer 4 is ethoxylated hexamethylene diamine polymer 5 is provided by Rohm&Haas Acusol 305 polymer 6 is a polyethylene glycol polymer branched by vinyl acetate. The protease provided by BASF is Purafect Prime®, 40.6 mg active substance/g, and the structurant provided by DuPont is hydrogenated castor oil.

The dimensions and values disclosed herein should not be construed as strictly limited to the precise values stated. In fact, unless otherwise stated, each such size means the stated value and the functionally equivalent range surrounding the value. For example, the size disclosed as "40 mm" is intended to mean "about 40 mm".

Unless expressly excluded or otherwise restricted, each document cited in this article, including any cross-references or related patents or applications, and any patent applications or patents for which this application claims priority or rights, shall be in full The way of reference is incorporated into this article. The citation of any document does not admit that it is the prior art of any invention disclosed or claimed herein or that it alone or in combination with any other references teaches, shows or discloses any such invention. In addition, if any meaning or definition of a term in this document contradicts any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to the term in this document shall prevail .

Although specific embodiments of the present invention have been illustrated and described, it will be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, it is intended to cover all such changes and modifications within the scope of the present invention in the scope of the attached patent application.

Claims (14)

A leuco composition comprising at least one leuco compound, the leuco compound comprising a leuco moiety and an alkyleneoxy moiety covalently bound to the leuco moiety, wherein the alkyleneoxy moiety contains at least One ethylene oxide group and at least one propylene oxide group, wherein the leuco compound has a structure of formula (CI):

Where the ratio of formula (CI) to its oxidized form is at least 1:3; wherein each individual R _o , R _m and R _p group on each of rings A, B and C is independently selected from the following components The group of: hydrogen, deuterium and R ⁵ ; wherein each R ⁵ is independently selected from the group consisting of halogen, nitro, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl , Substituted alkylaryl, -(CH ₂ ) _n -OR ¹ , -(CH ₂ ) _n -NR ¹ R ² , -C(O)R ¹ , -C(O)OR ¹ , -C(O ^{) O -, -C (O)} NR 1 R 2, -OC (O) R 1, -OC (O) OR 1, -OC (O) NR 1 R 2, -S (O) 2 R 1, - ^{_{S (O) 2 OR 1,}} -S (O) 2 O -, -S (O) 2 NR 1 R 2, -NR 1 C (O) R 2, -NR 1 C (O) OR 2, -NR ¹ C(O)SR ² , -NR ¹ C(O)NR ² R ³ , -P(O) ₂ R ¹ , -P(O)(OR ¹ ) ₂ , -P(O)(OR ¹ )O ^- and ^{-P (O) (O -)} 2; wherein the index n is an integer of 0 to 4; wherein G is independently selected from the lines of the group consisting of: hydrogen, deuterium, C ₁ -C ₁₆ alkoxide, phenoxide , Bisphenoxide, nitrite, nitrile, alkylamine, imidazole, arylamine, polyalkylene oxide, halide, alkyl sulfide, aryl sulfide and phosphine oxide; where R ¹ , R ² And R ³ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl and alkyleneoxy moieties ; Wherein any charge present in the compound is balanced by suitable independently selected internal or external relative ions: and where the maximum molar extinction coefficient of the leuco compound at a wavelength in the range of 400 to 750nm is less than 1000M ^-1 cm ^-1 . The leuco composition of claim 1, wherein the alkyleneoxy moiety contains 1 to 20 ethylene oxide groups and 1 to 20 propylene oxide groups. The leuco composition of claim 1, wherein the alkyleneoxy moiety is covalently bonded to the leuco moiety via a nitrogen atom, and the nitrogen atom and the alkyleneoxy moiety have the structure -NR ¹ (C ₂ H ₄ O) _n (C ₃ H ₆ O) _q H, where n and q are independently selected from integers 1 to 5, and R ¹ is selected from the group consisting of hydrogen, alkyl, and substituted alkane Group, aryl, substituted aryl, alkaryl, substituted alkaryl and alkyleneoxy moieties. The leuco composition of claim 1, wherein the leuco compound contains two alkyleneoxy moieties, each alkyleneoxy moiety is covalently bonded to the leuco moiety via a nitrogen atom, the nitrogen atom and the The alkyleneoxy moieties have the following structure together

Wherein n, q, r, and s are independently selected from integers 0 to 5, the sum of n and r is 2 to 10, and the sum of q and s is 2 to 10. For example, the leuco composition of claim 4, wherein the sum of n and r is 2 to 5, and the sum of q and s is 2 to 5. Such as the leuco composition of claim 1, wherein G is hydrogen. Such as the leuco composition of claim 1, wherein the leuco composition further comprises a solvent selected from the group consisting of water, ethylene glycol, propylene glycol, glycerol, poly(ethylene glycol), poly(propylene glycol) , Copolymers of ethylene oxide and propylene oxide and their mixtures. The leuco composition of claim 1, wherein the leuco compound is present in the composition in an amount of 10% by weight or more. The leuco composition of claim 1, wherein the leuco composition further contains an antioxidant compound. Such as the leuco composition of claim 9, wherein the antioxidant compound is selected from the group consisting of hindered phenol, diarylamine, benzofuranone and mixtures thereof. The leuco composition of claim 10, wherein the leuco composition contains 0.01 to 20% by weight of sterically hindered phenol. A leuco composition is obtained by the following steps: (i) providing one molar equivalent of aromatic aldehyde, (ii) providing two molar equivalents of aryl coupling agent or aryl coupling agent mixture, wherein at least one aromatic The base coupling agent contains a covalently bonded oxyalkylene or polyoxyalkylene moiety, wherein the oxyalkylene or polyoxyalkylene moiety contains at least one ethylene oxide group and at least one propylene oxide group , (Iii) Combine the aromatic aldehyde and aryl coupling agent in a suitable reaction vessel, (iv) add 0.01 to 0.5 equivalents of urea, (v) add crude hydrochloric acid to make the pH between 0 and 3. , (Vi) heating the mixture at 60 to 120°C for 2 to 12 hours, (vii) adjusting the pH to at least 7, and (viii) separating at least a portion of the salt formed during neutralization from the liquid product; wherein the The leuco composition includes at least one leuco compound, the leuco compound including a leuco moiety and an alkyleneoxy moiety covalently bonded to the leuco moiety, wherein the alkyleneoxy moiety includes at least one epoxy An ethylene group and at least one propylene oxide group, and the maximum molar extinction coefficient of the leuco compound at a wavelength in the range of 400 to 750 nm is less than 1000 M ^-1 cm ^-1 . The leuco composition of claim 12, wherein the leuco compound has the formula (CVII)

Where each index c is independently 0, 1 or 2; each R ⁴ is independently selected from the group consisting of H, Me, Et, ((CH ₂ CH ₂ O) _a (C ₃ H ₆ O) _b ) H and mixtures thereof; wherein each index a is independently an integer 1-50; each index b is independently an integer 0-25 and wherein the sum of all the independently selected integers a in the leuco colorant does not exceed 100, and The sum of all the independently selected integers b in the leuco colorant is at least 1 and not more than 50. The leuco composition of claim 13, wherein the leuco compound has the formula (CVIII)

Where R ⁸ is H or CH ₃ and the average value of each index b is independently 1 to 2.