JPS61243899A - Multipurpose detergent for hard surface - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention is a builder-free, suspension-stable, aqueous, liquid, multi-purpose cleaner for hard surfaces which, when diluted and applied to hard surfaces, produces an abrasive or polishing agent. The present invention relates to a cleaning agent that acts as a typical hand dishwashing water-soluble detergent or as a non-abrasive all-purpose cleaner for hard surfaces, depending on the degree of dilution with tap water.

[Prior Art] Liquid dishwashing detergents for hand washing, which are usually used at slightly high temperatures, originally contain about 4 to 6 synthetic anionic surfactants as active ingredients.
0% by weight, and optionally small amounts of nonionic surfactants (preferably alkanolamides) or mixtures of amphoteric surfactants, as well as solvents, solubility promoters, hydrotropes, fragrances and dyes, preservatives, viscosity modifiers, Contains pH14 regulator and electrolyte. To protect the skin, the pH is about 5.5-8.0. Although not common, small amounts of builders or complexing agents (such as hexametaphosphate or ethylenediaminetetraacetic acid) may be added to the cleaning agent when water with a high iron content is used. Such cleaning agents are known, for example, from EP-A-36625.

Multi-purpose cleaning agents, i.e. formulations for cleaning various hard surfaces domestically as well as industrially and commercially, are
Preferably, the active ingredients include a combination of anionic and nonionic surfactants (total amount of about 5-15% by weight) together with about 0.5-5% by weight of detergency-enhancing pill goo. Other detergency-enhancing ingredients that may be used, typically solvents (including terpene compounds), have the general formula: ] Polyethylene glycol shown in the following is used as an organic polymer to enhance the cleaning effect. These detergents also contain dyes and fragrances, electrolytes and viscosity modifiers. In such a cleaning agent, the cleaning power to be exerted mainly at room temperature is usually better in an alkaline system than in a neutral or acidic system, so the pH of the cleaning agent is preferably 8.
．． 5 to 11. Such multipurpose cleaning agents are also known, for example from German Patent No. 2709690 and corresponding European Patent No. 9193. No abrasive cleaning agents are provided.

Mild polishes may also be used to clean movable or immovable hard surfaces (eg, walls, tiles, stoves, sinks, etc.).

These mild polishes may be solid, liquid or paste-like. The surfactant content of these is relatively low, but the mildly alkaline inorganic builders are relatively high. Polishing agents typically contain large amounts of water-insoluble abrasives, such as feldspar, silica or pumice.

That is, two types of cleaning agents with different compositions are commonly commercially available and are used for related but different cleaning objects. However, at home, especially in the kitchen, hand dishwashing detergents are also often used for cleaning hard surfaces, but as mentioned above their cleaning effectiveness may not be optimal in this case. In this connection, it is immaterial whether the dishwashing detergent is used in concentrated or diluted form. Conversely, hand washing dishes using commercially available all-purpose cleaners or liquid polishes does not yield satisfactory results.

Therefore, a multipurpose cleaner with high detergency and skin compatibility, along with the high emulsifying power of conventional multipurpose cleaners and the mild abrasive action of polishing agents, provides a level of cleaning power that can only be obtained with alkaline, builder-containing cleaners. A multi-purpose cleaner with a pH range was needed.

Can be used on the one hand for polishing and on the other hand for dishwashing, i.e. as a dual-purpose cleaning agent, with 20-35% by weight of anionic surfactant, 2-15% of foam-stabilizing nonionic surfactant % by weight, water-insoluble abrasive (particle size 15-150 μm and Mohs height 2-7) 1
A builder-free liquid cleaning agent containing ~20% by weight and 20-75% water is disclosed in European Patent Publication No. 21545
Known by No. A similarly usable abrasive-containing cleaner containing two different anionic surfactants, preferably with a nonionic surfactant, and necessarily containing a builder in some proportion, is disclosed in Canadian Patent No. 11432.
It is described in No. 40. However, when these known cleaners are used as multi-purpose cleaners (usually without water) they foam excessively and therefore have to be wiped unduly vigorously with a damp sponge to prevent the formation of residues due to abrasive particles. No.

[Object of the invention].

The object of the present invention is to provide a single new cleaner composition which can be used in particular for polishing and hand dishwashing, as a multi-purpose cleaner and optionally also as a polish.

[Structure of the Invention] The present invention contains an abrasive, water, and a surfactant base that is an anionic surfactant mixture or an anionic surfactant and an amphoteric surfactant mixture, and has a pH of 5.5.
~9.5, suspension-stable multi-purpose liquid cleaning agents for hard surfaces without builder and their use as dishwashing agents, multi-purpose cleaners, polishes and/or polishes.

The anionic surfactants used are preferably synthetic surfactants, at least two of which (in particular sulfonate and sulfate type surfactants) are used together, as in the case of customary dishwashing detergents. .

Sulfonate type surfactants are mainly CIl Cl5 (
Preferably Cps Cps) Alkylbenzenesulfonate having an alkyl group, preferably .Cps-C
, (preferably C, --Cr.) alkanesulfonates obtained by sulfochlorination or sulfooxidation of alkanes followed by hydrolysis or neutralization, or by addition of bisulfites to olefins, and C6Cl. (preferably C+tC+a) olefin sulfonate. That is, for example, alkenes and hydroxyalkanesulfonates and disulfonates obtained by sulfonating monoolefins with terminal or non-terminal double bonds with sulfur trioxide gas and then alkaline or acidic hydrolysis of the sulfonation product. It is a mixture. Other suitable surfactants are:
Esters of α-sulfo fatty acids, such as the α-sulfonated methyl or ethyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids.

Particularly suitable surfactants of the sulfate type are sulfuric acid monoesters of natural and synthetic primary alcohols, i.e. fatty alcohols such as, for example, coconut oil fatty alcohol, tallow fatty alcohol, oleyl alcohol or CIO-C2° oxo alcohol; It is a sulfuric acid monoester of a secondary alcohol with a long carbon chain. Other suitable sulphate-type surfactants are sulphate monoesters of aliphatic primary alcohols ethoxylated with 1 to 6 moles of ethylene oxide, or sulphate monoesters of ethoxylated secondary alcohols or alkylphenols. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.

All these anionic surfactants are preferably used in the form of their salts, especially the sodium salts, but also in the form of their potassium or ammonium salts or in the form of soluble salts of organic bases (e.g. mono-, di- or triethanolamine). May be used in

The detergents of the invention may also contain 0-15% by weight, preferably 0.5-5%, more preferably 1-2% by weight of amphoteric surfactants.

Suitable amphoteric surfactants include acid groups (e.g. carboxyl,
sulfonic acid, sulfonic acid semiester, phosphonic acid and phosphonic acid partial ester groups) and basic groups (e.g.
If the surfactant is not a surfactant that has 4-, 2-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 3-, 4-tin ammonium, or 4-tin ammonium groups in its molecule, it cannot be used as a betaine or zwitterionic surfactant. i do

Such compounds are particularly characterized in that one of the aliphatic groups is C,
It is a derivative of an aliphatic quaternary ammonium compound consisting of ~CI8 groups, the other aliphatic group having an anionic water-solubilizing carboxy, sulfo or sulfate group. Typical examples of such surface active betaines include, for example, 3-(N-
Hexadecyl-N.

N-dimethylammonio)-propanesulfonate, 3
-(N-tallow alkyl-N,N-dimethylammonio)
-2-hydroxypropanesulfonate, 3-(N-hexadecyl-N, N-bis-(2-hydroxyethyl)
-ammonio)-2-hydroxyprovir sulfate,
3-(N-cocoalkyl-N,N-bis-(2,3-
dihydroxypropyl)ammonio)-propanesulfonate, N-tetradecyl-N,N-dimethylammonioacetate, N-hexadecyl-N,N-bis-(2
゜3-dihydroxypropyl)-ammonioacetate. Preference is given to using CI2 Cps-acylamidopropyldimethylammonium betaine.

The total surfactant content is preferably 10-35% by weight, more preferably 15-25% by weight. When using an amphoteric surfactant, the weight ratio of anionic surfactant to amphoteric surfactant is preferably 20:1 to 1:1. More preferably 15:1 to 1:1, still more preferably 8:1 to 1:
It is 1.

Suitable abrasives are mainly water-soluble substances having an average particle size of 5 to 100 μm, preferably 5 to 50 μm, more preferably 5 to 15 μm. In order to vary the polishing effect, for example Degussa, "Technical Information"
rIIlation, sident (S + dent)
(Trademark) 12, toothpaste abrasive silica described as Cident (Trademark) 12DS and Giulini Chemy (G
Aluminum oxide
Particular preference is given to the use in combination with the polishing silicas described in "Niumoxid/Poliertonerde").Suitable polishing aluminas are, for example, P2O5, ATSFGSP,
It is described under the names of 10 reinst, PS reinst, P9O9 reinst, and P2O0 reinst. With such very fine abrasives, which have no abrasive action and can therefore also be called "polishers", to prepare particularly mild abrasives that can polish sensitive metal surfaces without dilution. is possible. The amount of abrasive is preferably 5 to 20% based on the total amount of the preparation.
% by weight, more preferably 10-15% by weight.

In order to maintain high suspension stability, the viscosity of the detergent of the present invention is
000-12000mPa5-sec, preferably 4
000~6000mPa5-sec, (D=58-1
) must be adjusted. Suitable viscosity modifiers include water-soluble neutral salts (e.g. NH4C12 or NaCl2),
Thickened silica (e.g. Sipernat)
) 22 S (trademark) (Degussa Products (De
manufactured by Gussa Product), molecular weight 200-4
x 10' polyethylene glycol)), organic polymers (e.g. polyacrylates, xanthan gum, cellulose and descipne derivatives) and inorganic layered silicates (
For example, bentonite). For this purpose, solvents and solubility promoters known per se, such as water-soluble organic solvents,
In particular, low molecular weight aliphatic alcohols having 1 to 4 carbon atoms (e.g. methanol, ethanol, isopropanol, ethylene glycol, propylene glycol and glycerol) and solubility promoters with a boiling point above 75°C (e.g. identical or different polyhydric It is also possible to combine alcohols (ethers of alcohols or partial ethers of polyhydric alcohols). Such solubility promoters include, for example, di- or triethylene glycol polyglycerols and moieties of ethylene glycol, propylene glycol, butylene gellicol or glycerol with aliphatic monohydric alcohols having 1 to 4 carbon atoms in the molecule. Contains ester. Suitable water-soluble or water-emulsifiable organic solubility promoters are ketones such as acetone and methyl ethyl ketone, as well as aliphatic, cycloaliphatic, aromatic and chlorinated hydrocarbons.

However, so-called low molecular weight alkylaryl sulfonate type hydrotropes (including, for example, toluene, xylene or cumene sulfonate) are also suitable as viscosity modifiers and therefore as solubility promoters. These may be present in the form of sodium and/or potassium and/or alkylamino salts. The viscosity of the cleaning agent produced according to the invention is adjusted in the laboratory and then the ingredients and amounts are scaled up for the actual manufacturing process. The viscosity modifier is about 0 to 10% by weight based on the total amount of detergent,
Preferably it is used in an amount of 2 to 6% precious.

So-called fatty solvents, i.e. commercially available terpene compounds preferably with a citrus-like aroma (e.g. limonene as terpene hydrocarbon or pine oil as terpene alcohol) and/or of high molecular weight (molecular weight 200,000 to 4
It is particularly advantageous to add glycol ethers (greater than along with other ingredients of
This makes it possible to improve the removal of difficult-to-remove hydrophobic stains when the formulation of the invention is used in concentrated form.

The fatty solvents are used in amounts of 0 to 4% by weight, preferably 0.3 to 1% by weight, based on the total amount of detergent.

The polyethylene glycol used in the present invention has the general formula: % formula % where n can vary within the range of 4800 to 64600. Such polymers are also commercially available, for example from Union Carbide Corporation (Uni
on Carbide Corporation, U
It is commercially available from CC) under the trade name "POLYOXX (trademark)".

Additionally, the cleaning agents of the present invention may contain additives such as dyes and fragrances, preservatives, and optionally various antimicrobial agents.

The pH of the cleaning agent of the present invention is 5.5 to 9.5, preferably 6.0 to 7.5. I) Suitable acid regulators used for the adjustment of H are the customary inorganic or organic acids or acid salts, such as hydrochloric acid, sulfuric acid, bisulfates of alkalis, aminosulfonic acids, phosphoric acid or other phosphorous acids. , especially phosphorus acid anhydride or its salts or its acid-reacted solid compounds with urea, or other lower carboxylic acid amides, phosphorus acids or partial amides of phosphoric anhydride, citric acid, tartaric acid, butyric acid, etc. Organic or inorganic compounds such as alkanolamines (ie mono-, di- or triethanolamine) or ammonia may be added as basic substances. Alkaline reaction builders and washing alkalis such as sodium tripolyphosphate, sodium carbonate and bicarbonate, potassium carbonate and bicarbonate, sodium silicate and sodium aluminosilicate are also suitable for adjusting the weak alkalinity. be.

Initially, the preparation of the cleaning agent according to the invention was carried out by premixing the solid and liquid components and then homogenizing the resulting premix in a high speed disperser. Then,
There have been major problems in removing large amounts of air in the detergent that is introduced with the powdered ingredients or enters the product in the premixer. Although the amount of air entrained by agitation could be minimized by using a properly designed premixer, the total amount of air still amounted to about 20% by volume. In practice, products with a high air content varied considerably in density and could not be stored without exception. For this reason, "Seiffen, Aμ, Fetch, V7
”/Habit (Seifen, Ole, Fette)
.

Wachse) J1 Mikami, (1975), 125-12
The method described on page 8 and in West German Published Patent Application No. 2,619,810 was adopted. This method is described below.

Abrasion-resistant material with an agitator with a horseshoe-shaped part at the beginning (
A stirrer (preferably of good quality R) (the walls of which are equipped with a puller of abrasion-resistant, low-friction material, preferably polytetrafluoroethylene), with a second shaft tilted at 90° to the horseshoe stirrer. surfactant and water are introduced into the blade (the blade is fixed), and the circumferential speed is 0.5 to 4 m/s, preferably l
- After operating the stirrer at 1,5 m/s, remove all other ingredients such as abrasives, stabilizers, pigments, viscosity modifiers, suspension stabilizers, solvents, solubility promoters and hydrotropes. Added to solution with stirring. In this way, the powder agglomerates, solid masses and wall coverings were homogenized without increasing the air content in the mixture originating from the raw materials by introducing air. The mixture was then pumped in a fluidized disperser, preferably of the rotor-stator type. The shear gap and/or set rate was adjusted to the average diameter of the abrasive particles to minimize disintegration of the abrasive during dispersion.

After dispersion, the resulting formulation was degassed using a fluidized vacuum degasser and the product was centrifugally distributed using a rotating disk and a perforated plate. The pressure was adjusted to 20-100 mmHH. This degassing step may be performed before dispersion. After degassing, a relatively volatile fragrance was added. The final temperature of the product is approximately 2
The throughput, degree of dispersion and degassing pressure were mutually adjusted so that the temperature was 5° C. and direct packaging was possible.

The preparation may be carried out continuously or batchwise.

[Example co-plate test] The cleaning effect of the detergent used for hand washing dishes according to the present invention was evaluated in the magazine [Fette, Seiffen, Anstrichmibutyl (Fette, 5eifen).

Anstrichmittel) J, 74 (197
2), pages 163 to 165, it was measured by the so-called plate test. Place a 14cm diameter plate in beef tallow (
Melting point 40-42°C, acid value 9-1 O) 2g and egg white,
Alternately smeared with 2 g of fat and carbohydrate mixture, +0~
It was left for 15 hours at +5°C and then rinsed with tap water at 45°C (hardness 16°d = German hardness).

The products tested were used at a concentration of 0.5 g/&water. The number of plates that were thoroughly washed with detergent solution 5Q was used as an index of the cleaning effect.

Cleaner solution (0.4-1.0g/&; tap water hardness 16°d/45°C) 1001172 at the concentration used in 250
In the IIl12 mixing cylinder, Kay Hoffman (K.

It was shaken using a shaker of the type manufactured by Hof'a+ann), Berlin (20 revolutions of the cylinder at 5S rpm). The foam volume was measured with and without heating (by addition of olive oil) by reading the foam height from the scale of the mixing cylinder.

The abrasive effectiveness of the cleaning agent was measured using a combination of Enran-guo carbohydrate/egg white/fat stain. For this purpose, the ``MilumilB abyn''
ahrung) J 60 g were mixed with 80 g of water at 75° C. and the resulting mixture was degassed by a water jet pump.

The agglomerated mixture was applied to a 130 cm'' area of a VA steel plate in a layer thickness of 250 μI.

Next, after pre-drying at 45°C for 1 hour, drying at 200°C for 2 hours.
Baked for an hour. After cooling and weighing, the contaminated plate is
Soft needle felt pad (DLW type #vRc
It was polished 5 times with a cleaning agent 5-5 at a constant pressure. For this purpose, a plate made of high quality steel was fixed on a stand and pressure was applied against the pad by a hydraulic system, which was rotated at 7 Srp- and simultaneously moved back and forth (polishing width 200 am). European Patent No. 2154
Standard product according to No. 5 (Cat-Cps fatty alcohol (ethoxy), -sulfate 24% by weight, C11
-C14 alkyldimethylamine oxide 3.5% by weight
, Cristobalite (average particle size 40-50 μm) 6
, 5% by weight, 4.0% by weight of trisodium sulfosuccinate salt, 6.5% by weight of ethanol, and the balance water, pigment and fragrance) could not completely remove the stain. was used. After rinsing the polished plates with water, they were dried and weighed again. Polishing is expressed as polishing effect, expressed absolute (mg) or relative (%) to a given standard.

Plexiglas plates were treated in the manner described above in order to determine how gentle the abrasive action is on sensitive surfaces. The surface of the treated plate is
Lange reflectometer (measuring head 60°)
Measured using The measurement results are expressed as the value for water (100
%).

Table 1 shows the composition of commercial hard surface cleaning agents (A-E) with and without abrasives and the composition of the cleaning agent of the present invention.

Table 2 shows the results of the test. ClICl3 fatty alcohol ether sulfate 18% by weight, CI! -C
4% by weight of I4 alkyldimethylamine oxide, 2% by weight of trisodium sulfosuccinate, 7% by weight of quartz powder (particle size 43-105 μm), 2.5% by weight of Aerosil (trademark) 200 as a suspension stabilizer.
The product according to EP 21 545, consisting of , balance water, pigments, electrolytes and fragrances, was used as standard.

It is clear from these results that the cleaning agent of the present invention is superior to standard cleaning agents. That is, the foaming power is not adversely affected by the abrasive, the polishing effect is surprisingly good despite the fineness of the abrasive, and surprisingly, limonene as a fatty solvent is also only 0.2-0. Even amounts of 8% by weight increase the viscosity of the detergents of the invention.

In addition to being suitable for cleaning soiled hard surfaces, cleaning agents made in accordance with the present invention are suitable for cleaning soiled hard surfaces.
If it contains an abrasive/polishing agent ultrafine powder such as NT (Trademark), it is also suitable for removing cloudiness from metal surfaces (cutlery, precious metals, etc.). In this case, the surface protection is no different than when using water alone (i.e. the cleaning agent produced according to the invention does not leave visible scratches)
.

For example, in cleaning silver, the effectiveness of the detergent of the present invention can be compared with commercially available silver cleaners (Puragan).

Trademark) and thiourea series).

The silver pieces were cleaned by hand using a soft cloth and then rinsed with water. After drying, 5 people visually evaluated it. The scoring criteria are shown in Table 3.

Table 3 Patent Applicant: Henkel Kommandit Gesellschaft Auf Akchen

Claims (1)

[Claims] 1. Contains an abrasive, water, and a surfactant base that is an anionic surfactant mixture or a mixture of an anionic surfactant and an amphoteric surfactant, and has a pH of 5.5 to 9.
5, a builder-free, suspension-stable, multi-purpose liquid cleaning agent for hard surfaces. 2. The cleaning agent according to item 1, which contains a mixture of at least two different anionic surfactants. 3. The cleaning agent according to item 1 or 2, which contains a mixture of one or more anionic surfactants and amphoteric surfactants. 4. The cleaning agent according to any one of items 1 to 3, containing 10 to 35% by weight, preferably 15 to 25% by weight of the surfactant mixture. 5. Nos. 1 to 4, wherein the weight ratio of anionic surfactant to amphoteric surfactant is 20:1 to 1:1, preferably 15:1 to 1:1, more preferably 8:1 to 1:1. The cleaning agent described in any of the paragraphs. 6. Water-insoluble abrasive with an average particle size of 5-100 μm
The first containing 20% by weight, preferably 10-15% by weight.
The cleaning agent according to any one of items 1 to 5. 7. The cleaning agent according to any one of items 1 to 6, which has a pH of 6.0 to 7.5. 8. Dishwashing detergents, multi-purpose cleaners, polishes and/or polishes comprising a cleaning agent according to any one of items 1 to 7.