WO2020027742A2

WO2020027742A2 - A semi viscous hydrogen peroxide containing hard surface cleaning composition

Info

Publication number: WO2020027742A2
Application number: PCT/TR2018/050412
Authority: WO
Inventors: Ahmet Ergun; Murat Uzumcu; Gunsu KOMURCUOGLU; Meral COBAN
Original assignee: Hayat Kimya Sanayi Anonim Sirketi
Priority date: 2018-08-03
Filing date: 2018-08-03
Publication date: 2020-02-06
Also published as: WO2020027742A3

Abstract

The present invention relates to peroxide containing cleaning compositions and use thereof. The present invention peroxygen containing cleaning compositions are semi-viscous form comprising sulphated anionic surfactants, amphoteric surfactants, non-ionic surfactants, inorganic magnesium salt and phosphonate salt. Said compositions can be used to clean surfaces such as bathroom or kitchen tiles, pan, dish, metal surfaces, rigid plastic surfaces, other tile containing areas and provides hygiene with oxygen based and chlorine-free composition.

Description

A SEMI VISCOUS HYDROGEN PEROXIDE CONTAINING HARD SURFACE CLEANING

COMPOSITION

FIELD OF THE INVENTION

The field of the present invention relates to cleaning compositions. The field of the present invention relates to hard surface cleaning compositions.

The field of the present invention relates to hydrogen peroxide containing composition and use thereof.

The field of the present invention relates to semi-viscous cleaning compositions with low pH.

The present invention compositions allow high rinsability and very less residue on the application surfaces.

The present invention compositions also allow comfortable breathing by direct application due to its chlorine-free content.

BACKGROUND OF THE INVENTION

Consumers not only want effective cleaners but want to be sure that the objects to be cleaned are not damaged during cleaning process. This changing perception leads them to be more selective about the effectiveness, performance and safety of the cleaning compositions. Consumers demand to choose detergent composition mainly according to the cleaning capability of the product. They judge the cleaning capability of a detergent composition according to the cues they receive during the cleaning process. Formation of foam and duration of it, having clean fragrance in detergent are some of the marks that consumers have confidence in that, the product is working effectively and sustaining its cleaning performance. In addition, consumers want to use products that not only do good cleaning but also do not harm their health, do not irritate their skin, and not deform their clothing when they come in contact with their clothes to the cleaning composition. As a result, the consumer no longer wants to lose health by demanding white plates, laundries or a surface with no water marks or stains.

By cleaning hard surfaces, it has always been a challenge to reach the complete cleaning due to the presence of ions which are responsible for water hardness. Tap water contains solubilized ions causing water hardness which leads to the deposition of salts of calcium l carbonate on surfaces with the consequent, formation of watermarks upon water evaporation. When surfaces become in contact with water, these salt deposits lead to anaesthetic appearance of the surfaces like reduced shine with increased paleness. This formation causes a bad appearance on the surface and it becomes difficult to clean up over time.

During the cleaning of hard surfaces, it is important but difficult to determine whether the deposited area is covered with the cleaning composition or not in order to achieve complete cleaning. Effective cleaning is also related to the cleaning time of the cleaner and the contact time of the stain with the cleaning composition. For this reason, the composition is expected to remain on the surface for some time.

During the cleaning of hard surfaces, it is difficult but important to determine whether the deposited area is covered with the composition or not in order to assist the attainment of complete cleaning.

Hard surface cleaners like bathroom or kitchen cleaners known for many years to have alkaline pH. They offer effective cleaning for removing most stains and especially the fatty soils. However, they are moderately effective to remove limescale deposits since limescale removal can be achieved by a chemical reaction in acidic media.

The formation of water marks, soap scums and limescale deposits on hard surfaces can be reduced when surfaces are treated with liquid acidic compositions. Although several liquid acidic hard surface cleaners have been known in the art, none of them has the ability to remove the limescale and fatty soils by its hydrogen peroxide containing and chlor-free composition.

Liquid hydrogen peroxide containing compositions are described in the art, especially for laundry pre-treatment, laundry wash or carpet cleaner.

Many efforts have been made to overcome the problems stated above.

W02003080782A1 discloses a hydrogen peroxide containing dish cleaning composition with a viscosity in the range of 100 to 1000 cps containing linear alkyl benzene sulphonate as anionic surfactant, a zwitterionic surfactant as amphoteric surfactant, alkyl glucoside surfactant as non-ionic surfactant and a solubilizier. This composition has high surfactant content such as around 30 % by weight as such difficult to formulate and needs solubilizer.

APG amounts such high that it causes cost problem by formulation. Linear alkyl benzene sulphonate causes skin irritations and high foam which makes rinsing difficult. There is a need to formulate new hydrogen peroxide containing hard surface cleaning composition with moderate viscosity avoiding above mentioned difficulties.

SUMMARY OF THE INVENTION

The present invention encompasses a semi-viscous cleaning composition comprising a hydrogen peroxide, a sulphated anionic surfactant, an amphoteric surfactant a non-ionic surfactant, inorganic magnesium salt and phosphonate salt.

Preferred semi-viscous cleaning compositions of the present invention have a hydrogen peroxide in the range of 0.1 -5.0 wt. %, a sulphated anionic surfactant in the range of 0.1 -7.0 wt. %, a amphoteric surfactant in the range of 0.1 -5.0 wt. %, non-ionic surfactant in the range of 0.1 -3.0 wt. %, inorganic magnesium salt in the range of 0.1 -2.5 wt. %.

The present invention comprising cleaning composition is used for treating hard surface areas e.g. bathroom or kitchen tiles, ceramic, toilet bowls, kitchen bench and similar surfaces.

The present invention also comprises chlorine-free cleaning composition and allows comfortable breathing and effective stain and limescale removal by direct application. Additionally, the present invention comprises use of sulphated anionic surfactant/hydrogen peroxide in a semi-viscous composition having a pH below 5 and said composition provides the effective stain and limescale removal benefits.

DISCLOSURE OF THE INVENTION

The compositions according to present invention are formulated in semi-viscous form contrary to the widely used solid or low viscous liquid form. Semi-viscous includes gel, sprayable liquid /gel and paste forms.

It has now been found that this object can be efficiently met by formulating a semi-viscous composition comprising a peroxygen bleach, sulphated anionic surfactant, amphoteric surfactant, non-ionic surfactant, Mg-salt, phosphonate salt and pH adjusting agents. The object of the present invention is to provide a semi-viscous composition providing effective cleaning performance and effective stain removal performance under hard surface treatment conditions, while exhibiting semi-viscous and acidic properties. The present invention composition includes essential elements which are contributing to the formation of semi-viscous form.

Bleaching is another desired effect of the cleaning composition of the present invention.

The bleaches are basically divided into two groups; -Oxidative bleaching

• Chlor based bleaching such as (sodium hypochlorite, sodium chlorite)

• Oxygen based bleaching (hydrogen peroxide or peroxide-containing solutions, such as sodium perborate, sodium percarbonate)

-Reductive bleaches constitute another category and are generally used for bleaching textile, paper and pulp.

World cleaning trend has been shifted away from chlorine-based bleaches because of the negative effect to the human’s health and oxygen-based bleaches begun to be preferred Amount of the hydrogen peroxide content is an important factor. High level of the hydrogen peroxide causes skin irritation by the consumer. Peroxygen bleach compounds are essential element of the cleaning composition of the present invention. Suitable peroxygen bleaches to be used in the present invention are selected from the group consisting of: hydrogen peroxide; organic or hydroperoxides; inorganic peracids; diacyl peroxides; and mixture thereof.

Peroxygen bleach compound according to present invention is hydrogen peroxide or sources thereof. As used in the present invention, hydrogen peroxide source refers to any compound which produces perhydroxyl ions when said composition is in contact with water. Indeed, the presence of a peroxygen bleach, preferably hydrogen peroxide, contributes to the excellent cleaning and bleaching benefits of the present invention.

Typically, the cleaning composition of the present invention comprise from 0.1 % to 5.0 %, preferably 1 % to 4% and more preferably from 2 % to 3% by weight of the total composition of said peroxygen or mixture thereof.

The present invention comprises an amphoteric surfactant which is a betaine surfactant including compositions, preferably selected from water dispersible and water soluble betaine surfactants. Examples of such water-soluble betaine surfactants include dodecyl dimethyl betaine and cocoamidopropyl betaine which is particularly preferred.

Formula of the cocoamidopropyl betaine surfactant was represented by;

Amphoteric surfactants are suitable for wide range of applications. In combination with anionic surfactants, synergistic effects are achieved which lead to a dermatological improvement of the consumer product.

Typically the compositions herein comprise from 0.1 % to 5%, preferably 1 % to 4% and more preferably from 2% to 3% by weight of the total composition of said amphoteric surfactants. The present invention also comprises an anionic surfactant. Said particularly suitable anionic surfactants are preferred in the present invention as they contribute to the stain removal performance of the cleaning compositions of the present invention.

The anionic surfactants of the present invention are; alkyl sulfates, alkyl ether sulfates or aryalkyl ether sulfate. The semi-viscous form formation of the cleaning composition was obtained by the sulphated anionic surfactant compounds. This objective could not be achieved with the sulfonated anionic surfactants.

With present invention compositions there exist no need for viscosity enhancing agents, such as xanthan, clay, viscosity enhancing cellulosic compounds. Sulphated anionic surfactant is compatible with other cleaning composition ingredients and exhibits effective cleaning performance by keeping semi-viscous and acidic conditions.

The preferred sulfated anionic surfactant for use in the present invention is an alkyl ether sulfate and shows an effective synergistic effect on the present invention cleaning composition. These synergistic effect is especially effective on the viscosity. More preferably said sulfated anionic surfactant used in the present invention is C12-14 alkyl ether sulfate. The clear aqueous cleaning composition of the present invention comprise, sulphated anionic surfactant wherein said surfactant comprises of SLES, SLES with 1-3 ethoxy group preferably SLES with 2 ethoxy groups.

SLES (Sodium Lauryl Ether Sulphate) is the suitable and preferred anionic surfactant for the semi-viscous cleaning composition of the present invention.

SLES improves the cleaning capability and provides skinmild benefits. SLES also provides solution of fatty soils with the cleaning composition of the present invention and contributes to the stability of hydrogen peroxide.

Semi-viscous form formation depends on the ratio of the surfactant used. Especially SLES plays a significant role in the composition of the present invention.

The cleaning composition according to present invention comprise from 0.1 % to 7.0%, preferably 1 % to 5% by weight of the total composition of said sulfated anionic surfactant.

Nonionic surfactants has established in the detergent and cleaner industry, and many other branches of industry an account of their pronounced surface activity. Nonionic surfactants are fully compatible with alkylaryl sulphonates, ether sulphates and other sulphated and sulphonated products. Synergistic effects enables high levels of washing performance.

The present invention composition also comprises a nonionic surfactant which is preferably based on a saturated, predominantly unbranched C_{13-15 OXO} alcohol, alcohol ethoxylates. The nonionic surfact conform to the following structural formula;

R0(CH₂CH₂0)XH wherein R is C_13-15 oxo alchol and wherein x is 3, 4, 5, 7, 8,11 or 30.

The cleaning composition according to the present invention comprise from 01.% to 3.0%, preferably 0.5 % to 3% by weight of the total composition of said noninoic surfactant. The pH of the semi-viscous composition of the present invention can range from 1.5-5. The acidic pH range contributes to the chemical stability of the compositions and the stain removal performance of the compositions.

The present invention composition comprises earth alkali metal salts as an ion source. Its use is crucial for obtaining enhanced viscous composition. Suitable alkali metal salts as an ion source are MgS0₄, MgCI. Preferred earth alkaline metal is Mg and its preferred salt is MgS0₄.

Advantageously the viscosity of the semi-viscous composition of the present invention can range up to 1000 cPs, preferably 100-800 cPs and more preferably 300-700 cPs; cPs: centi poise. Rinsability was provided by the low pH and preferred viscosity range of the cleaning composition of the present invention.

The object of the present invention is a hydrogen peroxide containing liquid aqueous composition providing effective cleaning performance under hard surface treatment conditions, while exhibiting semi-viscous and acidic properties. Advantageously the composition of the present invention exhibit effective stain removal performance for limescales, water marks, fatty soils and other kitchen or bathroom stains. At the same time, the present invention does not cause harm to the surface and provides color protection. This feature gives consumers the feeling at safe compared to chlorine based cleaners. In view of changing cleaning concept, the present invention provides a chlorine-free composition, which comprises hydrogen peroxide containing aqueous hard surface cleaner.

The present invention provides to the controlled usage of the detergent on the applied surface by the presence of color of the cleaning composition, thus the user easily can distinguish between detergent applied surface and non-applied surface. Additionally, the present invention offers a visual indication of the completeness of cleaning process.

The present invention comprises a liquid hard surface hydrogen peroxide containing composition especially suitable for the hard surface areas, such as limescales, water marks, fatty soils and other kitchen or bathroom stains. The composition has a clear appearance and low viscosity form and sufficient hydrogen peroxide stability which is provided with help of sulphated anionic surfactant; SLES.

The present invention also allows comfortable breathing and low skin irritation when used in direct application due to its chlorine-free content. The present invention allows high rinseabilty and very less residue on the applied surfaces consumers are in everyday contact.

The present invention cleaning composition of the present invention has overcome above mentioned problems by chlorine-free composition.

The cleaning composition of the present invention comprises from 0.1 % to 5.0 %, preferably 0.5% to 3.0% and more preferably from 0.5-1.5 % by weight of the total composition of said peroxygen or mixture thereof.

The cleaning composition according to the present invention comprises from 0.1 % to 7.0%, preferably 1.0 -5.0% by weight of the total composition of said sulphated anionic surfactant.

Typically the compositions herein comprise from 0.1 - 5.0 %, preferably 0.5-4.0 % weight of the total composition of said amphoteric surfactants.

The cleaning composition according to the present invention comprises from 0.1 % to 3%, preferably 0.5-3.0 % by weight of the total composition of said noninoic surfactant.

The cleaning composition according to the present invention comprises 0.1 -2.5 wt. % Mg salt preferably 0.5-2.0 % by weight of said cleaning composition. The cleaning composition according to the present invention comprises 0.1-2% by weight of phosphonate of said cleaning composition.

The present invention also comprises optionally one or more constituents which provide a technical or aesthetic benefit to the present invention composition such as perfume, pH adjusting agent, clay, cellulose derivatives and dye. Advantageously the viscosity of the semi-viscous composition of the present invention can be up to 1000 cPs, preferably range between 300-800 cPs. The pH of the semi-viscous composition of the present invention can be 1.5-5, targeted pH range is 2-4 obtained with pH adjusting agents.

EXAMPLES EXAMPLES l-IX The following examples were made by mixing the listed ingredients for the gel formation of the present invention, in the listed proportions (weight % unless otherwise specified).

Added a color and perfume and pH is adjusted to 2.7±0.3.

Phosphonate is added for the purpose of hydrogen peroxide stabilization and water to complete,

SLES: Sodium Lauryl Ether Sulphate Dehyton PK 45: Cocoyl Amide Propyldimethyl Glycine Solution

Lutensol A07: Oxo alcohol ethoxylates that are based on predominately linear alcohols, with a medium degree of ethoxylation

Dequest 2066 A: Diethylenetriamine penta(methylene phosphonic acid), sodium salt DTPMP.Na TEXAPON V 95 G: Sodium C 12-14 fatty alcohol sulfate/ Sodium Lauryl Sulfate LABSA: Linear Alkyl Benzene Sulphonic Acid BETAIN: Cocamidopropyl Betaine EDTA: Ethylenediaminetetraacetic acid COMPARATIVE EXAMPLE: Includes; 4.20 wt.% amphoteric surfactant,

0.75 wt.% fatty acid,

35.0 wt. % hypochlorite,

0.30 wt.% phosphonate, 2.5 wt.% caustic and water to complete.

The pH of the comparative example composition ranges between 12.75±0.75.

The viscosity of the comparative example composition is between 2500±1500 cps.

Example I; cleaning composition has viscosity value in the desired ranges but this is achieved with excess surfactant amounts causing high costs.

Example II; cleaning composition has desired viscosity value but still has high surfactant content.

Example III; cleaning composition has viscosity value still in the desired range but still has high surfactant content. The decrease in viscosity indicates that SLES and amphoteric are viscosity related.

Example IV; cleaning composition surfactant amounts range in total in the desired amount range but has very low viscosity therefore not desired. The low viscosity value indicates to insufficient amount of surfactant. Decreased amount of SLES and amphoteric surfactant seems to be related to decreased viscosity. Example V; The achieved low viscosity reveals that although the content of the ingredients of this example compositions is in the desired amount ranges no viscosity increase is achieved.

Besides increased non-ionic surfactant amount did not lead to viscosity increase.

Example VI; By maintaining SLES and amphoteric surfactant ingredients in the same amount range compared to Example V, by adding MgS0₄ the viscosity increases in desired viscosity ranges of 500 cps from 25 cps. The non-ionic amount is decreased to the for the cleaning composition sufficient amounts.

Example VI; compound is the composition of the present invention. It comprises the necessary amounts of surfactant all three classes; anionic, amphoteric and non-ionic, and has the desired viscosity. Example VII; changing surfactant ingredients did not contributed to viscosity level increases. Obtained cleaning composition has viscosity values of below the desired level. Example VIII; cleaning composition has viscosity value in the desired range due to apparently by adding MgS0₄ added in sufficient amounts.

But used sulphated anionic surfactant has higher skin irritancy properties compared to SLES and comprises no non-ionic surfactants which are necessary for removing oily stains. Conclusively although having desired viscosity range this composition is not suitable for the targeted hard surface cleaning composition with desired skin mild, washing performance properties.

For the desired washing performance such as foaming, rinsing, oil removal, skin mildness and cleaning performance. So that consumers are satisfied, necessary surfactant amounts are given in Example VI.

TESTS

RINSABILITY TEST

Test Equipment: 8 glass cups, 8 soaked sponges, reference detergent and the cleaning composition of the present invention. Method: The amount of detergent is kept under control, the amount of foaming; washing and rinsing types are not controlled.

Sample Preparation:

1. 6 ml of cleaning product are dropped to previously unused soaked sponges

2. The sponge is bubbled and wring.

3. A glass is washed with that sponge.

4. Glass is rinsed with top water until the whole glass surface is clear.

Measurement: The volume of water consumed to rinse the glass cups are measured;

-Water amount to rinse the present invention cleaning composition of example IX: 362,5 ml

-Water amount to rinse the cleaning composition of comparative example: 1350 ml Evaluation: 8 people have attended the rinsing test. Water amounts needed to rinse with Example VI composition and Comparative Example composition wash liquor soaked glass cups are measured. The amount of water needed by rinsing with present invention composition soaked glass cups are compared with the amount of water needed by rinsing with comparative example composition soaked glass cups.

The results reveals that with present invention composition soaked glass cups need less rinsing water than with the comparative example soaked glass cups.

The amounts of water needed by rinsing with present invention and comparative example composition were given in Table 1.

Table 1. The amounts of Water Needed by Rinsing with Present Invention Composition Example VI and Comparative Example Composition

LIME REMOVAL TEST

Test equipment: Marble slabs, ethanol, oven, comparative example and present invention cleaning compositions.

Method: IKW SOFW J129:2003 (IKW- The German Cosmetics, Toiletries, Perfumes and Detergent) Sample Preparation: Prior to the testing marble slabs are degreased with ethanol and rinsed under running water with a brush. The slabs are dried at 105°C for 1 hour and weighed (W1). 250 ml cleaner (lime removal product) are transferred to a cuvette. Then the whole slab is soaked for 10 minutes in the cleaner. Afterwards, the slap is removed and rinsed under running top water while brushing. The slaps are dried at 105°C for 1 hour and weighed (W2). The quantity of dissolved calcium carbonate is determined by the difference in weight (W1 - W2). The measurement is carried out using 5 marble tiles. Table 2. Limescale Removal Performance Results of the Present Invention Cleaning Composition Example VI; and Comparative Example cleaning composition

Evaluation: the present invention cleaning composition removes more lime scale than comparative example cleaning composition from hard surfaces.

RESIDUE TEST

Test equipment: a. Total organic carbon analyzer(Shimadzu TOC-VCPH), using combustion techniques b. Sampling, injection, and sample preparation accessories, as prescribed by instrument manufacturer. c. Sample blender or homogenizer. d. Magnetic stirrer and PTFE-coated stirring bars. e. Filtering apparatus and 0.45-pm-pore-diam filters. Preferably use FIPLC syringe filters with no detectable TOC blank. Glass fiber or silver membrane filters also can be used. Rinse filters before use and monitor filter blanks.

Method: Standard Method 5310 for the Examination of Water and Waste Water High Temperature Combustion Method -Approved by Standard Method Committee, 2014.

Applied with the present invention cleaning composition; samples are washed and rinsed. Sample preparation: A glass of cup, metallic surface, plastic glove, tile, plate, swab are washed and the wash water is analysed for the determination of the total organic carbon.

Result and Evaluation: Obtained TOC (Total Organic Carbon) values for all samples are all under 1 mg/I thus suffice to fulfill the requirements. The present invention compositions are capable to remove the oil stains sufficiently.

VISCOSITY MEASUREMENT

Viscosity is measured at 20°C by using Brookfield viscometer (LVT) with spindle No. 2 at 12 rpm in a 150 ml sample. All of the results are average of three measurements. All of the viscosity values are in cPs.

Claims

1. An acidic, colored clear aqueous hard surface cleaning composition in semi viscous form comprising

0.1 -5.0 wt. % Hydrogen peroxide 0.1 -7.0 wt. % sulphated anionic surfactant

0.1 -5.0 wt. % amphoteric surfactant 0.1 -3.0 wt. % non-ionic surfactant 0.1 -2.5 wt. % inorganic Mg salt By weight; Wherein the composition exhibits viscosity in the range of 300-800 cPs.

2. A cleaning composition according to claim 1 , wherein said hydrogen peroxide comprises preferably 0.5-3.0 % more preferably 0.5-1.5 % by weight of said cleaning composition.

3. A cleaning composition according to claim 1 , wherein said sulphated anionic surfactant comprises alkyl sulphate, alkyl ether sulphate, aryl alkyl sulphate, alkyl ethoxylated ether sulphates, Sodium Lauryl Ether Sulphate (SLES).

4. A cleaning composition according to claim 1 and claim 3, wherein said sulphated anionic surfactant is preferably SLES with 1-3 ethoxy groups, more preferably with 2 ethoxy groups.

5. A cleaning composition according to claim 1 , wherein said sulphated anionic surfactant comprises preferably 1.0 to 5.0 % by weight of said cleaning composition 6. A cleaning composition according to claim 1 , wherein said amphoteric surfactant comprises

0.5-4.0 % by weight of said cleaning composition.

7. A cleaning composition according to claim 1 , wherein said non-ionic surfactant comprises preferably 0.5-3.0 % by weight of said cleaning composition.

8. A cleaning composition according to claim 1 , wherein said inorganic magnesium salt is MgC or MgS0₄, preferably MgS0₄ salt.

9. A cleaning composition according to claim 1 and claim 8, wherein said inorganic Mg salt comprises preferably 0.5-2.0 % by weight of said cleaning composition.

10. A cleaning composition according to preceding claims, wherein said composition further comprises 0.1-2 % phosphonate by weight.

11. A cleaning composition according to claim 1 , wherein said composition excludes thickeners based on clays and cellulose derivates and polymeric thickeners.

12. A cleaning composition according to claim 1 , wherein said acidic composition as a pH in the range of 1.5-5.0 preferably 2.0-4.0.

13. A cleaning composition according to preceding claims comprising; 0.5- 3.0 wt.% hydrogen peroxide.

1.0-5.0 wt.% sodium lauryl ether sulfate with 1-3 ethoxy groups 0.5-4.0 wt.% cocamidopropyl betaine as amphoteric surfactant 0.5-3.0 wt.% alcohol ethoxylates as non-ionic surfactant 0.5-2.0 wt.% MgS0₄.

14. A cleaning composition according to Claim 1 , wherein said composition is well rinsable after applying on the surfaces and requires less water.

15. A cleaning composition according to preceding claims, used in dishwashing, hard surface, lavatory, tiles, bathroom, kitchen, metal surfaces, rigid plastic surfaces.