CN108368456B

CN108368456B - Fabric conditioning composition

Info

Publication number: CN108368456B
Application number: CN201680072911.2A
Authority: CN
Inventors: E·A·克洛威斯; R·A·孔特; K·G·K·琼斯; S·E·A·姆乔恩斯特; J·佩瑞
Original assignee: Unilever NV
Current assignee: Unilever IP Holdings BV
Priority date: 2015-12-15
Filing date: 2016-11-29
Publication date: 2021-01-26
Anticipated expiration: 2036-11-29
Also published as: EP3390600B1; BR112018011971A2; BR112018011971B1; WO2017102307A1; CN108368456A; EP3390600A1; TR201907715T4

Abstract

A fabric conditioning composition comprising from 0.5 to 20 wt% of a fabric softening active which is a quaternary ammonium compound; a cationic polysaccharide; a non-ionic polysaccharide; block copolymers of polypropylene glycol and polyethylene glycol; and water.

Description

Fabric conditioning composition

Technical Field

The present invention relates to fabric conditioner compositions comprising fabric softening actives, cationic polysaccharides, nonionic polysaccharides and block copolymers of polypropylene glycol and polyethylene glycol with excellent stability.

Background

Fabric conditioners require a long "shelf life" as a commercial product. There may be a considerable period of time between the production of the product and the use of the product by the consumer. Over time, the fabric conditioner becomes unstable and the product becomes unusable. Various attempts have been made to improve the stability of fabric conditioner products.

WO 2015107155 discloses a fabric conditioning composition comprising at least one fabric conditioning compound, preferably a biodegradable and cationic fabric conditioning compound, and a cationic polysaccharide. The composition has excellent stability and long shelf life, as well as excellent softening properties.

However, there is still a need to further extend the useful life of fabric conditioners before they become unstable.

We have surprisingly found that improved stability is demonstrated by incorporating a nonionic polysaccharide and a block copolymer of polypropylene glycol and polyethylene glycol into a fabric conditioning composition comprising a fabric softening active and a cationic polysaccharide.

Disclosure of Invention

A first aspect of the present invention provides a fabric conditioning composition comprising:

0.5 to 20 wt% of a fabric softening active which is a quaternary ammonium compound;

b. a cationic polysaccharide;

c. a non-ionic polysaccharide;

d. block copolymers of polypropylene glycol and polyethylene glycol; and

e. and (3) water.

A second aspect of the present invention provides a method of improving the stability of a fabric conditioning composition by adding to the composition: 0.5 to 20 wt% of a fabric softening active; a cationic polysaccharide; a non-ionic polysaccharide; block copolymers of polypropylene glycol and polyethylene glycol; and water.

Detailed Description

Definition of

As used herein, the term "cationic polysaccharide" refers to a polysaccharide or derivative thereof that has been chemically modified to provide the polysaccharide or derivative thereof with a net positive charge in a pH neutral aqueous medium. Cationic polysaccharides may also include those that are not permanently charged, such as derivatives that may be cationic below a given pH and neutral above that pH. Unmodified polysaccharides, such as starch, cellulose, pectin, carrageenan, guar gum, xanthan gum, dextran, curdlan, chitosan, chitin, and the like, may be chemically modified to impart a cationic charge thereon. Common chemical modifications incorporate quaternary ammonium substituents onto the polysaccharide backbone. Other suitable cationic substituents include primary, secondary or tertiary amino groups or quaternary sulfonium or phosphonium groups. Additional chemical modifications may include crosslinking, stabilization reactions (e.g., alkylation and esterification), phosphorylation, hydrolysis.

As used herein, the term "nonionic polysaccharide" refers to a polysaccharide or derivative thereof that has been chemically modified to provide the polysaccharide or derivative thereof with a net neutral charge in a pH neutral aqueous medium; or unmodified polysaccharides.

Fabric softening actives

The compositions of the present invention contain a fabric softening active.

The fabric conditioning compositions of the present invention typically contain from about 0.5 to 20 wt%, preferably from 1 to 11 wt%, more preferably from 2 to 8 wt% of softening active.

The softening active used in the rinse conditioner compositions of the present invention is a Quaternary Ammonium Compound (QAC). Preferred quaternary ammonium compounds for use in the compositions of the present invention are so-called "ester quaternary ammonium compounds (quats)" comprising an ester linkage. A particularly preferred material is an ester-linked Triethanolamine (TEA) quaternary ammonium compound comprising a mixture of mono-, di-, and tri-ester linked components. Most preferably, the ester-linked quaternary ammonium compound is an ester-linked triethanolamine quaternary ammonium compound comprising an unsaturated fatty chain.

Typically, TEA-based fabric softening actives comprise a mixture of mono-, di-and tri-ester forms of the compound, wherein the di-ester linked component comprises no more than 70% by weight of the fabric softening compound, preferably no more than 60%, for example 55% or 45% of the fabric softening compound, and at least 10% of the mono-ester linked component, for example 11% mono-ester. Preferred actives of the sclerosant type have a typical monoester to diester to triester distribution of 18-22 monoester to 58-62 diester to 18-22 triester; such as 20:60: 20. The soft TEA quaternary ammonium compound can have 25-45%, preferably 30-40% monoester: typical monoester to diester to triester distribution of 45-60%, preferably 50-55% diester to 5-25%, preferably 10-15% triester; for example 40:50: 10.

A first group of Quaternary Ammonium Compounds (QACs) suitable for use in the present invention is represented by formula (I):

wherein each R is independently selected from C_5-35Alkyl or alkenyl radicals；R¹Represents C_1-4Alkyl radical, C_2-4Alkenyl or C_1-4A hydroxyalkyl group; t is typically O-CO (i.e., an ester group bonded to R through its carbon atom), but may alternatively be CO-O (i.e., an ester group bonded to R through its oxygen atom); n is a number selected from 1 to 4; m is a number selected from 1,2 or 3; x^-Are anionic counterions, such as halides or alkylsulfates, for example chloride or methylsulfate. Diester variants of formula I (i.e., m ═ 2) are preferred, and typically have monoester and triester analogs associated with them. Such materials are particularly suitable for use in the present invention.

Particularly preferred agents are formulations rich in the diester of triethanolammonium methylsulfate, otherwise known as "TEA ester quats".

Commercial examples include Stepancex from Stepan^TMUL85, Prapagen from Clariant^TMTQL, Tetranyl from Kao^TMAHT-1 (di [ hardened tallow ester ] which is triethanolammonium methylsulfate]) (ii) a AT-1 (di- [ tallow ester of triethanolammonium methylsulfate)]And L5/90 (di [ palmityl ester of triethanolammonium methylsulfate)]) All from Kao; and Rewoquat^TMWE15 (with C-derived)₁₀-C₂₀And C₁₆-C₁₈Diesters of triethanolammonium methylsulfate of the fatty acyl residues of unsaturated fatty acids) from Evonik.

Also suitable are soft quaternary ammonium actives such as Stepandex VK90, Stepandex VT90, SP88 (from Stepan), Ceca Noramine, Prapagen TQ (from Clariant), Dehyquat AU-57 (from Cognis), Rewoquat WE18 (from Degussa) and tetrayl L190P, tetrayl L190SP and tetrayl L190S (both from Kao).

A second group of QACs suitable for use in the present invention are represented by formula (II):

wherein each R¹The groups are independently selected from C_1-4Alkyl, hydroxyalkyl or C_2-4An alkenyl group; and wherein each R²The groups are independently selected from C_8-28An alkyl or alkenyl group; and wherein n, T and X^-As defined above.

Preferred materials of this second group include 1, 2-bis [ tallowoyloxy ] -3-trimethylammonium propane chloride, 1, 2-bis [ hardened tallowoyloxy ] -3-trimethylammonium propane chloride, 1, 2-bis [ oleoyloxy ] -3-trimethylammonium propane chloride and 1, 2-bis [ stearoyloxy ] -3-trimethylammonium propane chloride. Such materials are described in US 4,137,180(Lever Brothers). Preferably, these materials also contain a certain amount of the corresponding monoester.

A third group of QACs suitable for use in the present invention is represented by formula (III):

(R¹)₂-N⁺-[(CH₂)_n-T-R²]₂X^- (III)

wherein each R¹The groups are independently selected from C_1-4Alkyl or C_2-4An alkenyl group; and wherein each R²The groups are independently selected from C_8-28An alkyl or alkenyl group; and n, T and X^-As defined above. Preferred materials of this third group include bis (2-tallowoyloxyethyl) dimethylammonium chloride and hardened forms thereof.

The iodine value of the quaternary ammonium fabric conditioning material is preferably from 0 to 80, more preferably from 0 to 60, most preferably from 0 to 45. The iodine value can be appropriately selected. Substantially saturated materials having an iodine value of from 0 to 5, preferably from 0 to 1, may be used in the compositions of the present invention. Such materials are known as "hardened" quaternary ammonium compounds.

A further preferred range of iodine value is from 20 to 60, preferably from 25 to 50, more preferably from 30 to 45. Materials of this type are "soft" triethanolamine quaternary ammonium compounds, preferably triethanolamine dialkyl methyl sulfate. Such ester-linked triethanolamine quaternary ammonium compounds contain unsaturated fatty chains.

The iodine value used in the context of the present invention relates to the fatty acids used to produce QACs, as measured by, for example, anal.341136(1962) measurement of the unsaturation present in the material by the method of NMR spectroscopy described in Johnson and Shoolery.

Another class of softening compounds can be non-ester quaternary ammonium materials represented by formula (IV):

wherein each R¹The groups are independently selected from C_1-4Alkyl, hydroxyalkyl or C_2-4An alkenyl group; each R²The groups are independently selected from C_8-28Alkyl or alkenyl, and X^-As defined above.

The compositions of the invention may optionally contain a non-cationic softening material, which is preferably an oily sugar derivative. Oily sugar derivatives are liquid or soft solid derivatives of Cyclic Polyols (CPE) or Reducing Sugars (RSE) resulting from 35-100% of the hydroxyl groups in the polyol or in the sugar being esterified or etherified. The derivative has independently attached to C₈-C₂₂Two or more ester or ether groups of an alkyl or alkenyl chain.

Advantageously, the CPE or RSE does not have any substantial crystalline character at 20 ℃. Rather, it is preferably a liquid or soft solid as defined herein at 20 ℃.

Liquid or soft solid (as defined below) CPEs or RSEs suitable for use in the present invention result from 35-100% of the hydroxyl groups of the starting cyclic polyol or reducing sugar being esterified or etherified with groups such that the CPE or RSE is in the desired liquid or soft solid state. These groups typically contain unsaturation, branching or mixed chain lengths.

Typically, the CPE or RSE has 3 or more ester or ether groups or mixtures thereof, for example 3 to 8, especially 3 to 5. If two or more of the ester or ether groups of the CPE or RSE are independently linked to C₈To C₂₂Alkyl or alkenyl chains are preferred. C₈To C₂₂The alkyl or alkenyl groups may be branched or straight carbon chains.

Preferably 35-85% of the hydroxyl groups, most preferably 40-80%, even more preferably 45-75%, for example 45-70%, are esterified or etherified.

Preferably, the CPE or RSE contains at least 35% tri-or higher esters, e.g. at least 40%.

The CPE or RSE has at least one chain independently linked to an ester or ether group having at least one unsaturated bond. This provides a cost effective way to make the CPE or RSE as a liquid or soft solid. It is preferred if predominantly unsaturated fatty chains derived from sources such as rape oil, cotton seed oil, soybean oil, oleic acid, tallow, palmitoleic acid, linoleic acid, erucic acid or other unsaturated vegetable fatty acid sources are attached to the ester/ether groups.

These chains are hereinafter referred to as ester or ether chains (of CPE or RSE).

The ester or ether chain of the CPE or RSE is preferably predominantly unsaturated. Preferred CPEs or RSEs include sucrose tetratallowate (tetratallowate), sucrose tetraoleate (tetrarapeate), sucrose tetraoleate, sucrose tetraesters of soybean or cottonseed oil, cellobiose tetraoleate, sucrose trioleate, sucrose pentaoleate, sucrose hexaoleate, sucrose triesters, pentaesters and hexaesters of soybean or cottonseed oil, glucose trioleate, glucose tetraoleate, xylose trioleate, or any mixed sucrose tetraesters, triesters, pentaesters or hexaesters having predominantly unsaturated fatty acid chains. The most preferred CPEs or RSEs are those having monounsaturated fatty acid chains, i.e. where any polyunsaturated degree has been removed by partial hydrogenation. However, some CPEs or RSEs based on polyunsaturated fatty acid chains, such as sucrose tetralinoleate, may be used, provided that most of the polyunsaturated degree has been removed by partial hydrogenation.

The most highly preferred liquid CPE or RSE is any of the above, but wherein the polyunsaturated degree has been removed by partial hydrogenation. Preferably 40% or more of the fatty acid chains contain unsaturated bonds, more preferably 50% or more, most preferably 60% or more. In most cases, 65% to 100%, for example 65% to 95%, contain unsaturated bonds.

CPE is preferably used in the present invention. Inositol is a preferred example of cyclic polyol. Inositol derivatives are particularly preferred.

In the context of the present invention, the term cyclic polyol includes all forms of saccharides. Indeed, saccharides are particularly preferred for use in the present invention. Examples of preferred saccharides for CPE or RSE to be derived therefrom are monosaccharides and disaccharides.

Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is particularly preferred. Examples of disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is particularly preferred. An example of a reducing sugar is sorbitan.

Liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of cyclic polyols or reducing sugars with acid chlorides; transesterification of cyclic polyols or reducing sugar fatty acid esters using various catalysts; acylating the cyclic polyol or reducing sugar with an acid anhydride and acylating the cyclic polyol or reducing sugar with a fatty acid. See, e.g., US 4386213 and AU 14416/88 (both P & G).

It is preferred if the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of esterification of 3 to 5, such as sucrose triesters, tetraesters and pentaesters.

In the case where the cyclic polyol is a reducing sugar, if each ring of the CPE has an ether or ester group, it is preferred to be at C₁At bit positions, it is advantageous. Suitable examples of such compounds include methyl glucose derivatives.

Examples of suitable CPEs include esters of alkyl (poly) glucosides, in particular alkyl glucoside esters having a degree of polymerization of 1 to 2.

The length of the unsaturated (and saturated, if present) chain in the CPE or RSE is C₈-C₂₂Preferably C₁₂-C₂₂. May include one or more C₁-C₈Chains, however, these are less preferred.

Liquid or soft solid CPE or RSE suitable for use in the present invention is characterized, e.g., by T₂A material having a solid to liquid ratio of 50:50 to 0:100 at 20 ℃, preferably 43:57 to 0:100, most preferably 40:60 to 0:100, for example 20:80 to 0: 100. T is₂NMR relaxation times are commonly used to characterize the solid to liquid ratio in soft solid products such as fats and margarines. For the purposes of the present invention, having a T of less than 100. mu.s₂Any component of the signal of (A) is regarded as a solid component and has a T₂Any component of ≧ 100 μ s is considered as the liquid component.

For CPE and RSE, the prefixes (e.g., four and five) merely indicate the average degree of esterification. The compounds are present as mixtures of materials ranging from monoesters to fully esterified esters. Which is used herein to define the average degree of esterification of CPE and RSE.

The HLB of a CPE or RSE is typically between 1 and 3.

When present, the CPE or RSE is preferably present in the composition in an amount of from 0.5 to 50 wt. -%, more preferably from 1 to 30 wt. -%, e.g. from 2 to 25 wt. -%, like from 2 to 20 wt. -%, based on the total weight of the composition.

CPE and RSE for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate.

Cationic and nonionic polysaccharides

According to the present invention, the fabric conditioner composition comprises a cationic polysaccharide and a nonionic polysaccharide. In one embodiment, these are premixed prior to addition to the composition, while in another embodiment, these components are added separately. Preferably, the cationic polysaccharide and the nonionic polysaccharide are mixed prior to addition to the fabric conditioner composition.

Cationic polysaccharides

The cationic polysaccharide comprises at least one cationic polysaccharide. Cationic polysaccharides can be obtained by chemically modifying polysaccharides, usually natural polysaccharides. By such modification, cationic side groups can be introduced into the polysaccharide backbone. In one embodiment, the cationic groups carried by the cationic polysaccharide according to the invention are quaternary ammonium groups.

Cationic polysaccharides of the present invention include, but are not limited to: cationic cellulose and derivatives thereof, cationic starch and derivatives thereof, cationic cellobiose (callose) and derivatives thereof, cationic xylan and derivatives thereof, cationic mannan and derivatives thereof, cationic galactomannan and derivatives thereof, such as cationic guar gum and derivatives thereof.

Cationic celluloses suitable for use in the present invention include cellulose ethers containing quaternary ammonium groups, cationic cellulose copolymers or celluloses grafted with a water soluble quaternary ammonium monomer.

Cellulose ethers containing quaternary ammonium groups are described in french patent 1,492,597, including in particular the polymers sold by the Dow company under the name "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M). These polymers are also defined in the CTFA dictionary as hydroxyethyl cellulose quaternary ammonium that has been reacted with an epoxide substituted with a trimethylammonium group. Suitable cationic celluloses also include LR3000 KC from Solvay corporation.

Cationic cellulose copolymers or cellulose grafted with water soluble quaternary ammonium monomers are described in particular in U.S. Pat. No. 4,131,576. For example hydroxyalkyl celluloses, such as, in particular, hydroxymethyl-, hydroxyethyl-or hydroxypropyl celluloses grafted with methacryloyl-ethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyl-diallylammonium salts. The commercial products corresponding to this definition are more particularly under the name Akzo Nobel

L200 and

h100 sold product.

Cationic starches suitable for use in the present invention include

(cationic starch from Sigma) to

And

product sold (cationic Starch from Avebe), CATO from National Starch.

Suitable cationic galactomannans may be those derived from fenugreek gum, konjac gum, tara gum, cassia gum or guar gum.

Preferably the cationic polysaccharide is cationic guar. Guar gum is a polysaccharide consisting of the sugars galactose and mannose. The backbone is a linear chain of β 1, 4-linked mannose residues to which galactose residues are on average 1, 6-linked at every two mannose residues, forming short side units. Within the context of the present invention, cationic guar is a cationic derivative of guar.

In the case of cationic polysaccharides, such as cationic guar, the cationic group can be a quaternary ammonium group carrying 3 groups, which may be identical or different, preferably chosen from hydrogen, alkyl, hydroxyalkyl, epoxyalkyl, alkenyl or aryl groups, preferably containing from 1 to 22 carbon atoms, more particularly from 1 to 14 and advantageously from 1 to 3 carbon atoms. The counterion is typically a halide. An example of a halide is chloride.

Examples of quaternary ammonium groups include: 3-chloro-2-hydroxypropyl trimethylammonium chloride (CHPTMAC), 2, 3-epoxypropyltrimethylammonium chloride (EPTAC), diallyldimethylammonium chloride (DMDAAC), vinylbenzyltrimethylammonium chloride, trimethylammonium chloride ethyl methacrylate, methacrylamidopropyltrimethylammonium chloride (MAPTAC) and tetraalkylammonium chloride.

One example of a cationic functional group in a cationic polysaccharide with a counterion (e.g., cationic guar) is trimethylamino (2-hydroxy) propyl. Various counter ions can be used including, but not limited to, halides such as chloride, fluoride, bromide and iodide, sulfate, nitrate, methylsulfate and mixtures thereof.

The cationic guar of the invention can be chosen from: cationic hydroxyalkyl guars, such as cationic hydroxyethyl guar, cationic hydroxypropyl guar, cationic hydroxybutyl guar, and cationic carboxyalkyl guars, including cationic carboxymethyl guar, cationic alkylcarboxyl guar, such as cationic carboxypropyl guar and cationic carboxybutyl guar, cationic carboxymethylhydroxypropyl guar.

In an exemplary embodiment, the cationic polysaccharide of the present invention is guar hydroxypropyltrimonium chloride or hydroxypropyl guar hydroxypropyltrimonium chloride.

The cationic polysaccharides of the present invention may have an average molecular weight (Mw) of from 100,000 daltons to 3,500,000 daltons, preferably from 100,000 daltons to 1,500,000 daltons, more preferably from 100,000 daltons to 1,000,000 daltons.

The composition of the present invention preferably comprises 0.01 to 2 wt% of cationic polysaccharide, based on the total weight of the composition. More preferably, from 0.025 to 1 wt% of cationic polysaccharide, based on the total weight of the composition. Most preferably, 0.04 to 0.8 wt% of cationic polysaccharide, based on the total weight of the composition.

In the context of the present application, the term "Degree of Substitution (DS)" of a cationic polysaccharide, such as cationic guar gum, is the average number of hydroxyl groups substituted per saccharide unit. DS may particularly denote the number of carboxymethyl groups per saccharide unit. DS can be determined by titration.

The DS of the cationic polysaccharide is preferably from 0.01 to 1, more preferably from 0.05 to 1, most preferably from 0.05 to 0.2.

In the context of the present application, the "Charge Density (CD)" of a cationic polysaccharide, such as cationic guar, means the ratio of the number of positive charges on the monomeric units comprised by the polymer to the molecular weight of said monomeric units.

The CD of the cationic polysaccharide, e.g., cationic guar gum, is preferably in the range of 0.1 to 3(meq/gm), more preferably 0.1 to 2(meq/gm), most preferably 0.1 to 1 (meq/gm).

Nonionic polysaccharides

The nonionic polysaccharide comprises at least one nonionic polysaccharide. The non-ionic polysaccharide may be a modified non-ionic polysaccharide or an unmodified non-ionic polysaccharide. The modified nonionic polysaccharide may comprise hydroxyalkylation and/or esterification.

In the context of the present application, the level of modification of the nonionic polysaccharide can be characterized by the Molar Substitution (MS), which represents the average number of moles of substituents, such as hydroxypropyl groups, per mole of monosaccharide unit. MS can be determined by Zeisel-GC method, especially based on the following references: K.L.Hodges, W.E.Kester, D.L.Wiederlich and J.A.Grover, "Determination of akoxyl catalysis in Cellulose Ethers by Zeisel-Gas Chromatography", Analytical Chemistry, Vol.51, No.13, 11 months 1979. Preferably, the MS of the modified nonionic polysaccharide is in the range of 0 to 3, more preferably 0.1 to 3, most preferably 0.1 to 2.

The nonionic polysaccharides of the invention may be chosen in particular from glucans, modified or unmodified starches (such as those derived, for example, from cereals, such as wheat, maize or rice, from plants, such as yellow peas, and tubers, such as potatoes or cassava), amylose, amylopectin, animal starch, dextran, cellulose and its derivatives (methylcellulose, hydroxyalkyl cellulose, ethyl hydroxyethyl cellulose), mannans, xylans, lignin, arabinans, galactans, galacturonans, chitin, chitosan, glucuronoxylan, arabinoxylans, xyloglucans, glucomannans, pectates and pectins, arabinogalactans, carrageenans, agar-agar, gum arabic, tragacanth gum, ghatti gum, carrageenan, carob gum, galactomannans such as guar gum and its nonionic derivatives (hydroxypropyl guar), and mixtures thereof. Among the celluloses that are particularly useful are hydroxyethyl cellulose and hydroxypropyl cellulose. Mention may be made of the company Aqualon under the name

EF，

H，

LHF，

MF and

g products sold by Amerchol, and

polymer PCG-10, and HEC, HPMC K200, HPMC K35M, sold by Ashland corporation.

Preferably the nonionic polysaccharide is nonionic guar. The nonionic guar may be modified or unmodified. Unmodified non-ionic guar includes those available under the name Unipectine

GH 175 and by Solvay Corp

And

c, the product sold. Modified nonionic guar gum, in particular with C₁-C₆And (3) hydroxyalkyl modification. Among the hydroxyalkyl groups, mention may be made, for example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. These guars are well known in the art and can be prepared, for example, by reacting the corresponding alkylene oxide, such as propylene oxide, with guar gum to obtain guar modified with hydroxypropyl groups.

The nonionic polysaccharides of the present invention, such as nonionic guar, can have an average molecular weight (Mw) of 100,000 daltons to 3,500,000 daltons, preferably 500,000 daltons to 3,500,000 daltons.

The composition of the present invention preferably comprises 0.01 to 2 wt.% of nonionic polysaccharide, based on the total weight of the composition. More preferably, from 0.025 to 1 wt% of a nonionic polysaccharide, based on the total weight of the composition. Most preferably, 0.04 to 0.8 wt% of the nonionic polysaccharide, based on the total weight of the composition.

Preferably, the fabric conditioning composition comprises from 0.02 to 4 wt%, more preferably from 0.05 to 2 wt%, most preferably from 0.08 to 1.6 wt% of the combined weight of the cationic polysaccharide and the nonionic polysaccharide.

Preferably, the ratio of the weight of cationic polysaccharide in the composition to the weight of non-ionic polysaccharide in the composition is between 1:10 and 10:1, more preferably between 1:3 and 3: 1.

In a preferred embodiment, the cationic polysaccharide and the nonionic polysaccharide are mixed prior to addition to the fabric conditioner composition. The mixture is preferably prepared as a suspension in water.

Preferably, the ratio of the weight of quaternary ammonium compound in the composition to the total weight of cationic and nonionic polysaccharide in the composition is between 100:1 and 2:1, more preferably between 30:1 and 5: 1.

Block copolymer

The block copolymer of the present invention comprises a combination of polypropylene glycol and polyethylene glycol.

The block copolymer of the present invention is preferably a poloxamer polymer. Poloxamer polymers are nonionic triblock copolymers comprising a polypropylene glycol central hydrophobic chain flanked by two polyethylene glycol hydrophilic chains.

The block copolymer preferably comprises polypropylene glycol blocks having a molar mass of 1400 to 4000g/mol and 30 to 80% by weight of the final molecule of polyethylene glycol.

More preferably, the polypropylene glycol block has a molar mass of 1400 to 2200g/mol and the percentage of polyethylene glycol is 30 to 80% by weight of the final molecule.

Most preferably, the polypropylene glycol block has a molar mass of 1400 to 2200g/mol and the percentage of polyethylene glycol is 65 to 85 wt% based on the weight of the final molecule.

Commercially available block copolymers suitable for use in the present invention are available, for example, from Croda and Croda under the trade name Synperonic

From BASF;

PE 6800 was obtained from BASF and Synperonic PE/L64 was obtained from Croda.

Preferably, the fabric conditioning composition comprises from 0.01 to 5 wt% of the block copolymer, more preferably from 0.025 to 2 wt% of the block copolymer, most preferably from 0.05 to 1 wt%.

Optional ingredients

Thickening polymer

The composition of the present invention may further comprise a thickening polymer.

Thickening polymers particularly suitable for use in the compositions of the present invention include those described in WO2010/078959(SNF s.a.s.). These are crosslinked water-swellable cationic copolymers of at least one cationic monomer and optionally other nonionic and/or anionic monomers. Preferred polymers of this type are copolymers of acrylamide and methacrylate. Most preferred are copolymers of acrylamide and chlorinated trimethylaminoethyl acrylate.

The composition may comprise a crosslinked water-swellable cationic copolymer. In one embodiment of the present invention, it may be preferred that the composition comprises at least two different crosslinked water swellable cationic copolymers.

Preferred polymers represent less than 25%, preferably less than 20%, most preferably less than 15% by weight of the total polymer of the water-soluble polymer, and a crosslinker concentration of from 500ppm to 5000ppm by weight, preferably from 750ppm to 5000ppm by weight, more preferably from 1000 to 4500ppm by weight, relative to the polymer, as determined by suitable metering methods such as the following method described on page 4 of patent EP 2373773B 1.

The process is based on the isolation of crosslinked polymer microgels from polymer solutions by centrifugation. The polymer content before and after centrifugation was determined by colloid titration based on the stoichiometric precipitation of charged colloidal particles by titrating the oppositely charged polymer with a visual indicator.

About 20 grams of the polymer dispersion in the non-aqueous liquid was weighed accurately and added to 200ml of acetone with stirring at room temperature. Stirring was continued for 5 minutes, then the precipitated polymer was filtered through a No.1 filter paper, air-dried in a drying oven for 1 hour, then dried at 50 ℃ for 2 hours, cooled in a desiccator and weighed. The percentage of polymer in the starting dispersion can thus be calculated.

Sufficient of this dispersion was added to deionized water with stirring to produce about 200g of a viscous paste containing 0.5 wt.% polymer. It was stirred at about 500rpm for 45 minutes using a 3-blade impeller.

To 40g of the paste was added 210g of deionized water containing 1.0g of sodium chloride dissolved therein, and the mixture was carefully mixed for 5 minutes to lower the viscosity for centrifugation.

By weighing together with the polymer solution (using about 40ml), fill and equilibrate the Nalgene centrifuge tube, and centrifuge for 1.5 hours (15300 rpm). The top 5g of the supernatant polymer solution was carefully removed with a pipette. Samples of the supernatant polymer solution and the intact aqueous composition before centrifugation were subjected to colloid titration to determine the amount of soluble polymer in the supernatant after centrifugation. It therefore gives the percentage value of soluble polymer in the initial polymer.

The colloid titration was performed as follows:

potassium polyvinyl sulfate (PVSK): 0.0025N solution.

-hydrochloric acid: 0.1N solution to adjust.

-toluidine blue indicator: 0.1% solution.

Titration was performed on polymer solutions acidified with hydrochloric acid (pH about 4) and stained with 2-3 drops of blue indicator. PVSK was slowly added until the color changed from blue to violet.

The percent solubles was then determined based on the PVSK volume, polymer weight, corresponding dilution and reagent molar concentration measured at equilibrium.

When the crosslinking agent used is methylene bisacrylamide, or other crosslinking agent at a concentration which results in an equivalent crosslinking level of 10 to 10,000ppm by weight, the concentration of crosslinking agent must be higher than about 500ppm by weight, preferably higher than about 750ppm by weight, relative to the polymer.

Suitable cationic monomers are selected from the following monomers and derivatives and quaternary salts or acid salts thereof: dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, diallylamine, methyldiallylamine, dialkylaminoalkyl acrylates and methacrylates, dialkylaminoalkyl acrylamides or methacrylamides.

The following is a non-limiting list of monomers that perform the non-ionic function: acrylamide, methacrylamide, N-alkylacrylamides, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, vinyl acetate, vinyl alcohol, acrylates, allyl alcohol.

The following is a non-limiting list of monomers that perform an anionic function: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and monomers which perform the function of a sulfonic acid or phosphonic acid, such as 2-acrylamido-2-methylpropanesulfonic Acid (ATBS) and the like

The monomers may also contain hydrophobic groups.

The following is a non-limiting list of cross-linking agents: methylenebisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, bisacrylamide, triallylamine, cyanomethacrylate, vinyloxyethyl acrylate or methacrylate and formaldehyde, glyoxal, glycidyl ether type compounds such as ethylene glycol diglycidyl ether, or epoxides (epoxydes) or any other means familiar to the expert which allows crosslinking.

It is particularly preferred that the crosslinking rate is preferably 800-5000ppm by weight, based on methylenebisacrylamide, relative to the polymer, or equivalent to a crosslinker of different efficiency.

The degree of non-linearity can additionally be controlled by including chain transfer agents (e.g. isopropanol, sodium hypophosphite, mercaptoethanol) in the polymerization reaction mixture to control polymer chain length and crosslink density, as described in US 2002/0132749 and Research Disclosure 429116.

The amount of polymer used in the composition of the present invention is suitably from 0.001 to 0.5 wt%, preferably from 0.005 to 0.4 wt%, more preferably from 0.05 to 0.35 wt%, most preferably from 0.1 to 0.25 wt% by weight of the total composition.

Examples of preferred polymers are Flosoft 270LS from SNF and Flosoft 222 from SNF.

Silicone-based fabric softeners (and other non-quaternary softening compounds)

The compositions of the present invention may further comprise a silicone-based fabric softener. Preferably the fabric softening silicone is polydimethylsiloxane.

Fabric softening silicones include, but are not limited to, 1) non-functional silicones, such as Polydimethylsiloxane (PDMS) or alkyl (or alkoxy) functional silicones; 2) functionalized silicones or copolymers with one or more different types of functional groups such as amino, phenyl, polyether, acrylate, silane, carboxylic acid, quaternized nitrogen, and the like.

Suitable silicones may be selected from polydialkylsiloxanes, preferably polydimethylsiloxanes, more preferably amino-functional silicones; anionic silicones and carboxy-functional silicones.

Aminosilicones may also be used, for example Arristan 64 from CHT or Wacker CT45E from Wacker.

In the case of silicone emulsions, the particle size may range from about 1nm to 100 microns, preferably from about 10nm to about 10 microns, including microemulsions (<150nm), standard emulsions (from about 200nm to about 500nm), and macroemulsions (from about 1 micron to about 20 microns).

Polyalkyl wax emulsions, such as polyethylene wax, may also be used as softeners in the compositions of the present invention.

Co-softeners and fat complexes

Co-softeners may be used. When used, they are generally present at 0.1 to 20%, especially 0.3 to 10%, based on the total weight of the composition. Preferred co-softeners include fatty acid esters and fatty N-oxides. Fatty esters which may be used include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed in WO 01/46361 (Unilever).

The composition of the invention may comprise a fat complexing agent.

Particularly suitable fat complexing agents include fatty alcohols and fatty acids. Among them, fatty alcohols are most preferred.

Without being bound by theory, it is believed that the fat composite improves the viscosity characteristics of the composition by complexing with the monoester component of the fabric conditioner material, thereby providing a composition with relatively higher levels of diester and triester linked components. The diester and triester linked components are more stable and do not adversely affect the initial viscosity as the monoester component does.

It is also believed that higher levels of monoester linked components present in compositions comprising TEA-based quaternary ammonium materials may destabilize the composition by depleting flocculation. By using a fat composite to complex with the monoester linked component, the depleted flocculation is significantly reduced.

In other words, as required by the present invention, the fatty complexing agent at an increased level "neutralizes" the monoester-linked components of the quaternary ammonium material. This in situ generation of diester from monoester and fatty alcohol also improves softening of the composition.

Preferred fatty acids include hardened tallow fatty acid (available under the trade name Pristerene)^TMFrom Croda). Preferred fatty alcohols include hardened tallow alcohol (available under the trade name Stenol^TMAnd hydranol^TMObtained from BASF and by Laurex^TMCS from Huntsman).

The fat complexing agent may preferably be present in an amount of more than 0.3 to 5 wt. -%, based on the total weight of the composition. More preferably, the fat component may be present in an amount of 0.4 to 4%. The weight ratio of monoester component of the quaternary ammonium fabric softening material to the fat complexing agent is preferably from 5:1 to 1:5, more preferably from 4:1 to 1:4, most preferably from 3:1 to 1:3, for example from 2:1 to 1: 2.

Nonionic surfactant

The composition may further comprise a nonionic surfactant. These may generally be included for the purpose of stabilizing the composition. Suitable nonionic surfactants include the addition products of ethylene oxide with fatty alcohols, fatty acids and fatty amines. Any of the specific types of alkoxylated materials described below may be used as the nonionic surfactant.

Suitable surfactants are substantially water-soluble surfactants of the general formula (V):

R-Y-(C₂H₄O)_z-CH₂-CH₂-OH (V)

wherein R is selected from primary, secondary and branched alkyl and/or acyl hydrocarbyl; primary, secondary and branched alkenyl hydrocarbyl groups; and primary, secondary and branched alkenyl substituted phenolic hydrocarbyl groups; a hydrocarbyl group of 8 to about 25, preferably 10 to 20, for example 14 to 18 carbon atoms in chain length.

In the general formula of the ethoxylated nonionic surfactant, Y is typically:

o-, -C (O) N (R) -or-C (O) N (R) R-

Wherein R has the meaning given above for formula (V), or may be hydrogen; z is at least about 8, preferably at least about 10 or 11.

Preferably, the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 18, for example from 12 to 16. Genapol based on coconut chains and 20 EO groups^TMC200(Clariant) is an example of a suitable nonionic surfactant.

If present, the nonionic surfactant is present in an amount of from 0.01 to 10 weight percent, more preferably from 0.1 to 5 weight percent, based on the total weight of the composition.

One preferred class of nonionic surfactants includes the addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines. These are preferably selected from the addition products of (a) alkoxides selected from ethylene oxide, propylene oxide and mixtures thereof with (b) fatty materials selected from fatty alcohols, fatty acids and fatty amines.

Suitable surfactants are substantially water-soluble surfactants of the general formula (VI):

R-Y-(C₂H₄O)_z-CH₂-CH₂-OH (VI)

wherein R is selected from primary, secondary and branched alkyl and/or acyl hydrocarbyl (when Y ═ c (O) O, R ≠ acyl hydrocarbyl); primary, secondary and branched alkenyl hydrocarbyl groups; and primary, secondary and branched alkenyl substituted phenolic hydrocarbyl groups; a hydrocarbon group having a chain length of 10 to 60, preferably 10 to 25, for example 14 to 20 carbon atoms.

In the general formula of the ethoxylated nonionic surfactant, Y is typically:

o-, -C (O) N (R) -or-C (O) N (R) R-

Wherein R has the meaning given above for formula (VI), or may be hydrogen; z is at least about 6, preferably at least about 10 or 11.

Lutensol based on coconut chains and 25 EO groups^TMAT25(BASF) is an example of a suitable nonionic surfactant. Other suitable surfactants include Renex 36 (trideeth-6), from Croda; tergitol 15-S3 from Dow Chemical co.; dihydril LT7 from Thai Ethoxylate Ltd; cremophor CO40 from BASF, and Neodol 91-8 from Shell.

Additional optional ingredients

The composition may comprise other ingredients of fabric conditioner liquids known to those skilled in the art. Among such materials, mention may be made of: antifoams, perfumes and scents (both free oils and encapsulating materials), insect repellents, hueing or shading dyes, preservatives (e.g. bactericides), pH buffers, perfume carriers, hydrotropes, antiredeposition agents, soil release agents, polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, dyes, colorants, sunscreens, preservatives, suspending agents, antistatic agents, chelating agents and ironing aids. The product of the invention may contain pearlizing agents and/or opacifiers. A preferred chelating agent is HEDP, which is an abbreviation for etidronic acid or 1-hydroxyethane 1, 1-diphosphonic acid.

Product form

The product of the invention comprises water.

The composition is a rinse added softening composition suitable for use in a laundry process. The composition is a pourable liquid.

The liquid composition has a pH of about 2.0 to 7, preferably about 2.5 to 5.5, most preferably about 3.5 to 4.5. The composition of the invention may also contain a pH adjusting agent, preferably hydrochloric acid, lactic acid or sodium hydroxide.

The composition is preferably a ready-to-use liquid comprising an aqueous phase. The aqueous phase may contain water-soluble substances, such as mineral salts or short chains (C)_1-4) An alcohol.

The composition is preferably used in the rinse cycle of a domestic textile laundering operation, in which it can be added directly to the washing machine in an undiluted state, for example via a dispenser drawer, or for a top-loading washing machine, directly into the drum. The compositions are also useful in domestic hand washing laundry operations.

Method of producing a composite material

The present invention provides a method of improving the stability of a fabric conditioning composition by adding to said composition: 0.5 to 20 wt% of a fabric softening active; a cationic polysaccharide; a non-ionic polysaccharide; block copolymers of polypropylene glycol and polyethylene glycol; and water. In a preferred embodiment, the block copolymer of polypropylene glycol and polyethylene glycol is added to the composition together with or after the fabric softening active.

For example;

in a preferred embodiment of the invention, the block copolymer is added to the main composition in a premix with the fabric softening active.

In an alternative preferred embodiment of the invention, the block copolymer is added to the main composition after the fabric softening active.

Examples

Example 1

Table 1: a composition according to the invention;

	by weight%
		TEA Quaternary ammonium Compounds¹	4
Free perfume	0.92
		Perfume with encapsulated materialMaterial²	0.86
Cationic polysaccharides³	0.2
		Nonionic polysaccharides⁴	0.2
Pluronic PE 6800⁵	0.5
		Dye material	0.005
Minor ingredients	0.031
		Water (W)	To 100

TEA Quaternary ammonium Compounds¹-partially hardened tallow TEA Quaternary ammonium Compound in IPA from Stepan

Encapsulated perfume²-melamine formaldehyde perfume microcapsules, by weight of encapsulated perfume as such, from IFF

Cationic polysaccharides³Guar hydroxypropyltrimonium chloride with average molecular weight below 1,500,000 daltons

Nonionic polysaccharides⁴Hydroxypropyl guar having an average molecular weight of 1,500,000 to 2,500,000 daltons and an MS of 0.9 to 1.6

Pluronic PE 6800⁵From BASF

Preparation 1-addition to the Fabric softening actives in premix

1) The water was heated to about 50 ℃.

2) The cationic polysaccharide and the non-ionic polysaccharide are premixed and then added to the heated water with stirring and the mixture is mixed thoroughly.

3) Adding minor ingredients.

4) Encapsulated perfume is then added.

5) The quaternary ammonium compound and PE 6800 premix were added slowly with stirring.

6) The dye was then added and the mixture was mixed thoroughly.

7) The composition is then cooled to about 35 ℃ and the perfume components are added with higher mixing.

8) The resulting composition is then cooled.

Preparation 2-addition after Fabric softening actives

1) The water was heated to about 50 ℃.

3) Adding minor ingredients.

4) Encapsulated perfume is then added.

5) The quaternary ammonium compound is added slowly with stirring.

6) The dye was then added and the mixture was mixed thoroughly.

8) PE 6800 was dissolved in water and added to the composition and mixed well.

9) The resulting composition is then cooled.

Example 2

Compositions were prepared and tested for stability according to example 1, preparation 1. Stability was assessed visually by looking for phase separation.

Composition 1 is an embodiment of the present invention

Composition a is a comparative example.

Table 2: test compositions

Table 3: stability results

The results of the stability tests clearly demonstrate that the formulation according to the invention (composition 1) is significantly more stable than the composition with cationic polysaccharide and fabric softening active alone.

Claims

1. A fabric conditioning composition comprising:

0.01 to 2 wt% of a cationic polysaccharide, wherein the cationic polysaccharide is a cationic guar gum;

0.01 to 2 wt% of a non-ionic polysaccharide;

0.01 to 5% by weight of a block copolymer of polypropylene glycol and polyethylene glycol; and

e. and (3) water.

2. The fabric conditioning composition of claim 1, wherein the block copolymer is a poloxamer polymer.

3. The fabric conditioning composition according to any preceding claim, wherein the block copolymer comprises polypropylene glycol blocks having a molar mass of 1400 to 4000g/mol and 30 to 80% by weight of the final molecule of polyethylene glycol.

4. The fabric conditioning composition according to claim 1 or 2, wherein the non-ionic polysaccharide is a non-ionic guar.

5. The fabric conditioning composition of claim 1 or 2, wherein the weight ratio of cationic polysaccharide in the composition to non-ionic polysaccharide in the composition is from 1:10 to 10: 1.

6. The fabric conditioning composition according to claim 1 or 2 wherein the combined weight of the cationic polysaccharide and the non-ionic polysaccharide in the composition is from 0.05 to 2 wt.% of the total composition.

7. The fabric conditioning composition according to claim 1 or 2 wherein the cationic polysaccharide and nonionic polysaccharide are mixed prior to addition to the fabric conditioner composition.

8. The fabric conditioning composition of claim 1 or 2 wherein the quaternary ammonium compound is an ester-linked quaternary ammonium compound.

9. The fabric conditioning composition of claim 1 or 2, wherein the ratio of the weight of the quaternary ammonium compound in the composition to the total weight of the cationic polysaccharide and the nonionic polysaccharide in the composition is from 2:1 to 100: 1.

10. A method of improving the stability of a fabric conditioning composition by adding to said composition: 0.5 to 20 wt% of a fabric softening active which is a quaternary ammonium compound; 0.01 to 2 wt% of a cationic polysaccharide, wherein the cationic polysaccharide is a cationic guar gum; 0.01 to 2 wt% of a non-ionic polysaccharide; 0.01 to 5% by weight of a block copolymer of polypropylene glycol and polyethylene glycol; and water.

11. The method of claim 10, wherein the block copolymer of polypropylene glycol and polyethylene glycol is added to the composition together with or after the fabric softening active.