EP3122853B1 - Liquid cationic formulation and method for the production thereof - Google Patents

Description

The present invention relates to a thickening concentrate for the continuous preparation of a liquid cationic formulation of household cleaners or softeners and to a process for the continuous production of a liquid cationic formulation of household cleaners or softeners in which a thickening concentrate according to the invention is used.

Liquid cationic formulations of household cleaners or fabric softeners are often aqueous or alcoholic formulations. In order to adapt the rheological properties of the respective formulation to the required application and to the customer's request, it is customary to add additives which influence the viscosity to the formulation. For example, these may be polymers. So describes WO 99/06455 A Thickening agents for acidic compositions comprising cationic homopolymers in a proportion of 50 to 600 ppm of crosslinking agent. Suitable polymers are, for example, in WO 2004/050812 A1 and WO 2005/073358 A1 described.

In the preparation of liquid formulations, however, it has been found that continuous metering of a corresponding polymer into the liquid cationic formulation is not possible or difficult, especially when present in solid form. Usually, liquid formulations are therefore produced in a batch mixer. In batch production, however, a constant quality over different batches can only be ensured with great effort, so that a consistent quality of the liquid cationic formulation is only possible within limits. Even within a batch, different concentrations of polymers can occur and thus quality differences.

Particularly suitable thickeners cationic acrylic polymers have emerged. These are usually present as a solid, for example in the form of a powder. Since the continuous metering of a powder is difficult to realize, solids are usually first dissolved in a suitable solvent or suspended in a suspending agent and then added as a solution or suspension to a liquid formulation. As solvents or suspending agents, preference is given to using those liquids which are also present in the actual formulation in order to obtain good intermixability. WO 2013/016029 A1 for example, discloses a method of making a composition comprising a rheological properties adjusting agent. In this process, a rheology additive is dispersed in an anhydrous but water-miscible liquid carrier material such as a surfactant, a humectant, a polymer, an oil, or mixtures thereof. It will be in Water-swellable polymers, non-water-soluble crystalline polymers or mixtures thereof used as a rheological additive.

If suitable cationic acrylic polymers are now introduced into a solvent which constitutes the main constituent of the liquid cationic formulation, they swell up. A tough, gummy mass is obtained which can no longer be added to the liquid cationic formulation in a continuous production process. There is therefore a need for the possibility of continuously producing a liquid cationic formulation in order to enable a cost-effective production process which at the same time enables a continuous, consistent quality of the product obtained EP 2399978 A discloses a nonaqueous liquid composition comprising: a cationic polymer in particulate form; a nonaqueous dispersing agent selected from the group consisting of ethanol, glycerol and polyethylene glycol having a molecular weight of 100 to 400; and less than 20% by weight of water, wherein the cationic polymer is stably dispersed in the nonaqueous liquid composition.

worin

R¹

für ein Wasserstoffatom steht oder gemeinsam mit R² unter Ringschluss eine Carbonylgruppe bedeutet und

R²

für ein Wasserstoffatom, eine Methylgruppe, eine 2-Hydroxypropoxy-Gruppe, eine 3-Hydroxypropoxy-Gruppe oder gemeinsam mit R¹ unter Ringschluss für eine Carbonylgruppe steht,

R³

für ein Wasserstoffatom, eine 1-Hydroxyprop-2-yloxy-Gruppe oder eine 2-Hydroxypropoxy-Gruppe steht, umfasst,

und wobei das Konzentrat das Suspensionsmittel in einer Menge von 70 Gew.-% bis 99 Gew.-% bezogen auf das Gesamtgewicht des Konzentrats, aufweist.The object underlying the present invention is achieved by a thickening concentrate for the continuous preparation of a liquid cationic formulation of household cleaners or softeners, which is in the form of a suspension and comprises a cationic acrylic polymer as thickener and a propylene oxide structure suspending agent for the acrylic polymer. A first aspect of the invention is therefore a thickening concentrate for the continuous preparation of a liquid cationic formulation of household cleaners or fabric softeners which is in the form of a suspension and a cationic acrylic polymer as thickening agent and at least one suspending agent for the acrylic polymer of the following general formula (A)

wherein

R ¹

is a hydrogen atom or together with R ^{2 is} a carbonyl group with ring closure and

R ²

represents a hydrogen atom, a methyl group, a 2-hydroxypropoxy group, a 3-hydroxypropoxy group or together with R ¹ with ring closure for a carbonyl group,

R ³

represents a hydrogen atom, a 1-hydroxyprop-2-yloxy group or a 2-hydroxypropoxy group,

and wherein the concentrate comprises the suspending agent in an amount of from 70% to 99% by weight, based on the total weight of the concentrate.

worin

R¹

für ein Wasserstoffatom steht oder gemeinsam mit R² unter Ringschluss eine Carbonylgruppe bedeutet und

R²

für ein Wasserstoffatom, eine Methylgruppe, eine 3-Hydroxypropoxy-Gruppe oder gemeinsam mit R¹ unter Ringschluss für eine Carbonylgruppe steht, umfasst.

In a specific embodiment, in said thickener concentrate as suspending agent for the acrylic polymer at least one compound of the formula (A-1) is contained,

wherein

R ¹

is a hydrogen atom or together with R ^{2 is} a carbonyl group with ring closure and

R ²

represents a hydrogen atom, a methyl group, a 3-hydroxypropoxy group or together with R ^{1 is} a ring-closing carbonyl group.

Preferably, the suspending agent is selected from the group consisting of dipropylene glycol (preferably with the CAS No. 25265-71-8 ), 1-butanol, 1-propanol and γ-butyrolactone and mixtures thereof. A thickening concentrate according to the invention is in the form of a suspension which can be used in a continuous production process of liquid cationic formulations of fabric softeners or household cleaners.

The thickening concentrate according to the invention may contain a suspending agent. It is also possible according to the invention that a mixture of two or more different suspending agents is contained in the thickening concentrate. Surprisingly, it has been found that the suspending agents according to the invention and mixtures thereof are suitable for suspending cationic acrylic polymers such that the suspension is not substantially thickened, so that continuous metering is possible for preparing the liquid cationic formulation of household cleaners or fabric softeners. The suspension of the suspending agent according to the invention and the cationic acrylic polymer is not necessarily sedimentation stable. However, there is a slight resuspendability of the acrylic polymer in said suspending agents. The suspending agents according to the invention have a high flash point and are not toxic. A low flashpoint and toxicity would preclude the production of liquid cationic formulations of household cleaners or softeners, since these would be excluded from household use.

From an economic point of view is also relevant that the suspending agent is inexpensive to obtain. In this case, the suspending agent can be used in technical purity. Surprisingly, it has been found that the thickening concentrate is stable to small amounts of water. Thus, according to the present invention, the concentrate may contain water in an amount of 5% by weight or less, more preferably 3% by weight or less, based on the total weight of the concentrate.

According to the invention, the concentrate comprises the suspending agent in an amount of 70% by weight to 99% by weight, in particular in an amount of 75% by weight to 90% by weight, based on the total weight of the concentrate. Preferably, the concentrate contains 1 to 30 wt .-%, in particular 10 to 25 wt .-% of cationic acrylic polymer, based on the total weight of the concentrate. In these areas, a thickening concentrate is obtained, which can be metered into liquid cationic formulations of household cleaners or fabric softeners using continuous production processes known in the prior art.

The suspending agent is compatible with the components of the liquid cationic formulation. In particular, with the solvent of the formulation, it is preferably miscible in any ratio. Reactions with the components of the formulation do not occur. The concentrate can therefore be added in any desired amount, so that the viscosity of the cationic formulation can be adjusted as required. If the concentrate has more than 30% by weight of cationic acrylic polymer, the concentrate itself already has a high viscosity. The flowability is impaired. An addition, for example by means of a pump is then difficult. Thus, even in this case, a continuous production is no longer possible because a continuous metering is no longer possible due to the high viscosity of the thickening concentrate. If the concentrate has less than 1% by weight of cationic acrylic polymer, economical preparation of the cationic formulation of household cleaners or fabric softeners is no longer possible.

The final product should preferably contain the thickening concentrate in a proportion of 1% by weight or more, based on the total weight of the formulation. If the proportion of cationic acrylic polymer in the concentrate is less than 1% by weight, the proportion of thickener in the end product is very low, so that a change in the viscosity is not or almost undetectable. Preferably, therefore, the concentrate has the acrylic polymer in an amount of 10% by weight. This allows economical addition of the concentrate with high variability in adjusting the viscosity of the liquid cationic formulation of household cleaners or fabric softeners.

In a preferred embodiment, the weight ratio of the suspending agent to the acrylic polymer ranges from 4: 1 to 1: 3. It has been found that in this weight ratio the thickening concentrate can be used well in continuous production processes known in the art. In conventional continuous production processes, the thickening concentrate is pumped by means of a pump into a liquid cationic formulation of household cleaners or fabric softeners which do not yet have a thickener in their formulation. In order to obtain a uniform dosage, the thickening concentrate should preferably be pumpable. This ensures that the concentrate with a commercial pump to a liquid cationic formulation of Household cleaners or fabric softeners can be pumped in a continuous manufacturing process.

Preferably, the cationic acrylic polymer is in the form of solid particles. The particles are preferably spherical particles, which in particular have a spherical shape. The average particle size (average volume diameter) of the solid particles is in particular in the range from 100 to 900 μm, preferably in the range from 200 to 800 μm, particularly preferably in the range from 250 to 750 μm. If the solid particles are in spherical form, the diameter of the sphere corresponds to the particle size. For all other spherical forms, the particle size corresponds to the size of the particles with the greatest spatial extent. The particle size can be determined by means of scanning electron micrographs (SEM).

The cationic acrylic polymer is hygroscopic. With a too small particle size of 100 microns or less, in particular of 200 microns or less, especially of 250 microns or less so much water can be accumulated on the surface of the particles that a stable suspension is no longer obtained. Rather, it then comes to a swelling of the cationic acrylic polymer, so that after mixing with a suspending agent according to the invention no meterable suspension, but a highly viscous, rubbery mass is obtained. On the other hand, if the particle size is more than 900 μm, these large and thus heavy particles can sediment faster than particles having a size of 900 μm or less, in particular of 800 μm or less, especially of 750 μm or less.

1. a) einem wasserlöslichen ethylenisch ungesättigten Monomer oder einer Mischung dieser Monomere, welche wenigstens ein kationisches Monomer umfasst,
2. b) wenigstens einem Vernetzungsmittel in einer Menge von mehr 50 ppm, bezogen auf das Gewicht der Verbindung a), und
3. c) wenigstens einem Kettenüberträger

gebildet.Suitable cationic acrylic polymers which can be used according to the invention as thickening agents are, for example, in WO 03/102043 A1 on pages 1 to 4, the content of which is fully incorporated by reference. The cationic acrylic polymers of the invention are therefore preferably made

1. a) a water-soluble ethylenically unsaturated monomer or a mixture of these monomers which comprises at least one cationic monomer,
2. b) at least one crosslinking agent in an amount of more than 50 ppm, based on the weight of the compound a), and
3. c) at least one chain transfer agent

educated.

in welcher unabhängig voneinander

R₁

Wasserstoff oder Methyl,

R₂

Wasserstoff oder C₁ bis C₄-Alkyl,

R₃

C₁-C₄-Akylen,

R₄, R₅ und R₆

jeweils unabhängig voneinander Wasserstoff oder C₁ bis C₄-Alkyl,

X

-O- oder -NH- und

Y

Cl, Br, I, Hydrogensulfat oder Methosulfat

darstellen.The cationic monomer preferably corresponds to a compound according to the following compound (I)

in which independently

R ₁

Hydrogen or methyl,

R ₂

Hydrogen or C ₁ to C ₄ -alkyl,

R ₃

C ₁ -C ₄ -alkylene,

R ₄ , R ₅ and R ₆

each independently of one another hydrogen or C ₁ to C ₄ -alkyl,

X

-O- or -NH- and

Y

Cl, Br, I, hydrogen sulfate or methosulfate

represent.

The respective alkyl groups may be linear or branched.

The crosslinking agent b) preferably comprises at least two ethylenically unsaturated units. Suitable preferred crosslinking agents are divinylbenzene, tetraallylammonium chloride, allyl acrylates and allyl methacrylates, diacrylates and dimethacrylates of glycols and polyglycols, butadiene, 1,7-octadiene, allylacrylamides and allylmethacrylamides, bisacrylamidoacetic acid, N, N'-methylenebisacrylamide and polyol polyallyl ethers such as polyallylsucrose and pentaerythritol triallyl ether , Particularly preferred crosslinking agents are tetraallylammonium chloride, allylacrylamides and allylmethacrylamides, bisacrylamidoacetic acid and N, N'-methylenebisacrylamide. Very particular preference is given to tetraallylammonium chloride and N, N'-methylenebisacrylamide as crosslinking agent. It is also possible to use mixtures of the crosslinking agents.

In a preferred embodiment, the cationic acrylic polymer comprises at least one crosslinking agent b) in a proportion of 50 to 1200 ppm, preferably 500 to 1000 ppm and more preferably 700 to 900 ppm, each based on the weight of component a).

The chain transfer agent c) is preferably selected from the group comprising mercaptans, malic acid, lactic acid, formic acid, isopropanol and hypophosphites. The content of chain transfer agent c) is preferably from 10 to 50,000 ppm, preferably from 100 to 10,000 ppm, in each case based on the weight of component a).

in welcher unabhängig voneinander

R1

Wasserstoff oder Methyl,

R2

Wasserstoff oder Methyl,

R3

C₁-C₂-Alkylen und

Y

Cl, Br oder I

darstellen und

1. i) das wenigstens eine Vernetzungsmittel ausgewählt ist aus der Gruppe, welche aus Divinylbenzol, Tetraallylammoniumchlorid, Allylacrylaten und Allylmethacrylaten, Diacrylaten und Dimethacrylaten von Glykolen und Polyglykolen, Butadien, 1,7-Octadien, Allylacrylamiden und Allylmethacrylamiden, Bisacrylamido-Essigsäure, N,N'-Methylenbisacrylamid und Polyolpolyallylether besteht, und in einer Menge von 50 bis 1.200 ppm, vorzugsweise in einer Menge von 50 bis 1.000 ppm, insbesondere bevorzugt in einer Menge von 700 bis 900 ppm, jeweils bezogen auf das Gewicht der Komponente a), enthält und
2. ii) wenigstens ein Kettenüberträger, der aus der Gruppe ausgewählt ist, die Äpfelsäure, Milchsäure, Ameisensäure, Isopropanol und Hypophosphite umfasst, in einer Menge von 1.000 bis 9.000 ppm, vorzugsweise in einer Menge von 2.000 bis 5.000 ppm, jeweils bezogen auf das Gewicht der Komponente a), enthalten ist.

In a particularly preferred embodiment, the cationic acrylic polymer is formed from the formula (Ia) shown below as a cationic monomer:

in which independently

R1

Hydrogen or methyl,

R2

Hydrogen or methyl,

R3

C ₁ -C ₂ -alkylene and

Y

Cl, Br or I

represent and

1. i) the at least one crosslinking agent is selected from the group consisting of divinylbenzene, tetraallylammonium chloride, allyl acrylates and allyl methacrylates, diacrylates and dimethacrylates of glycols and polyglycols, butadiene, 1,7-octadiene, allylacrylamides and allylmethacrylamides, bisacrylamidoacetic acid, N, N ' -Methylenbisacrylamid and Polyolpolyallylether, and in an amount of 50 to 1200 ppm, preferably in an amount of 50 to 1000 ppm, more preferably in an amount of 700 to 900 ppm, each based on the weight of component a), and
2. ii) at least one chain transfer agent selected from the group consisting of malic acid, lactic acid, formic acid, isopropanol and hypophosphites in an amount of 1,000 to 9,000 ppm, preferably in an amount of 2,000 to 5,000 ppm, each based on the weight of Component a) is included.

In a further embodiment, the present invention relates to a process for the continuous preparation of a liquid cationic formulation of household cleaners or fabric softeners. The process is characterized in that a concentrate according to the invention with a liquid, aqueous premix is added. This premix is a solution that includes the active ingredients of the formulation. Thickeners are not included in the premix. The premix is thus the formulation, but without thickener. In a first embodiment, the concentrate according to the invention is metered into a stream of the premix. A mixing between the premix and the concentrate according to the invention takes place on the basis of the flow properties of the premix or of the concentrate. In an alternative embodiment, the liquid, aqueous premix and the concentrate according to the invention in the stream by means of a circulating pump or a static mixer, preferably mixed by means of a static mixer with each other.

Contrary to prior art production in batches, the process of the invention relates to a continuous production process in which a thickening concentrate in the form of a premix is added to the formulation. This allows continuous production with consistent quality. At the same time, the amount of concentrate added to the formulation can be changed at any time so that it can respond quickly and easily to changing customer requests or other changes in formulation.

The pH of the formulation is preferably 6 or less, more preferably 4 or less. The formulation is preferably an acidic cationic formulation. If the formulation according to the invention is a household cleaner, the pH is preferably in the range from 2 to 5, in particular from 3 to 4. If the formulation according to the invention is a fabric softening agent, the pH is preferably in the range from 1 to 6, particularly preferably from 1.5 to 3.5.

The liquid cationic formulation of household cleaners or fabric softeners obtainable by the process according to the invention preferably comprises the thickening concentrate in an amount of 1% by weight or more, based on the total weight of the formulation. With a small amount of concentrate in the formulation, an influence on the viscosity is barely detectable. The use of the thickening concentrate would therefore not be economical here.

"Formulation of household cleaners or fabric softeners" means domestic cleaners, such as bathroom cleaners, toilet cleaners, hard surface cleaners, as well as fabric softeners.

In addition to the thickening concentrate according to the invention, the liquid cationic formulation furthermore comprises customary constituents known in the prior art. The suspension agent for the acrylic polymer according to the invention is therefore soluble in water or the alcoholic solution.

Preferably, the formulation is a fabric softener. This comprises the thickening concentrate according to the invention in a proportion of 1% by weight or more. In addition, for laundry softeners it comprises customary constituents, such as one or more fabric softening compounds, fragrance compositions and other additives, for example alcohols, amphoteric or nonionic surfactants, pH buffer substances, enzymes, fungicides or antioxidants.

In addition to the thickening concentrate according to the invention, a fabric softener usually comprises a fabric softening compound. It is preferred that the fabric softening compound is selected from the group of quaternary Ammonium compounds, polysiloxanes, fabric softening clays and mixtures thereof. These compounds are effective and commercially available fabric softening compounds.

wobei

R⁴

für einen aliphatischen Alk(en)ylrest mit 11 bis 21 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen und/oder gegebenenfalls mit Substituenten steht;

R⁵

steht für H, OH oder O(CO)R⁷,

R⁶

steht unabhängig von R⁵ für H, OH oder O(CO)R⁸, wobei R⁷ und R⁸ unabhängig voneinander jeweils für einen aliphatischen Alk(en)ylrest mit 11 bis 21 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen steht,

m, n und p

können jeweils unabhängig voneinander den Wert 1, 2 oder 3 haben und

X-

kann entweder ein Halogenid-, Methosulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen Anionen sein.

Furthermore, it is particularly advantageous that the fabric softener contains a quaternary ammonium compound as fabric softening compound. It is particularly preferred that the quaternary ammonium compound is a compound of the following general formula (B):

in which

R ⁴

is an aliphatic alk (en) yl radical having 11 to 21 carbon atoms with 0, 1, 2 or 3 double bonds and / or optionally with substituents;

R ⁵

is H, OH or O (CO) R ⁷ ,

R ⁶

is independently of R ^{5 is} H, OH or O (CO) R ⁸ , wherein R ⁷ and R ⁸ are each independently an aliphatic alk (en) yl radical having 11 to 21 carbon atoms having 0, 1, 2 or 3 double bonds,

m, n and p

can each independently have the value 1, 2 or 3 and

X

may be either a halide, methosulfate, methophosphate or phosphate ion as well as mixtures of these anions.

In fabric softeners containing quaternary ammonium compounds and in particular mono-, di- and / or triesters of fatty acids with alkanolamines as fabric softening compounds, a particularly strong increase in viscosity is achieved by a C ₁₆ fat material, which in a preferred embodiment in the final product is.

Examples:

1. a) In a beaker, 80 g of dipropylene glycol ( CAS No. 25265-71-8 ) and 20 g of a commercially available acrylate polymer in the form of solid beads (Rheovis® CSP) from BASF and weighed by means of a laboratory stirrer (propeller). Although the acrylate polymer sediments, it could easily be stirred up again.
2. b) 3 g of water were added to the mixture prepared under a). A thickening or other change in the dispersion did not occur, that is, the system was insensitive to raw material fluctuations.

The thickening concentrates from 1a) and 1b) were pumpable and could be used in a continuous process for the preparation of liquid formulations by means of commercially available metering pumps.

2. Non-inventive example:

As described under 1a), instead of dipropylene glycol 20 wt .-% diethylene glycol were used. Upon addition of the acrylate polymer, the mixture became highly viscous (rubbery) and was unsuitable for thickening aqueous solutions in this form.

Claims (11)

1. A thickening concentrate for continuously producing a liquid cationic formulation of household cleaners or fabric softeners, wherein the concentrate is present in the form of a suspension and comprises a cationic acrylic polymer as a thickening agent and at least one suspending agent for the acrylic polymer of the following general formula (A)

   

   where

   R¹ represents a hydrogen atom, or together with R² for ring closure represents a carbonyl group and

   R² represents a hydrogen atom, a methyl group, a 3-hydroxypropoxy group, or together with R¹ for ring closure represents a carbonyl group,

   R³ represents a hydrogen atom, a 1-hydroxyprop-2-yloxy group or a 2-hydroxypropoxy group,

   and wherein the concentrate comprises the suspending agent in an amount of from 70 wt.% to 99 wt.%, based on the total weight of the concentrate.
2. The thickening concentrate according to claim 1, characterized in that, as the suspending agent, said concentrate comprises at least one suspending agent for the acrylic polymer of the following general formula (A-1)

   

   where

   R¹ represents a hydrogen atom, or together with R² for ring closure represents a carbonyl group and

   R² represents a hydrogen atom, a methyl group, a 3-hydroxypropoxy group, or together with R¹ for ring closure represents a carbonyl group.
3. The thickening concentrate according to claim 1 or claim 2, characterized in that the suspending agent for the acrylic polymer is selected from the group consisting of dipropylene glycol, 1-butanol, 1-propanol, and γ-butyrolactone, and mixtures thereof.
4. The concentrate according to claims 1 to 3, characterized in that it comprises the suspending agent in an amount of from 75 wt.% to 90 wt.%, based on the total weight of the concentrate.
5. The concentrate according to one of claims 1 to 4, characterized in that it also contains water in an amount of 5 wt.% or less, and in particular of 3 wt.% or less, based on the total weight of the concentrate.
6. The concentrate according to one of claims 1 to 5, characterized in that the weight ratio of the suspending agent to the acrylic polymer is in the range of from 4:1 to 1:3.
7. The concentrate according to one of claims 1 to 6, characterized in that the cationic acrylic polymer is present in the form of particles, in particular having a spherical particle size in the range of from 0.2 µm to 1.5 µm, and particularly preferably in the range of from 0.5 µm to 1.0 µm.
8. The concentrate according to one of claims 1 to 7, characterized in that it contains at least one cationic acrylic polymer which is formed by

   a) a water-soluble, ethylenically unsaturated monomer, or a mixture of these monomers, comprising at least one cationic monomer,

   b) at least one cross-linking agent in an amount of more than 50 ppm, based on the weight of compound a), and

   c) at least one chain transfer agent.
9. The concentrate according to claim 8, characterized in that the cationic monomer corresponds to a compound according to the following compound (I)

   

   in which, independently of one another,

   R¹ represents hydrogen or methyl,

   R2 represents hydrogen or C₁ to C₄ alkyl,

   R₃ represents C₁-C₄ alkylene,

   R₄, R₅ and R₆ each represent, independently of one another, hydrogen or C₁ to C₄ alkyl,

   X represents -O- or -NH- and

   Y represents Cl, Br, I, hydrogen sulfate or methosulfate.
10. A method for continuously producing a liquid cationic formulation of household cleaners or fabric softeners, characterized in that a concentrate according to one of claims 1 to 9 is added to the formulation.
11. The method according to claim 10, characterized in that the pH value of the formulation is 6 or less, in particular 4 or less.