JP2006509930A - Concentrated fabric softener composition comprising a rheology modifier that maintains stability and fluidity upon dilution - Google Patents

Abstract

A stable concentrated aqueous fabric softening composition having a viscosity of about 3000 cp to about 15,000 cp, preferably 4000 to 15000 cp, wherein the resulting diluted softening composition is physically stable and has an intermediate viscosity of about 90 cp to To have a composition of about 300 cp, the composition can be diluted with water at a 4: 1 weight ratio of water to concentrated softening composition prior to use.

Description

  The present invention relates to a concentrated fabric conditioning composition, and more particularly to an aqueous rinse cycle concentrated fabric softener composition comprising a cationic polymer or a mixture of cationic polymers, wherein the concentrated composition is prior to use. Can be diluted with water in a 4: 1 weight ratio of water to concentrate to provide a softener composition that is physically stable in both concentrated and diluted form. The composition is physically stable and reveals a commercially desirable level of viscosity.

  Traditionally, most liquid fabric conditioning or fabric softener compositions utilize the thickening properties of surfactant components or added salts to provide the desired rheology. More recently, the trend has been to incorporate certain thickeners into fabric softening compositions to provide the desired viscosity that remains stable over time.

  In commercial liquid fabric softener formulations, the rheological properties of the product are important for consumer acceptance. A common way to improve product appeal and convey a sense of product richness and efficacy is to make the apparent viscosity of a liquid product exceed at least 50 cp (measured on Brookfield RVT, 50 rpm, spindle 2). To increase. Cationic linear or cross-linked polymers are well known in the prior art as components that provide apparent viscosity in fabric softener compositions.

  Another common technique to improve the attractiveness of products is the flow of liquid products to reduce flow, thereby making the properties more syrupy and at the same time avoiding non-uniform flow of viscous aesthetics. It is to adjust the elastic component. However, as long as rheological elasticity is a function of the cationic polymer structure itself and its level in the product composition, there is no known method for adjusting rheological properties at a given level of viscosity.

  It is well known that linear cationic polymers having high molecular weights provide high fluid elasticity to liquid fabric softeners. However, the resulting compositions are often sensitive to inorganic electrolytes and high shear, resulting in liquid products that are generally unstable upon aging and separate into various phases.

  The formulation of a concentrated fabric softening composition that can be diluted by the consumer prior to use and introduced into the rinse cycle in diluted form poses a particularly difficult problem. This is because such a concentrate is a physically stable and adequately flowable composition in both concentrated and diluted forms, i.e. both before and after the consumer has diluted the concentrate. This is because it is absolutely necessary commercially. If the desired dilution is about 4: 1 (which is the weight ratio of water to the concentrated composition), its physical stability can be maintained and still remains to consumers with both concentrate concentrate and diluted compositions. It is difficult to provide a softening composition that provides an acceptable flow viscosity.

  In EP 394 133 (Colgate-Palmolive), a di-long chain, di-chain combined with an aliphatic alcohol and a water-soluble polymer to improve the rheological properties and improve the softening performance of the composition. A stable aqueous fabric softening composition comprising a short chain quaternary ammonium softening compound is described.

  WO 90/12862 (BP Chemicals Ltd. (BP Chemicals Ltd.)) is a water-soluble cationic ethylenic polymer crosslinked by a water dispersible cationic softener and a 5-45 ppm crosslinker containing polyethylene functional groups. Disclosed is an aqueous-based fabric conditioning formulation that includes a crosslinked cationic polymer as a thickening agent that can be derived from a saturated monomer or blend of monomers. An example of such a cross-linking agent is methylene bisacrylamide.

  EP-A-0 799 887 (Procter & Gamble) describes a liquid fabric softening composition that is said to exhibit excellent viscosity and phase stability and softness performance. The composition comprises: (a) 0.01 to 10% by weight of a fabric softener component, (b) (i) a hydrophilic backbone and an association having at least two hydrophobic groups per molecule attached to the hydrophilic backbone A polymer, (ii) a crosslinked cationic polymer as described in the above-mentioned WO 90/12862 cross-linked by 5-45 ppm of a crosslinker containing polyethylene functional groups, and (iii) (i) and (ii) At least 0.001% thickener selected from the group of: and (c) a component capable of sequestering metal ions.

  In WO 02/057400 (Corgate Permorib), an increase in cationic polymer obtained by polymerization of a water-soluble cationic vinyl addition monomer, 0-95 mol% acrylamide and 70-300 ppm of bifunctional vinyl addition monomer crosslinker A fabric conditioning composition comprising a sticking agent is described. The thickened softening composition is stated to be particularly effective for delivering the fragrance material in the softening composition to the fabric to be treated.

  The use of polymeric thickeners to enhance consumer appeal is well known in the prior art, but is highly viscous, physically stable and flowable, and is about to be used in a rinse cycle. A need for a concentrated liquid fabric softener that can be diluted with water at a ratio of 4: 1 and at the same time remains physically stable and easily pourable within a range of medium viscosity liquids as a diluted composition But it still exists.

The present invention is a stable concentrated aqueous fabric softening composition having a viscosity of about 3000 cp to about 15,000 cp, preferably 4000-15000 cp, wherein the resulting diluted softening composition is physically stable, Prior to use, the composition can be diluted with water at a 4: 1 weight ratio of water to a concentrated softening composition so that the viscosity has a viscosity of about 90 cp to about 300 cp, and the composition is:
a) about 5 to about 30% by weight of a cationic fabric softener;
b) at least about 0.01% by weight of (i) a cationic linear homopolymer derivable from the polymerization of acrylic acid and / or methacrylic acid; or (ii) of acrylic acid and / or methacrylic acid and acrylamide or acrylamide. A linear copolymer derivable from polymerization, said homopolymer or copolymer having a molecular weight of about 10,000 to about 30 million; or (iii) 5 to 100 mol% of a cationic vinyl addition monomer, 0 to 95 mol % Acrylamide and a cationic crosslinked polymer derivable from polymerization of 70 ppm to 300 ppm of bifunctional vinyl addition monomer crosslinking agent; or c) a cation as defined herein in (i) or (ii) respectively Linear homopolymers or linear copolymers, and (iii) herein A mixture of at least about 0.01% by weight of polymer comprising a cationic cross-linked polymer as defined above (selecting the respective amount of (i) or (ii) or (iii) in said concentrated softening composition) Providing a desired intermediate viscosity of about 90 cp to about 300 cp in the diluted composition).

  The present invention uses a cationic homopolymer or copolymer or cross-linked polymer as defined herein in an aqueous concentrated rinse cycle fabric softening composition, or a mixture of such cationic polymers, Flow elasticity and viscosity to achieve the desired concentrated flow characteristics and ability to be poured easily at a viscosity of 4,000-15,000 cp in the composition and an intermediate viscosity of 90 cp-300 cp in the diluted composition. Based on the discovery that it is possible to adjust the rheological properties. Thus, flow elasticity can be easily controlled and adjusted according to the present invention regardless of the Brookfield viscosity adjustment.

Liquid viscosity, as used herein, is expressed in centipoise as measured on a Brookfield RVT using spindle 2 at 50 rpm.
The term “fluid elasticity” or “fluid elasticity index” is defined as “Viscoelastic Properties of Polymers”, John D. Ferry, 3rd Edition, John Wiley & Sons, Inc., Chapter 1, shear rate 2500 S ^−1. It refers to the difference in primary normal stress measured in Pascal.

  In fact, when pouring liquid fabric softeners, high fluid elasticity reduces flow, thereby making the flow appear more syrupy, which is often perceived by consumers as a sign of richness. The higher the flow elasticity, the slower the flow. If the flow elasticity becomes excessively high, the fabric softener flow becomes sticky and sticky, causing problems when discharging liquid products into the washing machine. This is clearly unfavorable from a commercial point of view.

For a given chemistry, the only way to adjust the elastic flow as defined herein is to adjust the molecular weight of the polymer, its degree of crosslinking or its concentration.
In the case of linear polymers, in order to establish an acceptable Brookfield viscosity without using large amounts of polymer, the molecular weight of the polymer must be high, which induces high flow elasticity. Although it is possible to reduce flow elasticity using low molecular weight polymers, to reach the same Brookfield viscosity, the level of polymer in the composition must be increased. This not only means higher costs, but also introduces stability problems into the emulsion due to high ionic strength.

  In contrast, the combination of linear and cross-linked polymers according to the present invention provides the desired viscosity and rheological elasticity, while using moderate amounts of polymer while at the same time avoiding product stability problems.

  In a preferred embodiment, the linear polymer used in the polymer mixture of the present invention is a homopolymer of quaternary ammonium acrylate having a molecular weight of about 8 million, which is a French SNF Florgel ( SNF Floerger of France) sold as Floerger EM 949 CT (Ethanaminium N, N, N-trimethyl-2-((1-oxo-2-propenyl) oxy-) -, Chloride homopolymer); the same structural polymer having a molecular weight of about 5 million is sold by the same manufacturer as Froer Jale EM 949 L.

  In another preferred embodiment, the cross-linked polymer used in the polymer mixture of the present invention is a cross-linked copolymer of acrylamide and methacrylate using 150 ppm of methylenebisacrylamide and having a molecular weight of less than 5 million prior to cross-linking. Yes; this polymer is sold as Flosoft DP 200 by the French SNF Froer Gers.

The invention also includes a method of softening a fabric comprising rinsing the fabric to be treated in an aqueous bath containing an effective amount of the fabric softening composition as defined above.
Preferred cationic softeners are esterquat compounds having the following structural formula:

Wherein, R4 represents an aliphatic hydrocarbon group having 8 to 22 carbon atoms, _{R 2} and _{R 3 represent (CH 2)} s -R _5, wherein, _{R 5} is 8 Represents an alkoxycarbonyl group containing ˜22 carbon atoms, benzyl, phenyl, (C1-C4) -alkyl-substituted phenyl, OH or H; R1 represents (CH ₂ ) _t R ₆ , wherein R ₆ is benzyl, phenyl, (C1-C4) - alkyl substituted phenyl, represent OH or H; q, s, and t each independently represent an integer from 1 to 3; X ^- is a softener compatible anion Ion. ]
Particularly preferred cationic softeners are fatty ester quaternary ammonium compounds derived from quaternization following reaction of an alkanolamine and a fatty acid derivative, wherein the fatty ester quaternary ammonium compound has the formula:

Wherein Q represents a carboxyl group having the structure —OCO— or —COO—; R 1 represents an aliphatic hydrocarbon group having 8 to 22 carbon atoms; R 2 represents —Q—R 1 or -OH represents; q, r, s and t each independently represent a number from 1 to 3; X- ^a is an anion of valence a;
The fatty ester quaternary ammonium compound is composed of a distribution of monoester, diester and triester compounds, and when each R ₂ is —OH, a monoester quat compound is formed; one R ₂ is —OH , and the when the other R ₂ is -Q-R1, diester click atto compound is formed; in each case R ₂ is -Q-R1, Trieste torque atto compound is formed; the fatty ester quaternary The normalized percentage of monoesterquat compound in the quaternary ammonium compound is about 28% to about 39%; the normalized percentage of diesterquat compound is about 52% to about 62%, and the normalized percentage of triesterquat compound Is from about 7% to about 14%; all percentages are by weight. ]
It is a fatty ester quaternary ammonium compound represented by:

  The weight percentages of mono-, di-, and triesterquats described above are expressed as "Characterisation of quaternized triethanolamine esters (esterquats) by HPLC, HRCGC and NMR" AJ Wilkes, C. Jacobs, G. Walraven and JM Talbot-Colgate Palmolive R & D Inc.- 4th world Surfactants Congress, Barcelone, 3-7 VI 1996, page 382, determined by quantitative analysis methods described in the publication. The weight percent of mono, di and triester quats measured on the dry sample is normalized to 100%. Normalization is required due to the presence of about 10-15% by weight of non-quaternized species such as ester amines and free fatty acids. Thus, normalized weight percent refers to the pure esterquat component of the raw material.

  The cross-linked copolymer used in the composition of the present invention was cross-linked using a bifunctional vinyl addition monomer cross-linking agent at a level of 70-300 ppm, preferably about 75-200 ppm, most preferably about 80-150 ppm. Cross-linked cationic vinyl polymer. Such polymers are further described in US-A-4,806,345 and above-mentioned WO 02/057400, which are hereby incorporated by reference.

  In general, such polymers are produced as water-in-oil emulsions in which the crosslinked polymer is dispersed in mineral oil and may contain a surfactant. During the production of the finished product, in contact with the aqueous phase, the emulsion is reversed, allowing the water-soluble polymer to swell.

  The most preferred thickener for use in the present invention is a crosslinked copolymer of quaternary ammonium acrylate or methacrylate in combination with an acrylamide comonomer.

  The linear polymer used in the composition of the present invention is a water-soluble linear cationic homopolymer of acrylate or methacrylate having a molecular weight of 10,000 to 30 million, most preferably 5 to 8 million.

Such polymers are usually prepared as water-in-oil emulsions that may contain a surfactant but are also supplied in powder form.
A preferred polymer for use in the present invention is a linear homopolymer of quaternary ammonium acrylate having a molecular weight of 5 million.

If necessary, the composition of the present invention may include an emulsifier to disperse one or more softening ingredients in the composition and ensure the physical stability of the composition. If desired, emulsifiers may be included in the softener composition, for example, aliphatic alcohol ethoxylates having an alkyl chain length of about 13-15 carbon atoms, where the number of ethylene groups per mole is About 15-20. Particularly preferred for such use is Synperonic A20 manufactured by ICI Chemicals, which is an ethoxylated C ₁₃ -C ₁₅ having 20 moles of ethylene oxide per mole of alcohol. It is a nonionic surfactant that is an aliphatic alcohol.

  The composition of the present invention may comprise 0% to about 5% perfume. As used herein, the term “perfume” is used in its ordinary sense to obtain any water-insoluble fragrance or natural (ie, flower, herb, blossom or plant extraction). ), Man-made (ie, natural oil or mixture of oil components) and synthetically produced odoriferous substances, including and including mixtures of substances. Typically, perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatics and various amounts of essential oils (eg, terpenes), where the essential oil itself has a volatile aroma. A releasing compound that also helps dissolve other ingredients of the perfume.

In the present invention, the particular composition of the perfume is not critical with respect to the performance of the liquid fabric softener composition as long as it meets the water immiscibility criteria and has a pleasant odor.
The composition of the present invention was mixed with 0% to about 2% preservative, for example, a solution of lactic acid or formaldehyde, bromonitropropanediol (Euxyl K446 from Schulke & Mayr). Dispersion of 1,2-dibromo-2,4-dicyanobutane or dispersion of 1,2-benzisothiazolin-3-one molecule (Proxel BD2 or Proxel GXL manufactured by Avecia Biocides) A system may be included.

A co-softener may optionally be included in the composition, such as an aliphatic alcohol, glycerol mono-stearate or glycerol mono-oleate.
Small amounts of other optional ingredients commonly used in fabric softening compositions may be added to improve the appearance or performance characteristics of the liquid fabric softener composition of the present invention. Typical ingredients of this type include, but are not limited to, colorants such as dyes or pigments, bluing agents and bactericides, and opacifiers.

  The fabric softener composition should be capable of being easily poured by the end user, whether in concentrated or diluted form. Thus, in general, the viscosity of the product should not exceed about 15,000 centipoise for products intended for dilution when used by consumers. Viscosity is measured at 25 ° C (22-26 ° C) using a Brookfield RVTD digital viscometer with spindle # 3 at 10 rpm.

  A sequestering or chelating compound may optionally be included in the fabric softening composition of the present invention at a concentration of 0-2% by weight. Useful sequestering compounds are capable of sequestering metal ions, preferably at a level of at least 0.001% by weight of the softening composition, preferably from about 0.001% (10 ppm) to 0.5%, more preferably About 0.005 to 0.25% by weight is present. Sequestering compounds that are acidic in nature exist in the acid form or as a complex / salt with an appropriate counter cation such as an alkali or alkaline earth metal ion, ammonium or substituted ammonium ion or any mixture thereof. Good.

  The sequestering compound is selected from aminocarboxylic acid compounds and organic aminophosphonic acid compounds, and mixtures thereof. Suitable aminocarboxylic acid compounds include: ethylenediaminetetraacetic acid (EDTA); N-hydroxyethylenediaminetriacetic acid; nitrilotriacetic acid (NTA); and diethylenetriaminepentaacetic acid (DEPTA).

  Suitable organic aminophosphonic acid compounds include: ethylenediaminetetrakis (methylenephosphonic acid); 1-hydroxyethane 1,1-diphosphonic acid (HEDP); and aminotri (methylenephosphonic acid).

In the following examples, linear homopolymers, linear copolymers and cationic cross-linked polymers are described below in connection with their trade names:
Flosoft DP 200 (from SNF) —a cationic crosslinked copolymer of quaternary ammonium acrylate or methacrylate having a molecular weight of less than about 5 million, preferably 4 million, in combination with an acrylamide comonomer.

Floeger 949 CT (manufactured by SNF)-water-soluble linear homopolymer of acrylate or methacrylate having a molecular weight of about 8 million.
Floeger EM 949 L (manufactured by SNF)-water-soluble linear homopolymer of acrylate or methacrylate having a molecular weight of about 5 million.

  Fluor gel DP / LC 2322A (manufactured by SNF) —combined with an acrylamide comonomer, bifunctional vinyl addition monomer crosslinker (MBA, ie methylenebisacrylamide) 70-300 ppm, preferably about 75-200 ppm, most preferably 80- A cationic cross-linked copolymer of quaternary ammonium acrylate or methacrylate used at a level of 150 ppm. This copolymer is similar to Flosoft DP 200, but contains more transfer agent (450-600 ppm) than Frosoft DP 200 with about 300-400 ppm transfer agent. The resulting Froger DP / LC 2322A is a water-swelling polymer that is more branched than Flosoft DP 200, characterized by an intrinsic viscosity <4 dl / g prior to crosslinking.

  Fluorgel DP / LC 2322B (from SNF)-used in combination with acrylamide comonomer, bifunctional vinyl addition monomer crosslinker (MBA) at a level of 70-300 ppm, preferably about 75-200 ppm, most preferably 80-150 ppm A cationic crosslinked copolymer of quaternary ammonium acrylate or methacrylate. This copolymer is similar to Flosoft DP 200, but contains more transfer agent (600-800 ppm) than Frosoft DP 200 with about 300-400 ppm transfer agent. The resulting Froger DP / LC 2322B is a water-swelling polymer that is more branched than Flosoft DP 200, characterized by an intrinsic viscosity <4 dl / g prior to crosslinking.

  Exemplary concentrated fabric softening compositions of the present invention intended for 4: 1 dilution are shown in Examples 1-7 below, which include about 34% monoester, about 56% diester and about 10%. Contains cationic softener Esterquat B (trade name L1-90; manufactured by KAO) characterized by distribution of triester compound (standardized weight% on dry sample). The viscosity of the concentrated (neat) product and the viscosity after 4: 1 dilution are shown in the examples.

  Concentrated softener compositions outside the scope of the present invention are shown in Examples 8-11 below, which include commercially available thickeners outside the scope of the claims.

  Examples 1-7 use cationic copolymers or homopolymers or copolymer-homopolymer mixtures according to the present invention in a 4: 1 weight ratio of water to concentrated softener composition prior to use. Provides a stable concentrated composition that can be diluted with a liquid, wherein the concentrated and diluted compositions are physically stable and have commercially desirable levels of viscosity (> 90 cp in diluted form and 3 in concentrated form). , 15,000 to 15,000 cp) is proved.

  Examples 8-11 use other types of well-known thickeners outside the scope of the present invention, such as association or cellulose-based thickeners, water-to-concentrate 4: It is demonstrated that once diluted at a weight ratio of 1, it provides a very thick and viscous concentrated composition that is not physically stable. Concentrated products as well as diluted products reveal a commercially undesirable level of viscosity.

Claims (10)

A stable concentrated aqueous fabric softening composition having a viscosity of about 3000 cp to about 15,000 cp so that the resulting diluted softening composition is physically stable and has an intermediate viscosity of about 90 cp to about 300 cp. The composition can be diluted with water at a 4: 1 weight ratio of water to concentrated softening composition prior to use, the composition comprising:
a) about 5 to about 30% by weight of a cationic fabric softener;
b) at least about 0.01% by weight of (i) a cationic linear homopolymer derivable from the polymerization of acrylic acid and / or methacrylic acid; or (ii) of acrylic acid and / or methacrylic acid and acrylamide or acrylamide. A linear copolymer derivable from polymerization, said homopolymer or copolymer having a molecular weight of about 10,000 to about 30 million; or (iii) 5 to 100 mol% of a cationic vinyl addition monomer, 0 to 95 mol % Acrylamide and a cationic crosslinked polymer derivable from polymerization of 70 ppm to 300 ppm of bifunctional vinyl addition monomer crosslinking agent; or c) a cation as defined herein in (i) or (ii) respectively Linear homopolymers or linear copolymers, and (iii) herein A mixture of at least about 0.01% by weight of polymer comprising a cationic cross-linked polymer as defined above (selecting the respective amount of (i) or (ii) or (iii) in said concentrated softening composition) Providing a desired intermediate viscosity of about 90 cp to about 300 cp in the diluted composition);
d) 0 to about 10% by weight of a sequestering compound selected from the group consisting of aminocarboxylic acid compounds, organic aminophosphonic acid compounds and mixtures thereof;
e) 0 to about 5% by weight of perfume;
f) 0 to about 10% by weight of an emulsifier;
g) 0 to about 10% by weight of one or more adjuvants selected from the group consisting of dyes, opacifiers, build agents and preservatives; and h) the balance water.
A composition comprising:   The fabric softening composition of claim 1, further comprising 0 to about 10% by weight of a co-softener selected from the group consisting of fatty alcohols, glycerin monostearate and glycerin monooleate.   The fabric softener composition of claim 1, wherein the emulsifier is an aliphatic alcohol ethoxylate nonionic surfactant.   The fabric softening composition of claim 1, wherein the cationic linear polymer comprises an acrylate or methacrylate quaternary salt.   The fabric softening composition of claim 1, wherein the cationic crosslinked polymer is a crosslinked vinyl polymer.   The fabric softening composition of claim 1, wherein the cationic cross-linked polymer comprises a quaternary salt of acrylate or methacrylate.   The fabric composition of claim 1, wherein the cationic softener is selected from the group consisting of quaternary ammonium compounds, ester quats, imidazolinium quats and difatty diamido ammonium methyl sulfates.   The fabric softening composition of claim 7, wherein the cationic softener comprises ditallow diester ammonium methosulfate.   The fabric softening composition of claim 7, wherein the cationic softening agent comprises esterquat.   A method of softening a fabric comprising forming an aqueous solution comprising an effective amount of the fabric softening composition of claim 1 and then contacting the fabric to be softened with the aqueous solution.