KR930007737B1 - Fabric softening composition - Google Patents

Abstract

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Description

Fabric softening composition

The present invention provides a fabric softening composition, in particular a fabric softening composition containing one or more fabric softening materials and optionally an optionally sufficiently dissolved electrolyte to impart a structure of lamella droplets dispersed in a continuous aqueous phase. It is about.

Lamellar droplets are described in several references, such as "Detergents" (Hach, A. Barnes, K. Walter, Chapter 2), "Rheometry: Industrial Applications" (J. Willie and Suns). , Leviswitz, 1980), a specific class of surfactant structures, among others.

Lamela textile printing compositions are described, for example, in EP303 473 (Albright and Wilson). The patent application describes a fabric softening composition containing an aqueous base material, a cationic fabric softener having two long alkyl or alkenyl groups, and a dissolved electrolyte, optionally forming an anisotropic spherical composition.

The presence of lamellar droplets in fabric softened products can be detected by methods known to those skilled in the art, such as optical techniques, various flow measurement methods, X-ray or neutron diffraction, and electron microscopy. .

Droplets consist of an array of onion peels, concentric layers of fabric softener molecules, with water or electrolyte solutions (aqueous phase) trapped in between. These droplet-rich systems provide a very desirable combination of physical stability and useful flow properties.

The viscosity and stability of the product depends on the fraction of the droplets in the liquid.

Generally speaking, the higher the volume fraction of the dispersed lamellae phase (droplet), the better the stability. However, if the volume fraction is high, the viscosity is increased to an unpourable level, that is, a gel-type product can be brought. Therefore, the two conditions must be harmonized. In other words, when the volume fraction is about 0.6 or more, the droplets are immediately contiguous (space filling). This provides an ideal stability with a tolerance of 2.5 Pas or less, preferably 1 Pas or less, at a shear rate of 21S- ¹ . Useful methods for measuring the volume fraction are known, as are conductivity measurements that compare the conductivity of continuous phases.

On the one hand the relationship between stability and viscosity and on the other hand the volume fraction of the lamellae droplets, the complexity is the degree of aggregation of the droplets. If aggregation occurs between lamellar droplets at a given volume fraction, the viscosity of the product will increase due to the formation of reticular tissue throughout the liquid. In addition, deformation of lamellar droplets due to agglomeration may result in unstable packing of the lamellar droplets more effectively. As a result, more lamellar droplets will be required for stability by the space-filling mechanism, which in turn will result in a greater increase in viscosity.

The volume fraction of the droplets increases with increasing softener concentration and may decrease with increasing electrolyte level. However, when certain threshold values of electrolyte concentration are crossed at a certain level (and a certain ratio between any other softening components) of the fabric softening material, aggregation between lamellar droplets may occur. Thus, in practice, the above-mentioned effects mean that there is a limit to the amount of fabric softening material and electrolyte that can be mixed in a range having acceptable product properties. Indeed, higher levels of fabric softening materials require convenience and cost savings. It is also possible to increase the level of electrolyte for better performance. That is, sometimes it seeks a second advantage, such as carry-over protection.

The present inventors have found that by mixing a hydrophilic backbone and a deagglomerated polymer having one or more hydrophobic side chains into the softening composition, the stability and / or viscosity depending on the volume fraction of the softening composition can be advantageously affected. I found that.

Accordingly, the present invention relates to a fabric softening composition containing an aqueous base material and at least one fabric softening material, wherein the composition has a structure of lamellar droplets dispersed in the aqueous base material, and the composition has a hydrophilic shrinkage and at least one It contains a deagglomerated polymer containing a hydrophobic side chain.

If desired, the deagglomerated polymer may be mixed with more than the amount of softener and / or electrolyte necessary to be suitable at any time to obtain a stable and easily dispersible product having a viscosity of acceptable value. It is also possible to mix larger amounts of certain other ingredients (if desired), and to date, lamellae dispersions have a highly sensitive stability to the above.

The present invention allows for the formulation of stable and pourable products that have not been possible until now in the formulation or concentration of ingredients, wherein the volume fraction of the dispersed phase is 0.5, 0.6 or more. However, formulation of components and formulation of concentrations have not been possible to date.

The volume fraction on the lamellae droplets can be measured by the following method. That is, if the composition is centrifuged at 40,000 G for 12 hours, the composition is separated into a clear (continuous aqueous) layer, a cloudy and reactive (lamellae) layer and a third layer (if solid or liquid is suspended). . The conductivity of the total aqueous phase before the continuous aqueous phase, lamellar phase and centrifugation is measured. From these, the Brugeman equetion, as described in "American Physics", vol. 24, pp. 636, 1035, is used to calculate or calculate the volume fraction of the lamellae phase.

The viscosity of the continuous aqueous phase is preferably 25 mPas or less, more preferably 15 mPas or less, particularly 10 mPas or less, and these viscosities are measured using a capillary viscometer, for example an Ostwald viscometer.

In terms of practical ease, i.e., in terms of product properties, the term "deagglomeration" for polymers means that the same amount of composition minus the polymers has a significant high viscosity or becomes unstable. It does not imply the use of a polymer that increases viscosity but does not increase the stability of the composition. It also does not imply a dilution effect, i.e. the use of polymers which can simply lower the viscosity by addition to the volume of the continuous phase. Although within the scope of the present invention, relatively high levels of deagglomerated polymers can be used in these systems where a decrease in viscosity occurs: usually at a low polymer level, such as about 0.01% to about 2.0% by weight, the viscosity at 21S- ¹ Can be reduced to level 2.

In particular, the product of the preferred embodiment of the present invention shows little phase separation during storage and has a lower viscosity than the same amount of composition without any deaggregating polymer.

The product of the preferred embodiment of the present invention exhibits a smaller droplet size than the equivalent amount of the composition without any deaggregating polymer. From US 3 974 076 it has been known that smaller droplet sizes increase fabric softening, but in the past these small droplets could only be obtained by high energy processes.

Based on no particular interpretation or theory, Applicants have assumed that the polymer exerts its action on the composition by the following mechanism. That is, the hydrophobic side chain (s) can be mixed only in the outer multilayer of lamells and droplets, leaving hydrophilic polyaxiality on the surface of the droplets. In addition, the polymer may be mixed into the inner depth of the droplet.

If the hydrophobic side chains are mixed only within the outer multilayer of the droplet, this has a decoupling effect of the force between the droplets and the inter-and intra-droplet force. That is, the difference between the forces between the softener molecules in the adjacent layer and the forces between the softener molecules in the adjacent droplets and the forces between the softener molecules in the adjacent droplets within each droplet means that the attraction between adjacent droplets is significantly reduced. do. This will generally result in an increase in stability due to lower cohesion and a decrease in viscosity due to a greater distance between droplets as the force between adjacent droplets becomes smaller.

If the polymer is mixed deeper into the interior of the droplet, less aggregation will also occur, resulting in increased stability. The influence on the viscosity of these polymers inside the droplets is governed by two opposing effects. First, the presence of the uncoupling polymer will reduce the attraction between adjacent droplets, resulting in a greater distance between droplets, resulting in a lower viscosity of the system. Secondly, the attraction between the layers within the droplets is equally reduced by the presence of polymer in the droplets, which generally leads to an increase in the thickness of the water layer, together with an increase in the lamellar volume of the droplets, together with an increase in viscosity. The ultimate effect of these two opposing effects can lead to a decrease or increase in the viscosity of the product.

In the patent specification relating to aqueous fabric softening compositions, it is possible to define the stability of the composition using the separation of the volumes observed during storage for a set period of time at a fixed temperature. In fact, this may be an oversimplification of what is actually observed. So, I would like to explain in more detail.

In the lamellar droplet dispersion, when the volume fraction of the lamellar phase is 0.6 or less and the droplets agglomerate, it is observed that instability is inevitable and phase separation occurs largely within a relatively short time. If the volume fraction is 0.6 or less but the droplets do not aggregate, the composition may be stable or unhappy. If unstable, phase separation occurs at a slower rate than agglomerated, and the degree of phase separation is less.

If the volume fraction of the lamellae is 0.6, it is possible to define the stability according to conventional methods, whether the droplets are agglomerated or not. The stability for these systems in the present invention can be defined as the maximum phase separation that is acceptable in most manufacturing and retail industries. That is, a "stable" composition is a composition that has a phase separation of 2% by volume or less, such that a phenomenon of separation into two or more layers is observed when stored at 25 ° C for 21 days from the time of manufacture.

In the case of compositions with a lamellae phase fraction of at least 0.6, it is not always easy to apply the above definition. In the case of the present invention, such a system may be stable or unstable, depending on whether or not the droplet is agglomerated. Even when unstable, ie when aggregated, the degree of phase separation is relatively low compared to, for example, unstable non-agglomerated systems with low volume fractions. In this case, however, phase separation does not appear to be the same as the pronounced appearance of other layers in the continuous phase, but may appear to split like a “crack” through the product. It is almost impossible to measure with very high precision the onset of these cracks and the volume of material contained. However, those skilled in the art can find out the instability because the technician can easily visually recognize the presence of phase separation divided by more than 2% by volume of the total composition. Thus, in formal terms, the above-mentioned "stable" provisions may apply to these situations, but ignore the requirement of phase separation to appear as a separation layer.

Particularly preferred embodiments of the present invention yield a visually apparent phase separation of less than 0.1 volume% after storage at 25 ° C. for 21 days from the time of manufacture.

It should also be realized that there may be some difficulties in measuring the viscosity of unstable fabric softening compositions.

When the volume fraction of the lamellae phase is 0.6 or less and the system is deaggregated, or when the volume fraction is 0.6 or more and the system is agglomerated, phase separation occurs relatively slowly, and precise viscosity measurement can usually be measured very easily. For all compositions of the present invention, these viscosities are preferably at most 2.5 Pas, more preferably at most 1.0 Pas, particularly at most 750 mPas, at a shear rate of 21S- ¹ .

When the volume fraction of the lamellae is below 0.6 and the droplets are agglomerated, phase separation often occurs quickly, making precise determination of the viscosity rather difficult. However, in the compositions according to the invention, it may be possible to obtain approximate values sufficient to present the effect of the deagglomerated polymer. This difficulty is then indicated in the illustrated compositions.

The composition according to the invention may comprise one deagglomerated polymer type or mixtures thereof. In practice, the term "polymer type" is used because almost all polymer samples have a structure and molecular weight and often spectra of impurities. Thus, the structure of any deagglomerated polymer described herein refers to a polymer believed to be effective for deagglomeration purposes as defined above. Indeed these effective polymers may constitute only a portion of the polymer sample if the amount of deagglomerating polymer in the total amount is sufficient to achieve the desired deagglomeration effect. Moreover, the structures described in the present invention for the individual polymer types refer to structures of polymers which exhibit excellent deagglomeration effect, wherein the above-mentioned molecular weight is the weight average molecular weight of the deagglomerating polymer.

이상, 더 바람직하게는 5g/

이상, 더욱 바람직하게는 10g/

이다.In general, the hydrophilic polyaxiality of a polymer is a linear, branched, or cross-cyclic molecular composition consisting of a small amount of relatively hydrophilic units, if possible, combining at least one relatively hydrophilic monomer unit. The only limitation to the structure of the hydrophilic polyaxiality is that the polymer must be able to be mixed into the active-structured aqueous liquid softener composition, while the hydrophilic polyaxiality is relatively water soluble, solubility in water at pH 7.0, 20 ° C. is preferably 1 g /

Or more, more preferably 5 g /

Or more, more preferably 10 g /

to be.

Hydrophilic polyaxiality is mainly linear in that the main chain of the polyaxial axis consists of at least 50% by weight, preferably at least 75% by weight and more preferably at least 90% by weight of the polyaxial axis.

Hydrophilic polyaxiality consists of monomer units, which can be selected from a variety of units used to prepare polymers. The polymer may be linked by any possible chemical ring, but the following forms of bonding are preferred.

이상, 더 바람직하게는 5g/

이상, 더욱 바람직하게는 10g/

이상을 형성한다.Water soluble monomers, suitably used to form hydrophilic polycondensation, are, for example, those which are soluble in water enough to form a solution of at least 1% by weight when dissolved in water, and are easily polymerized, resulting in pH Preferably 1 g / polymer of water soluble under 3.0-12.5 and at ambient temperature

Or more, more preferably 5 g /

Or more, more preferably 10 g /

It forms an ideal.

Examples of monomers soluble in water include acrylamide, methacrylamide and their N-substituted derivatives, namely 2-acrylamino-2-methylpropanesulfonic acid, N- (dimethylaminomethyl) acrylamide, N- (trimethylammonium). Ethylenically saturated amides such as ummethyl) acrylamide chloride and N- (trimethylammoniumpropyl) methacrylamide chloride: acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citracon Dicarboxylic acids such as acids or ethylenically unsaturated carboxylic acids: and other ethylenically unsaturated quaternary ammonium compounds such as vinylbenzyl trimethyl ammonium chloride: hydroxyethyl (meth) acrylate: sulfoalkyl of unsaturated carboxylic acids such as 2sulfoethyl methacrylate Ester: 2-amino ethyl methacrylate, dimethyl aminoethyl (meth) acrylate, diethyl amino Aminoalkyl esters of unsaturated carboxylic acids such as ethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, and quaternary ammonium salts thereof: with vinyl pyridine and vinylmorpholine or allylamine Such as vinyl or allylamine: diallylamine and diallyl ammonium compounds such as diallyl dimethyl ammonium chloride: vinyl heterocyclic amides such as vinyl pyrrolidone: sodium alkyl sulfonate: vinylaryl sulfonate such as vinylbenzyl sulfonate: vinyl Vinyl alcohol obtained by hydrolysis of acetate: vinyl acetic acid: sodium vinyl sulfonate: sodium allyl sulfonate similarly to the salt of the monomer mentioned above. These monomers may be used alone or as a mixture thereof.

이하인 중합체로 부터 유도된 것들을 함유할 수 있다. 비교적 물에 녹지않는 중합체의 예로는 폴리비닐 아세테이트, 폴리메틸 메쓰아크릴레이트, 폴리에틸 아크릴레이트, 폴리에틸렌, 폴리프로필렌, 폴리스티렌, 폴리부틸렌 산화물, 폴리프로필렌 산화물, 폴리히드록시프로필 아크릴레이트가 있다.In some cases, the hydrophilic polyaxiality has a solubility in water of 1 g / a provided that the total solubility of a small amount of relatively hydrophobic units, for example the hydrophilic polymer polyaxial, meets the solubility requirements specified above.

It may contain those derived from the following polymers. Examples of relatively water insoluble polymers are polyvinyl acetate, polymethyl methacrylate, polyethyl acrylate, polyethylene, polypropylene, polystyrene, polybutylene oxide, polypropylene oxide, polyhydroxypropyl acrylate.

In general, suitable hydrophobic monomers for forming side chains are (1) insoluble in water, i.e., 0.2 parts by weight or less of hydrophobic monomer is dissolved in 100 parts by weight of water, and (2) ethylenically unsaturated compounds having hydrophobic moieties. .

이하, 더 바람직하게는 0.5g/

이하, 더욱 바람직하게는 0.1g/

이하이다.Hydrophobic moieties (if separated from their polymerizable bonds) are relatively insoluble in water and solubility in water at pH 3.0-12.5 and room temperature is preferably 1 g /

Or less, more preferably 0.5 g /

Or less, more preferably 0.1 g /

It is as follows.

The hydrophobic moiety is preferably an organic group accessory having 5 carbon atoms and more preferably having hydrophobicity comparable to the following: aliphatic having 5 or more carbons such as C ₅ -C ₅₀ alkyl and cycloalkyl Hydrocarbon group: Polynuclear aromatic hydroxyl group such as naphthyl: Alkylaryl having an alkyl group of at least one carbon: Haloalkyl having at least 5 carbons, preferably perfluoroalkyl: Alkylene is propylene or Polyalkyleneoxy groups with higher alkylene and at least one alkyleneoxy unit per hydrophobic moiety: and siloxane moieties. Typical hydrophobic monomers include dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, male Octylhalp esters of acid anhydrides, doictyl diethyl maleate, and other alkyl esters and alkanols having 5-50 carbon atoms, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and aconic acid Higher alkyl esters of alpha, beta-ethylenically unsaturated carboxylic acids, such as half esters derived from the reaction of ethylenically unsaturated carboxylic acids, such as nonyl-phenyl methacrylate, dodecyl-phenyl acrylate and dodecyl-phenyl methacrylate. Alkylaryl esters of ethylenically unsaturated carboxylic acids like: N-octadecyl a N-alkyl, such as krillamide, ethylenically unsaturated amides: N-octadecyl methacrylamide, N, N-dioctyl acrylamide, such as octene-1, decene-1, dodecine-1 and hexedecene-1- and Analogous derivatives thereof, -olefins: vinyl alkylates in which alkyl has four or more carbon atoms such as vinyl laurate and vinyl stearate: vinyl alkyl ethers such as dodecyl vinyl ether and hexadecyl vinyl ether: N-vinyl lauamide And N-vinyl amide, such as N-vinyl stearamide, and alkyl styrene, such as t-butyl styrene.

Hydrophobic monomers may be used alone or in a mixture thereof. The ratio of hydrophilic monomers to hydrophobic monomers can vary from about 500: 1-5: 1. The resulting weight average molecular weight (Mw) of the polymer varies from 500-500,000 or more when measured as compared to gel permeation chromatography using polyacrylate standard or standard viscosity (SV) measurement using polyacrylate standard. Can be.

It is preferable that the product of this invention contains the polymer of the following general formula.

Where Z is 1, (x + y): Z is 5: 1-500: 1, and the monomer units may be in any order. y is preferably a number from 0 to at most x and n is at least 1. R ¹ may be —CO—O, —O—, —O—CO—, —CH ₂ , —CO—NH—, or may be omitted. R ² is possible when the alkylene tableware, preferably ethylene oxide groups or propylene oxide groups or 1 to 50 of a group selected independently from, or omitted, which is not R ³ and R ⁴ represents hydrogen, R ² Is assumed to contain an alkyleneoxy group having at least 3 carbon atoms: R ³ is a phenylene bond or omitted: R ⁴ represents hydrogen or a C _5-24 alkyl or C _5-24 alkenyl group (a ) When R ¹ is -O-CO-, R ² and R ³ are omitted, R ⁴ must contain at least 5 carbon atoms, and (b) when R ² is omitted, R ⁴ must not be hydrogen and R ^{If 3} is omitted, it is assumed that R ⁴ must contain at least 5 carbon atoms: R ⁵ represents hydrogen or a group of formula —COOA ⁴ : R ⁶ represents hydrogen or C _1-4 alkyl: and A ¹ , A ^2, A ³ and A ⁴ is hydrogen, alkali metal, alkaline earth metal, ammonium and amine It is independently selected from the group.

Another class of polymers according to the invention contains those of general formula II:

Where: Q is a molecular unit with the general formula (IIa):

Wherein Z and R ^1-6 are as defined in formula (I): A ^1-4 is as defined in formula (I).

Q ¹ is a multifunctional monomer that allows for pruning of the polymer, and the monomers of the polymer can be combined with Q ¹ in any direction and in any order, thereby allowing the result of the pruned polymer. Q ¹ is preferably trimethyl propane triacrylate (TMPTA), methylene bisacrylamide or divinyl glycol:

n and Z are as defined above: V is 1: and (x + y + p + q + r): Z is 5: 1-500: 1: The monomer units may be in any order: And it is preferred that either p and q are 0, or r is 0: R ⁷ and R ⁸ represent —CH ₃ or —H: R ⁹ and R ¹⁰ represent amino, amine, amide, sulfonate, sulfate , A phosphonate, phosphate, hydroxyl, carboxyl and oxide group, or a substituent such as (C ₂ H ₄ O) _t H, where t is 1-50, and the monomer units may be in any order. These are -SO ₃ Na, -CO-OC ₂ H ₄ -OSO ₃ Na, -CO-NH-C (CH ₃ ) ₂ -CH ₂ -SO ₃ Na, -CO-NA ₂ , -O-CO-CH ₃ It is preferable to select from -OH. In particular the sample of polymeric material in the polymers of formulas (I) and (II) is formed of salts. Usually some polymers can be completely salts (A ¹ -A ⁴ are all other than hydrogen), some polymers can be completely acids (A ¹ -A ⁴ are all hydrogen), and some polymers are partially Salts (at least one of A ¹ -A ⁴ and at least one other than hydrogen).

The salts of the polymers in formulas (I) and (II) are formed with any organic or inorganic cation defined for A ¹ -A ⁴ , which can form salts that are soluble in water with lower molecular weight carboxylic acids. have.

Another class of polymers according to the invention contains those of the general formula (III);

Wherein Q ³ is derived from monomer unit (IIIa):

Q ⁴ is derived from molecular units having the general formula (IIIb):

And Q ⁵ is derived from a molecular unit having the general formula (IIIc).

R ¹ -R ⁶ are defined as in general formula (I): (a + b + c): Q ⁴ is 5: 1-500: 1, and the monomer units may be in any order.

a, b, c, d, e, f, g, h are integers or 0 and n is at least ¹ : B ¹ , B ² , B ³ , B ⁴ is an organic or inorganic anion: W is 0-4 R ¹¹ and R ^{11 *} are independently selected from hydrogen or C ₁ -C ₄ alkyl: and R ¹² is independently from C ₅ -C ₂₄ alkyl or alkenyl, aryl cycloalkyl, hydroxyalkyl or alkoxyalkyl Is selected.

Examples of the anions represented by B ¹ , B ² , B ³ , B ⁴ include halide ions, sulfates, sulfonates, phosphates, hydroxides, borates, cyanides, carbonates, bicarbonates, thiocyanates, sulfides, cyanates , Acetates, and other common inorganic and organic ions. Preferred anions are chloride and methosulfate.

Another class of polymers according to the invention contains those of formula (IV);

Wherein R ¹ -R ⁶ are as defined in general formula (I). R ^{6 *} represents H or C _1-4 alkyl, Z is 1 and J: Z is 5: 1-500: 1. The monomer units may be in any order, n is one or more: R ¹³ may represent or omit -CH _2- , -C ₂ H _4- , C ₃ -H _6- . R ¹⁴ may represent or omit 1-50 groups independently selected from alkyleneoxy groups, preferably ethylene oxide groups. R ¹⁵ represents -OH or hydrogen.

The general formulas (I), (II), (III) and (IV) are to be interpreted as including these mixed copolymer forms, in which n is at least 2 and R ¹ -R ¹⁵ are individually within a particular polymer molecule. Is different between monomer units.

For polymers of formulas (I), (II) and (IV) and their salts, when measured by GPC using polyacrylate standards, their weight average molecular weight is 500-500,000, preferably 1000-200,000 More preferably in the region of 1500-50,000.

For the purpose of this definition, the molecular weight of a standard is absolute absolute published by Noda, Tsogge, and Nagasawa in the Journal of Physical Chemistry, 1970, Vol. 74, pp. 710-719. It is measured by the viscosity intrnsic viscosity method.

It is difficult to accurately measure the molecular weight distribution of the polymer of formula (III). It is due to the high cationic nature of these polymers and their subsequent absorption on the GPC column. Instead, the measurement of molecular weight can be made by measuring standard viscosity (S, V), which is a Brookfield synchro-electric (R) (Model LVT) with LCP adapter at a speed of 60 RPM. BrooKfield synchro-lectic (R)) was used to measure at 23 ° C., 15% solids in 1.0 molar sodium chloride solution. The polymer preferably has an S.V of 1-100 mPas, more preferably 2-50 mPas, more preferably 3-25 mPas.

Empirically, it has been found that the following relationship exists between SV and mW (polyacrylamide basis).

log ₁₀ MW = 1.4 log ₁₀ Sv + 2.5

The polymers for use in the compositions of the present invention are preferably prepared by the process as described in UK patent application 8813966.2.

In general, the deagglomerated polymer can be used in the composition at 0.01-5.0% by weight, more preferably 0.1-2.0% by weight.

Many emollient materials form lamellae dispersions of emollients only in water, although in some cases they are more preferred in aqueous continuous phases containing dissolved electrolytes. As used herein, the term "electrolyte" means an ionic material that is soluble in any water. However, in the lamellar dispersion, the electrolyte does not necessarily need to be dissolved, but may be suspended as solid particles because the total electrolyte concentration of the liquid is larger than the solubility limit of the electrolyte. Mixtures of electrolytes may also be used, which have at least one electrolyte dissolved in the aqueous phase and at least one electrolyte sufficient only in the suspended solid phase. Also, more than 12 electrolytes can be distributed roughly in proportion between these two phases. In part, this may depend on the manufacturing process, for example the order of addition of the components.

The only limitation on the total content of emollient material and electrolyte (if any) is that they together form an aqueous lamellar dispersion in the composition of the present invention. Thus, within the scope of the present invention, a wide range of variations in softener type and level may be possible. In order to obtain a stable liquid with the required structure, the choice of softener types and their properties can be entirely within the skill of the person skilled in the art.

The composition of the present invention preferably contains 1-80% by weight of the fabric softening composition, more preferably 10-70% by weight, more preferably 20-60% by weight of the composition. Fabric softening compositions can be selected from cationic, nonionic, amphoteric or anionic fabric softening compositions. The level of dissolved electrolyte is typically 0-20% by weight, more preferably 0.01-10% by weight, more preferably 0.1-5% by weight of the composition.

보다 적은 농도의 미립자 분산을 형성하는, 직물을 본래의 상태에 가깝도록 하는 양쪽성 물질이다. 본 발명의 목적을 위해서, 직물을 본래의 상태에 가깝도록 하는 양쪽성 물질은, 단지 한개의 긴 히드로카빌 측쇄이거나 두개의 긴 히드로카빌 사슬을 갖는 양쪽성 또는 쯔비터이온성 3차 또는 4차 암모늄 화합물인 것이 바람직하다. 이들 화합물로부터, 두개의 긴 히드로카빌 사슬을 갖는 양쪽성 또는 쯔비터이온성 암모늄 화합물의 사용은 비용, 제조공정의 용이성 및 더 나은 안정성 및 실용성 등의 많은 이유로 특히 바람직하다. 적합한 양쪽성 물질의 예로는 EP326 213에 기술되어 있다.Suitable amphoteric fabric conditioning materials for use in the compositions according to the invention are at least one temperature between 0-100 ° C., preferably at least one temperature between 10-90 ° C., more preferably 20-80 ° C. At the temperature of 1g /

It is an amphoteric material that brings the fabric closer to its original state, forming a smaller concentration of particulate dispersion. For the purposes of the present invention, the amphoteric material which brings the fabric closer to its original state is an amphoteric or zwitterionic tertiary or quaternary ammonium compound having only one long hydrocarbyl side chain or two long hydrocarbyl chains. Is preferably. From these compounds, the use of amphoteric or zwitterionic ammonium compounds with two long hydrocarbyl chains is particularly desirable for many reasons, including cost, ease of manufacturing process and better stability and practicality. Examples of suitable amphoteric materials are described in EP326 213.

In the present specification, the expression hydrocarbyl chain refers to a linear or branched alkyl or alkenyl chain, and in some cases substituted or interrupted by a functional group such as -OH, -O-, -CONH-, -COO- and the like. do.

이하인 것이 바람직하다.Amphoteric materials which bring the fabric closer to its original state are preferably soluble in water, with a water solubility of 10 g / 20 at 20 °, pH 2.5.

It is preferable that it is the following.

Preferably, the HLB of the amphoteric material to bring the fabric close to its original state is 10.0 or less.

이하이다.Suitable cationic fabric softener materials for use in the compositions according to the invention are water insoluble cationic materials and the solubility of these materials in water at pH 2.5 and 20 ° C. is 10 g /

It is as follows.

Most preferred are cation quaternary ammonium salts with two C _12-24 hydrocarbyl chains.

Known kinds of quaternary ammonium compounds that are not sufficiently soluble in water have the following formula;

Wherein R ₁ and R ₂ represent a hydrocarbyl group having from about 12 to about 24 carbon atoms: R ₃ and R ₄ represent a hydrocarbyl group containing from 1 to about 4 carbon atoms: and X is an anion, preferably Is selected from halides, methosulfate and ethylsulfate radicals.

Typical examples of these quaternary chlorides include ditallow dimethyl ammonium chloride; Dietel dimethyl ammonium methyl sulfate; Dihexadecyl dimethyl ammonium chloride; Di (hydrogenated tallow) dimethyl ammonium methyl sulfate: dihexadecyl diethyl ammonium chloride: di (coconut) dimethyl ammonium chloride. Also preferred are ditallow dimethyl ammonium chloride di (hydrogenated tallow) dimethyl ammonium chloride, di (coconut) dimethyl ammonium chloride and di (coconut) dimethyl ammonium methosulfate.

Also suitable are dialkyl ethoxyl methyl ammonium methosulfate based on soft fatty acids, dialkyl ethoxyl methyl ammonium methosulfate based on hard fatty acids and R ₃ and R _{4 represented} by methyl, wherein R ₁ is C _13-15 , R ₂ is CH ₂ CH ₂ OCOR, where R is stearyl, and X is methosulfate. Preferred are ditallow dimethyl ammonium chloride, di (hydrogenated tallow alkyl) dimethyl ammonium chloride, di (coconut alkyl) dimethyl ammonium chloride and di (coconet alkyl) dimethyl ammonium methosulfate.

The following cationic compounds include these materials as described in EP239,910 (P & G), which is incorporated herein by reference.

Other preferred materials are those of the formula:

R ₅ is a tallow, commercially available from Stefan under the trademark Stepanetex VRH 90. And

R ₈ , R ₉ and R ₁₀ are each alkyl, a hydroxyalkyl group containing 1-4 carbon atoms, or a benzyl group. R ₆ and R ₇ are each an alkyl or alkenyl chain containing 11-23 carbon atoms, and X ⁻ is an anion that is well soluble in water. These materials and their preparation are described in US 4 137 180 (LEVER BROTHERS).

Another preferred class of insoluble cationic materials is the hydrocarbylimidazolinium salt believed to have the formula:

Wherein R ₁₃ is a hydrocarbyl group containing 1-4 carbon atoms, preferably 1-2 carbon atoms. R ₁₁ is a hydrocarbyl group containing 8-25 carbon atoms. R ₁₄ is a hydrocarbyl group containing 8-25 carbon atoms, and R ₁₂ is hydrogen or a hydrocarbyl containing 1-4 carbon atoms. A ⁻ is an anion, preferably a halide, methosulfate or ethosulfate.

Preferred imidazolinium salts are 1-methyl (tallowyl amido) ethyl-2-teloyl-4,5-dihydroimidazolinium methosulfate and 1-methyl-1- (palmitoylamido) Ethyl-2-octadecyl-4,5-dihydro-imidazolinium chloride. Other useful imidazolinium materials include 2-heptadecyl-1-methyl-1 (2-stearyl amido) -ethyl-imidazolinium chloride and 2-lauryl-1-hydroxyethyl-1-ore Mono-imidazolinium chloride. Also suitable here is the imidazolinium fabric chloride composition of US Pat. No. 4,127,489, mixed by reference.

Typical commercially available materials of this class are Aquad 2HT (AKZO), a quaternary ammonium compound: Noramium M2SH (CHCA) 1 Arikuat-2HT (trademark of General Mills, Inc.), Stefanex Q185 (Stephan) : Stefanepex VP85 (Stephans): Stephenpans VRH 90 (Stephans): Cynproram FS (ICI) and imidazolinium compound Barisoft 475 (trademark of Colombos Ohio, Sherex) and Ryuquat W 7500 (Ryuo's trademark).

The compositions according to the invention may also contain one or more amine softeners in addition to the softeners mentioned above.

The term "amine" as used herein may be mentioned as follows.

(i) amines of the formula:

Wherein R ₁₅ , R ₁₆ and R ₁₇ are defined as follows.

(ii) amines of the formula:

Wherein R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , m and n are defined as follows.

(iii) imidazolines of the formula:

Wherein R ₁₁ , R ₁₂ and R ₁₄ are defined as above.

(iv) The condensation product is formed by reaction of a fatty acid with a polyamine selected from the group consisting of hydroxy alkylalkylenediamine and dialkylenetriamine and mixtures thereof. Suitable materials are described in European Patent Application No. 199 382 (Procter and Gamble), which are incorporated herein by reference.

In the above, when the amine is of formula (I), R ₁₅ is a C ₆ -C ₂₄ hydrocarbyl group, R ₁₆ is a C ₁ -C ₂₄ hydrocarbyl group, and R ₁₇ is a C ₁ -C ₁₀ hydrocarbyl group. Suitable amines contain these materials derived from the quaternary ammonium compounds described above, wherein R ₁₅ is R ₁ , R ₁₆ is R ₂₂ and R ₁₇ is R ₃ . The amine is most preferably C ₆ -C ₂₀ alkyl wherein both R ₁₅ and R ₁₆ AH have C ₁₆ -C ₁₈ , R ₁₇ is C _1-3 alkyl, or R ₁₅ is alkyl having at least 22 carbon atoms or An alkenyl group, and R ₁₆ and R ₁₂ are C _1-3 alkyl. These amines are preferably protonated using hydrochloric acid, artophosphoric acid (OPA), C _1-5 carboxylic acid or any other similar acid for use in the fabric conditioning composition. .

When the amine is of formula (II), R ₁₈ is a C ₆ -C ₂₄ hydrocarbyl group, R ₁₉ is an alkoxylated group of formula-(CH ₂ CH ₂ O) _y H, wherein y is in the range of 0-6 Mine R _20y is an alkoxylated group of the _formula- (CH ₂ CH ₂ O) _Z H, wherein Z is in the range of 0-6. m is an integer in the range of 0-6, Preferably it is 3. When m is 0, R ₁₈ is C ₁₆ -C ₂₂ alkyl, and the sum of Z and y is preferably in the range of 1-6, more preferably 1-3. When m is 1, R ₁₈ is C ₁₆ -C ₂₂ alkyl and the sum of x and y is preferably in the range of 3-10.

Typical commercially available materials of this class include exomine (amor) and exoduomin (amor).

It is also preferred that the form (ii) or (iii) of the amine is protonated for use in the fabric softening composition of the present invention.

In case the amine is in the form (iv) given above, the following substances are particularly preferable;

Wherein R ₂₂ and R ₂₃ are divalent alkenyl chains having 1-3 carbon atoms, and R ₂₄ is an acrylic aliphatic hydroxylcarbon chain having 15-21 carbon atoms. A commercially available substance of this class is Seranine HC39 (Sandoz).

Another class of polymers according to the invention contains the general formula (IV) as follows.

Wherein R ¹ -R ⁶ are defined as in formula (I), Z is I and J: Z is 5: 1-500: 1. The monomer units may be in any order, n is one or more: R ¹³ may be —CH ₂ —, C ₂ H ₄ —, C ₃ H ₆ — or may be omitted. R ₁₄ may be omitted from 1-50 groups independently selected from alkyleneoxy, preferably ethylene oxide groups. R ¹⁵ represents -OH or hydrogen.

The composition according to the invention preferably has a pH of 0.6 or less, more preferably 5.0 or less and more preferably 2.0-4.0.

The composition also comprises one or more optional components selected from non-aqueous alcohols such as C ₁ -C ₄ alkanols and polyhydric alcohols, pH-buffering agents such as phosphoric acid, benzoic acid, citric acid, non-wetting agents as weak acids. re-wetting agents, viscosity modifiers, aluminum chlorohydrates, antigelling agents, fragrance-reducing fragrances, fragrance carriers, hydrocarbons, fluorescents, colorants, hydrotrope, foam inhibitors, re-deposition Stabilizers such as inhibitors, enzymes, optical brightening agents, bleaches, guar gums and polyethylene glycols, shrinkage agents, silicones, dirt release agents, antioxidants, corrosion inhibitors, to preserve textile treatment compositions Preservatives, such as bronopol (trademark), commercially available in the form of 2-bromo-2-nitropropane-1,3-diol, bleach precursors, wrinkle-imparting agents Antistatic agents and ironing aids.

If added, these optional ingredients may each be present at levels up to 5% by weight of the composition.

The invention is further illustrated by the following examples.

Example I-XII

In Examples I-XII, the following polymers are used. Each polymer is obtained from National Starch and Chemicals, Specialty Polymer Division, as an aqueous solution containing 30-60% by weight of solids. All percentages for polymers refer to 100% active polymers.

Basic structure of a polymer: general formula (I)

Where R ₁ = COO, R ₂ is omitted, R _{3 is} omitted

R ₅ = H, R ₆ = CH ₃ and y = 0 and A ¹ = H

Basic structure of the polymer: general formula (II)

Where R ₈ = H, R = 0, B = 1: Q ₂ : x = y = 0, R ₁ = COO, R ₂ and R ₃ are omitted

R ₅ = H, R ₆ = CH ₃

Basic structure of a polymer: general formula (III)

Where b = c = 0, R ₆ = CH ₃ , d = 1

In IIIa, R ₁₁ = H, R ₁₁ * = CH ₃ , B ₂ = C ₁

In IIIb, e = 1, f = g = h = i = 0, R ₁ = COO

R ₃ is omitted, R ₅ = H, B ₃ = Cl

Basic structure of a polymer: general formula (IV)

Where R ₁ = 100, R ₂ and R ₃ are omitted, R ₆ = CH ₃ , R ₁₃ are omitted

Example I

The fabric softening composition was prepared by adding the deagglomerating polymer and electrolyte to water under stirring and then adding the softening material which had been preheated to 50 ° C. The fabric softener was Aquad 2T (Dimethyl Ditalo Ammonium Chloride = DMDTAC, manufactured by Atlas). The pH of the composition was adjusted to 4.0 using ortho phosphoric acid.

The following composition was obtained:

Preheated to remove solvent.

Compositions A and B were stable fabric softening compositions that were found at room temperature for several weeks and found no initial phase separation. They had a viscosity of about 400 mPas at 21S- ¹ and had a good dispersion that was well dispersed in water at room temperature. Composition C was in gel form, translucent and exhibited an unsuitable degree of dispersion in water.

Example II

The following composition was prepared as in Example (I). The fabric softener was Stepanetex VRH 90, an ester-ring quaternary ammonium material that was preheated to remove any solvent present.

Preheated to remove solvent

** C _9-11 alcohol ethoxylated with 6EO group (shell product)

Formulation A-D was a fabric softening composition that found no visible phase separation after several weeks of storage at room temperature. Compositions B-D had a viscosity that met the conditions and could be well dispersed in water at room temperature. Composition A exhibited unsuitable viscosity and poor dispersion.

Example III

The following composition was prepared as in Example (I).

* Polyethylene of 200 molecular weight

** Preheated to remove with solvent.

The composition AD was a stable fabric softening composition, which was not found any temporal phase separation even when stored at room temperature. Composition AC had a viscosity of about 400 mPas at 21S- ¹ and had a good dispersion. Composition D was unsuitable viscosity.

Example IV

Citrate was added to water at room temperature followed by the addition of fabric softener to prepare the following formulation. The polymer was added as final component at room temperature.

In addition to the formulation

** 70% active / 20% isopropyl alcohol / 10% water

Compositions A and B were more stable than composition C. Compositions A and B are pourable milky liquids, while composition C was a milky gel that exhibited 12% by volume phase separation in day storage at room temperature.

Example V

The following composition was prepared as in Example (I).

* 70% active / 20% isopropyl alcohol / 10% water

Compositions A and B were stable, pourable milky liquids. Composition C was an unstable translucent milky gel.

Example VI

The following composition was prepared as in Example (I).

* 70% active / 20% isopropyl alcohol / 10% water

Composition D was a pourable translucent liquid that separated into two translucent layers within two days. Compositions A-C were pourable milky liquids with the correct stability.

Example VII

The following formulation was prepared as in Example (I).

* 70% active / 20% isopropyl alcohol / 10% water

Composition D was a pourable milky white liquid that separated into two layers in one minute. Compositions A-C had suitable stability and could be poured out and show no discoloration during storage.

Example VIII

The following fabric softening composition was prepared according to Example (I). All compositions were stable transparent products with viscosities of about 21 S ⁻¹ to about 250 mPas and could be well dispersed in water at room temperature.

* 70% active / 20% isopropyl alcohol / 10% water

Example IX

The following fabric softening composition was prepared according to Example (I). All compositions were stable milky white translucent products with a viscosity of about 21S ⁻¹ to about 400 mPas. The degree of dispersion of the product in water at room temperature was good.

* 70% active / 20% isopropyl alcohol / 10% water

Example X

The following composition was prepared as in Example (I). All products are stable and have a viscosity and dispersion to suit the conditions.

* A mixture of 1,2-di tallow oxytrimethyl ammonium propane chloride and 1-tallow 2-hydroxy trimethyl ammonium propane chloride 70/30

** Same as Example I

Example XI

Calcium chloride was added to water, premixed to add heated fabric softener and nonionic material, and finally polymer was added to prepare a fabric softening composition. The fabric softener was Aquad 2HT (dimethyl dihydrogenated tallow ammonium chloride DMDHTAC) from Atlas. The nonionic material was Xenopol T050 from Chast product as tallow alcohol ethoxylated with 5 moles of ethylene oxide. pH was adjusted to between 3.5-4 using orthophosphoric acid.

The following composition was obtained:

Compositions A and B were stable fabric softening compositions that found no visible phase separation after several weeks of storage at room temperature. They had a viscosity of about 400 mPas at 21S- ¹ .

Example XII

The following composition was prepared by dispersing the polymer in the aqueous base material before adding the fabric softener.

These compositions were found to have a droplet size of 1 micron when measured by face contrast microscopy. Formulations that do not contain a polymer generally have a droplet size of at least 3 microns.

Claims (13)

In a fabric softening composition containing an aqueous base material and at least one fabric softening material, the composition has a structure of lamellar droplets dispersed in the aqueous base material, and the composition further comprises a hydrophilic backbone and A fabric softening composition comprising a deagglomerated polymer comprising at least one hydrophobic side chain. The fabric softening composition of claim 1 wherein the deagglomerated polymer is of formula (I) as defined below:

[Wherein Z is 1 and (X + Y): Z is 5: 1-500: 1 and the monomer units may be in any order. Y is a number from 0 to X and n is at least ¹ : R ¹ is -CO-O, -O-, -O-CO-, -CH ₂ , -CO-NH- or can be omitted: R ² Is an alkyleneoxy group, preferably 1-50 groups independently selected from ethylene oxide groups or propylene oxide groups, or may be omitted, which when R ³ is omitted and R ⁴ is represented by hydrogen, R ² is It is assumed that it must contain an alkyleneoxy group having at least 3 carbon atoms: R ³ represents or may be omitted from the phenyl bond: R ⁴ represents hydrogen or C _5-24 alkyl or C _5-24 alkenyl groups, (a) when R ¹ is -O-CO-, R ² and R ³ are omitted, R ⁴ must contain at least 5 carbon atoms, and (b) when R ² is omitted, R ⁴ is hydrogen And if R ³ is omitted, it is assumed that R ⁴ must contain at least 5 carbon atoms: R ⁵ represents hydrogen or the group -COOA ⁴ Yields: R ⁶ represents hydrogen or C _1-4 alkyl: and A ¹ , A ² , A ³ and A ⁴ are independently selected from hydrogen, alkali metal, alkaline earth metal, ammonium and aminebase.] The fabric softening composition of claim 1 wherein the deagglomerated polymer is of formula (II) as defined below:

[Wherein, Q ² is a molecular unit having the formula (IIa):

(Where Z and R ^1-6 are as defined in formula (I) and A ^1-4 are as defined in formula (I)) Q ¹ is multifunctional to allow pruning of the polymer It is a monomer, and the monomer of the polymer may be combined with Q ¹ in any direction and in any order, thereby allowing the result of the branched polymer. It is preferred that Q ¹ is trimethyl propane triacrylate (TMPTA), methylene bisacrylamide or divinyl glycol: n and Z are as defined above: V is 1 and: (x + y + p + q + r): Z is 5: 1-500: 1: The monomer units may be in any order: and it is preferred that either p and q are 0, or r is 0: R ⁷ and R ⁸ are Represents —CH ₃ or —H: R ⁹ and R ¹⁰ are amino, amine, amide, sulfonide, sulfate, phosphonate, phosphate, hydroxyl, carboxyl and oxide groups, or (C ₂ H ₄ O) _t Substituents such as H, where t is 1-50 and the monomer units may be in any order. These are -SO ₃ N, -CO-OC ₂ H ₄ , -OSO ₃ Na, -CO-NH-C (CH ₃ ) ₂ -CH ₂ -SO ₃ Na, -CO-NA ₂ , -O-CO-CH ₃ , -OH is preferably selected.] The fabric softening composition of claim 1 wherein the deagglomerated polymer is of formula (III) as defined below:

[Wherein, Q ³ is derived from monomer unit (IIIa):

Q ⁴ is derived from molecular units having the general formula (IIIb):

And Q ⁵ is derived from molecular units having the general formula (IIIc).

R ¹ -R ⁶ are defined as in general formula (I): (a + b + c): Q ⁴ is 5: 1-500: 1, and the monomer units may be in any order. a, b, c, d, e, f, g, h are integers or 0 and n is at least ¹ : B ¹ , B ² , B ³ , B ⁴ are organic or inorganic anions: W is 0-4 : R ¹¹ and R ^{11 *} are independently selected from hydrogen or C ₁ -C ₄ alkyl: and R ¹² are independently selected from C ₅ -C ₂₄ alkyl or alkenyl, aryl cycloalkyl, hydroxyalkyl or alkoxyalkyl do. The fabric softening composition of claim 1 wherein the deagglomerated polymer is of formula (IV) as defined below:

[Wherein, R ¹ -R ⁶ are as defined in general formula (I). R ^{6 *} represents H or C _1-4 alkyl, Z is 1 and J: Z is 5: 1-500: 1. The monomer units may be in any order, n is one or more: R ¹³ may represent or omit -CH ₂ , -C ₂ H ₄ , -C ₃ H _6- . R ¹⁴ may represent or omit 1-50 groups independently selected from alkyleneoxy groups, preferably ethylene oxide groups. R ¹⁵ represents -OH or hydrogen.] The fabric softening composition according to claim 1, wherein the fabric softening composition contains 0.1-2.0% by weight of the composition. The fabric softening composition of claim 1 wherein the softener material comprises a cationic fabric softening material. The fabric softening composition according to claim 1, which contains 20 to 60% by weight of fabric softening material. The fabric softening composition according to claim 1, wherein the fabric softening composition contains 0.1-5.0% by weight of the dissolved electrolyte. The fabric softening composition of claim 1 having a pH of 6.0 or less. A method of producing a fabric softening composition containing an aqueous base material and at least one fabric softening material, having a structure of lamellar droplets dispersed in the aqueous base material, and containing a hydrophilic polyaxial and at least one hydrophobic side chain, A process for dispersing a deagglomerated polymer in an aqueous base material before adding softeners. Fabric softening in an aqueous liquid containing an aqueous base material and at least one fabric softening material and having a structure of lamellar droplets dispersed in the aqueous base material and containing a fabric softening composition containing hydrophilic polyaxiality and at least one hydrophobic side chain. A fabric processing method comprising contacting a fabric with said aqueous liquid when the concentration of material is 1-1000 ppm. In a fabric softening composition containing an aqueous base material and at least one fabric softening material, the composition is a fabric having a viscosity of 2.5 Pas or less in the use of a deagglomerated polymer containing hydrophilic polyaxiality and at least one hydrophobic side chain. Use of a deagglomerating polymer having a structure of lamellar droplets dispersed in an aqueous base material suitable for producing a softening composition.