WO2013075827A1

WO2013075827A1 - Use of polymers obtainable by means of radical emulsion polymerisation, as thickeners for cleaning agents

Info

Publication number: WO2013075827A1
Application number: PCT/EP2012/004831
Authority: WO
Inventors: Aleksandrovic-Bondzic Vesna; Mertens Sascha
Original assignee: Centrum Für Angewandte Nanotechnologie (Can) Gmbh
Priority date: 2011-11-25
Filing date: 2012-11-22
Publication date: 2013-05-30
Also published as: WO2013075827A4; DE102011119332A1

Abstract

The invention describes the use of novel polymers as thickeners for surfactant-containing cleaning agents, which comprise various cleaning products and also washing agents. The thickeners are obtained through the radical emulsion polymerisation of respectively: at least one acidic vinyl monomer or a salt thereof, a non-ionic vinyl monomer, a monomer with an unsaturated end group, and a polyoxyalkylene part and a cross-linking monomer. Said novel polymers can be used to thicken cleaning agents with persistent high transparency.

Description

Use of polymers obtainable via free-radical emulsion polymerization as thickeners for cleaning agents

The invention relates to the use of a novel polymer with thickening properties as thickener for inanimate surface cleaners. The invention does not relate to the use of a novel polymer having thickening properties as thickener in cosmetic or dermatological preparations such as shampoos or shower preparations.

Thickening polymers are able to interact in hydrophilic, especially in aqueous preparations, both with itself and with other substances in such a way that they influence viscosity and flow behavior.

EP 1 465 932 B1 describes alkali-swellable and alkali-soluble associative polymers prepared from a monomer mixture of (a) at least one acidic vinyl monomer or a salt thereof, (b) at least one nonionic vinyl monomer, (c) a first associative monomer having a first hydrophobic end group, (d) a second associative monomer having a second hydrophobic end group or a semihydrophobic monomer or a combination thereof and optionally (e) a crosslinking monomer or chain transfer agent or a combination thereof.

WO 2009/019225 A2 describes an aqueous dispersion of a copolymer having polymerized units a) at least one ethylenically unsaturated carboxylic acid, b) at least one nonionically unsaturated surfactant monomer, c) at least one C ₁ - to C ₂ -alkyl acrylate, wherein the number of alkyl groups the alkyl acrylate average alkyl chain length 2.1 to 4, is. After neutralization with alkali, the dispersion serves as an associative thickener, in particular for liquid washing and cleaning agent formulations.

According to EP 1 465 932 B1 as well as according to WO 2009/019225 A2, the preparation of a thickener with satisfactory properties requires the addition of associative monomers. The object of the present invention is therefore to find as transparent as possible thickeners, with which it is possible to thicken storage-stable surfactant-containing detergent preparations without any turbidity, but at the same time have the best possible thickening properties, ie shear thinning in the thickened preparation, ie a very high viscosity at rest and have a low viscosity under the action of high shear forces, and, moreover, have low tan δ values, but in the preparation do not necessarily require the addition or only a small addition of associative monomers.

By "associative monomers" is meant according to the invention monomers of the type "A-P-H", where A is an ethylenically unsaturated group, such as a

Methacrylic, acrylic, allyl or vinyl group, P contains a spacer of one

Polyoxyalkylene chain having 2 to 300 alkylene oxide units, such as polyethylene glycol, polypropylene glycol or polybutylene glycol, and H is a hydrophobic group, such as an alkyl and / or aryl group, having at least 4, preferably at least 8 carbon atoms, for example, a lauryl group.

The object is achieved by the use of a polymer as a thickener for cleaning products for inanimate surfaces, in particular for household cleaning products, cleaning products for cleaning hard surfaces, automotive cleaning products and detergents, characterized in that the polymer by free-radical emulsion polymerization of (A) at least one acidic Vinyl monomer or its salt, (B) at least one nonionic vinyl monomer, (C) at least one monomer containing an unsaturated end group and a polyoxyalkylene part, (D) at least one crosslinking monomer, the polymerization being controlled so as to be at least temporarily the gel effect occurs, achieved by that

at a reaction volume of 100 ml to 15 l, the metering time is 30-40 minutes, based on a reaction vessel without internal cooling, when the monomers are added together; at a reaction volume of 100 ml to 15 I, the metering time up to 90 minutes, preferably 60 minutes, based on a reaction vessel without internal cooling, when the monomer (D) is added delayed by up to 10 minutes;

with a reaction volume of more than 15 l, the metering time is at least 40 minutes, preferably 60-120, particularly preferably 120-180 minutes, based on a reaction vessel without internal cooling.

Surprisingly, it has been found that when using the polymer according to the invention a suitable cleaning agent for inanimate surfaces, in particular for household cleaning products, cleaning products for cleaning hard surfaces, automotive cleaning products and detergents, is present, which does not have the disadvantages known from the prior art. The metering-time-dependent preparation of such a polymer to be used according to the invention is described, for example, in DE 10 2010 022 063 for a monomer addition during 40 minutes. For the details of the production, reference is made to the content of this document. Further embodiments of the preparation according to the invention to be used polymers from the four mentioned monomer groups are described in DE 10 201 1 078 087, for a monomer for 120 minutes, wherein the crosslinking monomer takes place earliest 10 minutes after the addition of the other monomers.

The thickeners used according to the invention are capable of stabilizing various pigments and other additives and air bubbles in a preparation. The thickeners used according to the invention show a higher transparency than other thickeners at the same pH.

In the case of free-radical emulsion polymerization for the preparation of the thickeners used according to the invention, preference is given to using a protective colloid. A suitable protective colloid is, for example, allyl-modified hydroxymethylcellulose.

The monomers in the preparation of the polymer used are preferably in contents of from 10 to 75 wt .-%, preferably 30 to 50 wt .-% of monomers (A), particularly preferably 35 to 49 wt .-%, monomers (B) of From 10 to 90% by weight, preferably from 30 to 80% by weight, particularly preferably from 47 to 60% by weight, of monomers (C) in amounts of from 0.5 to 40% by weight, preferably from 1 to 10% by weight, particularly preferably from 2 to 6% by weight, and monomers (D) in contents of up to 1% by weight, preferably 0 , 05 to 0.5 wt .-%, particularly preferably 0, 1 to 0.35 wt .-% used.

The acidic vinyl monomer (A) used is preferably one from the group of vinyl monomers having carboxyl groups, more preferably from the group of acrylic acid or methacrylic acid or the alkali metal, alkaline earth metal, ammonium or alkylammonium salts of methacrylic acid, most preferably from the group the methacrylic acid or the alkali, alkaline earth, ammonium or alkylammonium salts of methacrylic acid.

The nonionic vinyl monomer (B) is preferably a hydrophobic nonionic vinyl monomer and / or selected from the group of Cr to C22 alkyl acrylates or C ₁ to C ₂ alkyl methacrylates or mixtures thereof.

The mass ratio of the monomers (A) to (B) is preferably 1: 2.2 to 2: 1.

The monomer (C) is preferably selected from the group of vinylpolyalkylene glycols or polymerizable surfactants or mixtures thereof, preferably from the group of allyl alcohol alkoxylate, allyl polyalkylene glycol ethers (EO 30 mol),

Allyl polyalkylene glycol ether (EO 20 mol), allyl polyalkylene glycol ether (EO 20 mol, PO 20 mol), 1,4-butanediol vinyl ether (EO / PO 30 mol), polyalkylene glycol allyl butyl ether (EO 25 mol, PO 8 mol), vinyl polyalkylene glycol ether (EO 40 mol),

Vinyl polyalkylene glycol ether (EO 20 mol).

The crosslinking monomer (D) is preferably selected from the group of polyol acrylates or polyol methacrylates having at least two acrylate groups or

Methacrylate groups and the mixed esters of polyols with acrylic acid and / or methacrylic acid selected.

Preferred uses according to the invention for such polymers are the use in all-purpose cleaners, in floor cleaners, in window cleaners, in dishwashing detergents, in bathroom cleaners, in toilet cleaners, in drain cleaners, in tile cleaners. in carpet cleaners, in glass cleaners, in hygiene cleaners, in oven cleaners, in furniture cleaners or in gel detergents. Preferred uses of the invention are also in the field of cleaning products for engines, car shampoos, car window cleaner, paint cleaner, brake cleaner, insect remover, convertible top cleaner, upholstery cleaner or rim cleaner.

Hard surfaces according to the invention, for example, floors, tiles, tiles, plastics and other hard surfaces in the home, in toilets, in public sanitary facilities, in swimming pools, saunas, sports facilities or in doctor or massage practices understood.

Detergents and cleaners according to the invention in the broadest sense surfactant-containing preparations in solid form (particles, powders, etc.), semi-solid form (pastes, etc.), liquid form (solutions, emulsions, suspensions, gels, etc.) and gas-like form (aerosols, etc .) understood, which may contain any type of surfactants, with regard to a beneficial effect in the application, usually in addition to other components that are customary for the particular application.

The detergents and cleaners may contain customary ingredients for this product group, such as builder substances, special polymers, for example those with co-builder properties, foam inhibitors, dyes and possibly additional fragrances (perfumes), pH adjusters, thickeners, polyethylene glycols, bleaches, such as peroxo Bleaches and chlorine bleaches, bleach activators, bleach stabilizers, bleach catalysts, enzymes, in particular proteases, amylases or cellulases, enzyme stabilizers, dye transfer inhibitors and scorch inhibitors, without the ingredients being restricted to these substance groups.

Also advantageous is an addition of nanoparticles, for example a combination of zinc oxide and copper or magnesium, prepared according to WO 201 1/033040 A2. These nanoparticles have antibacterial properties. Often important ingredients of the detergent compositions are also washing aids, for example, and not limiting optical brighteners, UV-protective substances and Soll Repellents, especially substances that counteract the re-soiling of fibers are mentioned.

Suitable optical brighteners are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavone acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, etc., which are described in [0090] of document DE 10 2007 036 910 A1 are called.

Suitable UV protective substances are the UV absorbers mentioned in [0101] of the document DE 10 2007 036 910 A1 or those mentioned in [0185] of the document DE 10 2007 058 342 A1.

Non-ionic cellulose ethers such as methylcellulose and. Serve as polymers with dirt-repellent and / or soil-dissolving properties

Methylhydroxypropylcellulose with a proportion of methoxy groups from 15 to 30 wt .-% and to hydroxypropoxy groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether, and the other polymers which in the document DE 10 2007 058 342 A1 are described. Substances which counteract the re-soiling of fibers are, for example, alcohol ethoxylate propoxylates, which are described in the document DE 10 2005 018 501 A1.

In the event that the preparations are at least partly present as shaped bodies, binding and disintegration aids may also be present.

As the binder, synthetic organic polymers having a suitable melting temperature, in particular, e.g. Polyethylene glycol, such as polyethylene glycol having an average molecular weight of 500 g / mol (PEG 1500). Other suitable binders are polyvinylpyrrolidone (PVP),

Polyacrylates and water-soluble acrylate copolymers. Further suitable binders are described, for example, in the document EP 0 71 1 828 A2. Known disintegration aids are, for example, carbonate / citric acid systems, it also being possible to use other organic acids, and also synthetic polymers such as polyvinylpyrrolidone or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives. Other disintegration aids based on cellulose are described in the document WO 1999/029826 A1.

The cleaning agents can each be solid or liquid. Likewise, they may also be in a form comprising solid and liquid components or subsets of the components side by side.

The thickeners used in the invention require in their preparation no addition of associative monomers or only an addition of these monomers in low concentrations of at most 1 wt .-%. In the production of the thickeners, however, associative thickeners can generally also be used in amounts of more than 1% by weight.

Surfactants for the cleaning products in use with the thickeners are, in particular, fatty alcohol ethoxylates, linear alkylbenzenesulfonates,

Sodium lauryl ether sulfate, sodium lauryl sulfate, as well as other cationic, anionic, nonionic, zwitterionic and amphoteric surfactants, including mixtures thereof. The surfactant is usually used in amounts of up to 50 wt .-%.

For thickening preparations for detergent products, preferably up to 20% by weight of the thickening polymer is used. In this concentration range added suspended matter does not settle. Suspending substances may be, for example, pearls, pigments or air bubbles.

The cleaning agents are, so far as they are gelatinized preparations with yield point, adjusted so that they have a yield value of 0.5 to 20 Pa, preferably 1 to 6 Pa. As a yield point, the critical shear stress of the Flow curve viewed. The flow limit is determined, for example, as follows: The flow curve is measured on a shear stress controlled rheometer (Malvern Gemini HR nano) at 25 ° C ± 1 ° C with 20 mm plate / plate geometry at a gap between 0.8 mm and 1, 2 mm. It is filled in a gentle way. A suitable constant shear stress ramp is specified. Before the test, a corresponding structure recovery time is maintained and the critical shear stress is specified at the maximum of the flow curve.

The cleaning agents preferably have a tan δ value of 0.05 to 0.6, preferably 0, 1 to 0.5. The "tan δ value" in the sense of the present invention is equal to the quotient of the loss modulus and the storage modulus, measured in each case at 40 ° C. The tan δ value is determined as follows: The loss and storage modulus are determined by a dynamic frequency test run with a shear stress controlled rheometer (Malvern Gemini HR nano) at 40 ° C ± 1 ° C with 20 mm plate / plate geometry measured at a gap between 0.8 mm and 1, 2 mm, whereby a structure-gentle filling takes place following parameters:

- minimum frequency: 0.06302 s ^"1 ;

- maximum frequency: 4.00 s ^"1 ;

- Number of samples: 10.

The measurement is started after a delay time (waiting time) of 10 seconds; 2048 measuring points are recorded. The shear stress is specified in the measurement method, whereby it increases during the measurement.

The frequency test is carried out with a corresponding structure recovery time before the test and the tan δ value in the frequency range between 0.05 rad / s and 3.0 rad / s specified, preferably between 0.08 rad / s and 1, 0 rad / s ,

Preferred formulations with the thickener used according to the invention have a turbidity value of NTU (Nephelometry Turbidity Unit) <20 at pH <6.2. However, preparations with a haze value> 20 can also be used as cleaning agents, where the use of transparent preparations does not matter. The turbidity value is measured with a turbidity meter, whereby distilled water with a value of NTU = 0 is the standard.

The detergents in which the thickener is used may have an acidic, basic or neutral pH. The cleaning product may be an aqueous cleaning product, preferably with a water content of 15 to 99% by weight. Likewise, the thickeners are used in alcoholic cleaning products according to the invention, in which the alcohol content is preferably 0.1 to 85 wt .-%.

It is also according to the invention, if not water or alcohol, but other polar liquids are thickened by polymers according to the invention. In particular, glycols, polyols, amines and organic acids such as acrylic acid can be thickened.

Examples

The following are some examples of the use of the thickener according to the invention, but which are not intended to limit the invention.

Example 1 :

Various polymers were prepared, as described in DE 10 2010 022 063. The dosing time was 30 min. The synthesis was carried out in a 1 l reactor.

Polymer A MAA: EA: ODA: R1 100: TM PTA = 37: 54.8: 5: 2.9: 0.3

Polymer B MAA: EA: ODA: A1 1 1 R: TM PTA = 37: 52.35: 5: 5.35: 0.3

Polymer C MAA: EA: A 1/1800: TM PTA = 37: 57.35: 5.35: 0.3

Polymer D MAA: EA: ODA: AB / 25-8: TM PTA = 37: 53.1: 5: 4.6: 0.3

The information on the ratios of the monomers is percent by weight. In each case about 1 kg of polymer was produced. Here is:

MAA methacrylic acid

EA ethyl acrylate

ODA octadecyl acrylate

R1 100 polyglycol R1 100 (Clariant)

Vinyl polyalkylene glycol ether (EO 20 mol)

TM PTA trimethylolpropane triacrylate

A 1 1 1 R Pluriol® A1 1 1 R (BASF)

Allylalkoholalkoxylat

A1 1/1800 Polyglycol A1 1/1800 (Clariant)

Allyl polyalkylene glycol ether (EO 20 mol, PO 20 mol)

AB / 25-8 Polyglycol AB / 25-8 (Clariant)

Polyalkylene glycol allyl butyl ether (EO 25 mol, PO 8 mol)

Example 2: Hand dishwashing detergent with beads

Polymer A was distributed in water. Texapon N 70 and Ufasan 50 were added. The solution was homogenized. The pH was adjusted to 6.2 with sodium hydroxide. Subsequently, ^Tego® Betain F 50 was added. With the homogenization, the finished mixture was obtained. Worlee beads Jojoba were carefully distributed in the resulting mixture.

The hand dishwashing detergent is transparent and colorless. The Worlee beads are prevented from sinking by the A polymer. Tan δ was measured. This was 0.13, which confirms the stabilization of the beads and air bubbles over a longer period of time.

Example 3: Glass cleaner with surface adhesion

Polymer A was dispersed in water and mixed with the two surfactants Tergitol 15-S-7 and Ufasan 50. The mixture was homogenized. After adjusting the pH to 6.2 with sodium hydroxide, the alcohol was added. The mixture was carefully homogenized.

The polymer A causes a slower course of the glass cleaner than the same composition without the thickener on a vertical surface and thus improved contact time and dirt removal. The glass cleaner is thin and sprayable.

Example 4: All-purpose cleaner, thickened and transparent

The procedure was as in Example 3, but with the difference that the pH was adjusted to a value of 8.0 with sodium hydroxide. The all-purpose cleaner can be easily dosed by the thickening. The air bubbles stabilized in the formulation are intended to arouse increased consumer interest in the consumer. The long-term stabilization of air bubbles was confirmed by measuring a tan δ of 0.28.

Example 5 Antibacterial gel with stabilized nanoparticles of CANdot series D

Zinc oxide / copper nanoparticles, size: about 30 nm long and 5-7 nm diameter, rod-shaped, about 10 wt .-% copper

The polymer C was mixed with water. Subsequently, the pH was adjusted to pH = 7 by addition of NaOH. As the pH was adjusted, the viscosity of the composition increased. The resulting product was stirred gently into CANdot®s Series D nanoparticles.

The CANdot ^® s of series D are prevented from sinking by the polymer C, so that the gel no longer needs to be homogenized before further processing.

Claims

claims

Use of a polymer as a thickener for inanimate surface cleaners, in particular for household cleaning products, cleaning products for cleaning hard surfaces, automobile cleaning products and laundry detergents, characterized in that

the polymer by free radical emulsion polymerization of

(A) at least one acidic vinyl monomer or its salt,

- (B) at least one nonionic vinyl monomer,

(C) at least one monomer containing an unsaturated end group and a polyoxyalkylene part,

- (D) at least one crosslinking monomer

available,

wherein the polymerization is controlled so that at least temporarily the

Gel effect occurs, achieved by that

at a reaction volume of 100 ml to 15 l, the metering time is 30-40 minutes, based on a reaction vessel without internal cooling, when the monomers are added together;

at a reaction volume of 100 ml to 15 I, the metering time up to 90 minutes, preferably 60 min, based on a reaction vessel without internal cooling, when the monomer (D) is added delayed by up to 10 minutes.

2. Use according to claim 1, characterized in that at a reaction volume of 100 ml to 5 I, the metering time is 30 - 40 minutes.

3. Use according to claim 1 or 2, characterized in that no associative monomers are used in the preparation of the polymer or at most in a concentration up to 1 wt .-%.

4. Use according to one of the preceding claims, characterized in that the acidic vinyl monomer (A) is selected from the group of vinyl monomers having carboxyl groups, particularly preferably from the group of acrylic acid or methacrylic acid or the alkali metal, alkaline earth metal, ammonium or Al - Kylammoniumsalze of methacrylic acid, most preferably from the group of methacrylic acid or the alkali metal, alkaline earth metal, ammonium or alkyl ammonium salts of methacrylic acid.

5. Use according to one of the preceding claims, characterized in that the nonionic vinyl monomer (B) is a hydrophobic nonionic vinyl monomer and / or is selected from the group of C to C ₂ 2-alkyl acrylates or C to C ₂ 2-alkyl methacrylates or their mixtures.

6. Use according to one of the preceding claims, characterized in that the monomer (C) is selected from the group of

Vinylpolyalkylene glycols or polymerizable surfactants or mixtures thereof, preferably from the group allyl alcohol alkoxylate, Allylpolyalkylenglycolether (EO 30 mol), Allylpolyalkylenglycolether (EO 20 mol), Allylpolyalkylenglycolether (EO 20 mol, PO 20 mol), 1, 4-butanediol vinyl ether (EO / PO 30 mol )

Polyalkylene glycol allyl butyl ether (EO 25 mol, PO 8 mol),

Vinyl polyalkylene glycol ether (EO 40 mol), vinyl polyalkylene glycol ether (EO 20 mol).

7. Use according to one of the preceding claims, characterized in that the crosslinking monomer (D) is selected from the group of Polyolacrylate or Polyolmethacrylate with at least two

Acrylate groups or methacrylate groups and the mixed esters of polyols with acrylic acid and / or methacrylic acid.

8. Use according to one of the preceding claims, characterized in that a protective colloid is used in the free-radical emulsion polymerization.

9. Use according to one of the preceding claims, characterized in that the monomers

- (A) in amounts of 10 to 75 wt .-%, preferably 30 to 50 wt .-%, particularly preferably 35 to 49 wt .-%,

- (B) in amounts of 10 to 90 wt .-%, preferably 30 to 80 wt .-%, particularly preferably 47 to 60 wt .-%,

- (C) in contents of 0.5 to 40 wt .-%, preferably 1 to 10 wt .-%, particularly preferably 2 to 6 wt .-%,

- (D) in amounts of up to 1 wt .-%, preferably 0.05 to 0.5 wt .-%, particularly preferably 0, 1 to 0.35 wt .-% present.

10. Use according to one of the preceding claims, characterized in that the monomers (A) :( B) in mass ratios of 1: 2.2 to 2: 1 are present.

1 1. Use according to one of the preceding claims, characterized in that the cleaning product is an aqueous cleaning product, preferably with a proportion of water of 15 to 99 wt .-%.

12. Use according to any one of claims 1 to 10, characterized in that the cleaning product is an alcoholic cleaning product, preferably with a proportion of alcohol from 0, 1 to 85 wt .-%.

13. Use according to one of the preceding claims, characterized in that the cleaning product is a gel.

14. Use according to one of the preceding claims, characterized in that the thickening polymer is used in amounts of up to 20 wt .-%.

15. Use according to one of the preceding claims, characterized in that the cleaning product at least one substance selected from the group of builders, other polymers, foam inhibitors, Dyestuffs and fragrances, pH adjusters, other thickeners, polyethylene glycols, bleaching agents, bleach activators, bleach stabilizers, bleach catalysts, enzymes, in particular proteases, amylases or cellulases, enzyme stabilizers, dye transfer inhibitors and grayness inhibitors.

16. Use according to one of the preceding claims, characterized in that the cleaning product is an all-purpose cleaner, a floor cleaner, a window cleaner, a dishwashing detergent, a bathroom cleaner, a toilet cleaner, a drain cleaner, a tile cleaner, a carpet cleaner, a glass cleaner, a hygiene cleaner, an oven cleaner, a furniture cleaner or a gel detergent is.

17. Use according to any one of claims 1 to 14, characterized in that the cleaning product is an engine cleaner, a car shampoo, a car window cleaner, a paint cleaner, a brake cleaner, an insect remover, a convertible top cleaner, a cushion cleaner or a rim cleaner.