JP2001520260A - Acid cleaning composition containing alkoxylated amine and use thereof - Google Patents

Abstract

(57) Abstract: By using 0.01 to 15% by weight of an alkoxylated aliphatic amine having 8 to 20 carbon atoms and 1 to 8 alkoxylated units, 0.01 to 15% by weight of sulfamic acid can be obtained. The antimicrobial effect of the acidic antimicrobial composition is improved. The present invention also provides 0.01 to 15% by weight of an alkoxylated aliphatic amine having 8 to 20 carbon atoms and 1 to 8 ethoxylated units, 0.01 to 15% by weight of sulfamic acid, and a peroxygen species. Also provided is an acidic antimicrobial composition comprising a source, and a method of disinfecting a surface, comprising treating the surface with an acidic antimicrobial composition of this type. Typically, the alkoxylated aliphatic amine has the general _{formula: H (A) x -N (} R) - (A) y H ( wherein, R is an alkyl or alkenyl group containing 8 to 20 carbon atoms And A is an ethoxy group, and x and y may be the same or different and are integers from 1 to 4). Preferably, x and y are both 1 or 2. In a preferred embodiment of the present invention, R is C ₁₄ -C ₁₈ alkyl, most preferably derived from oleic acid, palmitic acid, or myristic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION [0001] The present invention relates to acidic cleaning compositions, particularly acidic antimicrobial cleaning compositions suitable for use on hard surfaces.

BACKGROUND OF THE INVENTION Many formulations for so-called "descaler" compositions have been proposed in the literature. These generally contain enough acid to produce a low pH, and may also contain a thickening agent that causes the composition to stick to and remain on the sloped surface, e.g., the interior of the toilet bowl. . As described in more detail below, known thickeners include both ethoxylated and non-ethoxylated tertiary amines, alone or in combination with a hydrotrope. Acids known for use in such compositions include sulfamic and phosphoric acids.

It is advantageous that such compositions are antimicrobial and that they exhibit this antimicrobial action against a wide range of microorganisms. To achieve this, various fungicides have been proposed as additives to these compositions.

[0004] GB 1443244 relates to acidic detergents and scale removers containing ethoxylated tertiary amines as thickeners, among which ethome (ETHOM)
EEN) S12 (N, N-dihydroxyethyl-oleylamine) is mentioned as an example. The composition also contains a mineral acid and a strong inorganic acid, such as an acid selected from acid salts of sulfamic acids. A fungicide is an additional optional ingredient.

[0005] FR 2459830 discloses a composition comprising a non-ethoxylated amine and an ethoxylated amine together with a sulfamic acid.

WO 95/27768 is a cleaning composition, especially for painted plastic surfaces, comprising 3-8 ethoxy units (preferably 4-6) and C ₆ -C ₁₀ carboxylic acids and / or organic or discloses a composition comprising an ethoxylated C ₁₀ -C _{1 8} aliphatic amines containing an inorganic chelating agent. It is not disclosed that these compositions have disinfecting properties.

[0007] AU-A-57022 / 86 relates to a cleaning system comprising a mixture of sulfamic acid and phosphoric acid and an acid-stable surfactant. The fungicide is optional, formalin is
It is disclosed as a bactericide to improve the antibacterial action of these acids.

[0008] EP-B-0276501 is a thickened aqueous cleaning composition comprising pK
> 2 (sulfamic acid is mentioned as an example)
50% by weight, 0.1-20% by weight of an amine optionally containing 2% of oleyl-bis- (2-hydroxyethyl) -amine, and 0.01% by weight of hydrotrope (an example is sodium xylene sulfonate) % Is disclosed. The disinfectant is optional.

[0009] EP-A-03142232 relates to compositions which have a viscosity increase upon dilution, wherein the thickened liquid detergent composition comprises amine oxides, amines (eg Etmeen S12 ^™ ), betaines. Or a quaternary ammonium compound, and a hydrotrope (sodium xylene sulfonate). In this specification, the amine oxide and the quaternary ammonium compound are
It is also described that it is known to be life-destructive, and furthermore that a bactericide containing an organic peracid is optional. These compositions may be of acidic, neutral, or alkaline pH.

From the above, it is known that certain thickening surfactants such as quaternary ammonium compounds and amine oxides have antibacterial properties, but antibacterial action is desired in addition to scale removal. It turns out that it was trivial to suggest adding additional antimicrobial components to such a descaling composition.

BRIEF DESCRIPTION OF THE INVENTION The present inventors have determined that compositions comprising both alkoxylated aliphatic amines and sulfamic acid exhibit improved antimicrobial activity. This is due to the synergistic interaction of these components, which is independent of the presence of other antimicrobial components (
That is, in the absence of this).

The present inventors have also determined that excellent descaling and disinfection can be obtained using a composition comprising: (a) an alkoxylated aliphatic amine, (b) sulfamic acid, And (c) a source of peroxygen species.

DETAILED DESCRIPTION OF THE INVENTION According to a first aspect of the present invention, in order to improve the antibacterial effect of an acidic antibacterial composition containing 0.01 to 15% by weight of sulfamic acid, 8 to 20 pieces of acidic antibacterial composition are used. There is provided the use of 0.01 to 15% by weight of an alkoxylated aliphatic amine having aliphatic hydrocarbon groups of carbon atoms and 1 to 8 alkoxylated units per mole of amine.

According to a second aspect of the present invention, there is provided: (a) 0.01 to 15 weight percent of an alkoxylated aliphatic amine having 8 to 20 carbon atoms and 1 to 8 alkoxylated units. %; (B) 0.01-15% by weight of sulfamic acid; and (c) a source of peroxygen species.

According to a third aspect of the present invention, (a) 0.01 to 15% by weight of an alkoxylated aliphatic amine having 8 to 20 carbon atoms and 1 to 8 alkoxylated units, b) A method for disinfecting a surface, comprising a step of treating the surface with an acidic antibacterial composition comprising 0.01 to 15% by weight of sulfamic acid.

Amine : Typically, the alkoxylated aliphatic amine is a tertiary amine of the general formula: H (A) _x -N (R)-(A) _y H wherein R is 8 An alkyl or alkenyl group containing from 20 to 20 carbon atoms,
A is an ethoxy or propoxy group, x and y may be the same or different,
Is an integer of ４4. Preferably R is 8 to 18, more preferably 10 to 18 carbon atoms, and x and y are preferably 1 to 3, more preferably 1 or 2. Preferred materials, A is -OCH ₂ CH ₂ - is a is ethoxylated amines. In a further preferred embodiment of the present invention, R is C ₁₄ -C ₁₈ alkyl or alkenyl, derived for example oleic acid, palmitic acid, or myristic acid.

Suitable ethoxylated aliphatic amines are, for example, the following:-from AKZO, under the trademark ETHOMEEN S1
N, available as 2, N-di (hydroxyethyl) - oleylamine; - a _C 12 _{-C 18} fatty amine ethoxylates containing 2 or 3 ethoxy groups, 20 to 40 aliphatic group wherein % what is unsaturated _{(i.e., R = C 12 ~C 18 20~40} % unsaturated, x = 1, and it is y = 1 or 2). One example of such a material is Etomein BTB / 12 ^TM , also available from Akzo, which contains N, from fully cured tallow.
It is a mixture of N-di (hydroxyethyl) aliphatic amine and oleyl derivative in a ratio of 65/35. Such admixtures can be prepared by synthesis using the combined starting materials mixed in appropriate ratios. Alternatively, it can be obtained by mixing commercially available materials, for example, Etmein HT12 ^™ and Etmein S12 ^™ in a desired ratio.

C _12- containing two or (more preferably still) three ethoxy groups.
C ₁₆ alkyl amine _{(i.e., R} = _C 12 _{~C 16} alkyl, x = 1, and y = 1 or preferably 2).

As can be seen, particularly suitable ethoxylated amines or mixtures of such amines are those in which the aliphatic groups predominantly (more than 50%) are derived from C ₁₆ and C ₁₈ fatty acids. Yes, and (average) x + y is 2-3.

[0020] Preferred levels of alkoxylated aliphatic amines are based on the product (on p
product) from 1 to 10% by weight, with levels of 2 to 6% by weight for the product being particularly preferred.

Acids : Typical levels of sulfamic acid (ie amino-sulfonic acid) are 1-10% by weight for the product, with levels of 2-6% for the product being particularly preferred.

Peroxygen source : A typical source of peroxygen, if present, includes one or more hydrogen peroxide, peracetic acid, and / or other organic or inorganic peroxygen sources. . Hydrogen peroxide is a preferred source of peroxygen species. Typical levels of hydrogen peroxide are 1 to 10% by weight of the product, with levels of 3 to 8% being particularly preferred.

Surfactants : Preferred compositions according to the invention further comprise a nonionic surfactant and / or a hydrotrope.

Suitable nonionic detergent active compounds (surfactants) are condensation of alkylene oxide groups, which are actually hydrophilic, with organic hydrophobic compounds, which may actually be aliphatic or alkylaromatic. Can be widely described. The length of the hydrophilic polyoxyalkylene groups condensed with special hydrophobic groups can be easily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Can be. Suitable nonionic surfactants include alkoxylated alcohols and alkyl phenols, preferably ethoxylated alcohols.

Preferred ethoxylated alcohols are of the general formula R _1- (OCH ₂ CH ₂ ) _m -OH wherein R ₁ is a linear or branched C ₈ -C ₁₈ alkyl or hydroxyalkyl (preferably alkyl), and m is an average of 1 to 14 It is. Ethoxylated alcohols suitable for use in the present invention include LIAL 1 from DAC.
Includes the LIAL series available on the market such as 11.10EO ™.
Typical levels of non-ionic surfactants in the products according to the invention are 0-5%.

Suitable hydrotropes include lower aliphatic alcohols, especially ethanol, urea,
And / or salts of alkylaryl-sulfonates such as toluenesulfonate, cumenesulfonate or xylenesulfonate, especially alkali metal salts.

A preferred hydrotrope is an alkylaryl sulfonate, most preferably sodium cumene-sulfonate. A suitable material is ELTESOL (ELTE
SOL) SC40 (Albright & Wilson, Inc. ((Albright
and Wilson). Typical levels of hydrotrope are 0.05-2% by weight of the product.

In a particularly preferred embodiment of the present invention, the alkoxylated aliphatic amine is present with the anionic surfactant at the following levels: That is, at a level where these materials interact to thicken the composition.

Preferably, the formulation containing the alkylarylsulfonate is formulated at pH 2 or lower, more preferably at pH 1.5 or lower, and even more preferably at pH 1 or lower. While not wishing to limit the invention with reference to operating theory, at such low pH,
The ethoxylated amine behaves as a cationic surfactant and interacts with the alkylaryl sulfonate to form a water-insoluble gel, which is believed to deposit as a monolayer on the surface. It is believed that this monolayer lowers the surface energy of the surface and slows or prevents further lime scale deposition.

The preferred molar ratio of the ethoxylated amine to the anionic surfactant is 3 to 3.
5, more preferably 3.25 to 3.5.

The preferred viscosity of the cleaning composition according to the present invention is 11.7 seconds ⁻¹ shear and 25 ° C.
In, Haake RV2 rotobiscometer
ter ^™ ) and MV1 Bob as measured from 50 mPas to 1000 m
Pas.

A particularly preferred composition according to the invention comprises: (a) 1 to 10% by weight of sulfamic acid, preferably 3 to 5% by weight, (b) 1 to 10% by weight of ethoxylated amines (C) 0 to 5% by weight of nonionic surfactant, preferably 0.05 to 1% by weight, (d) 0.05 to 2% by weight of anionic surfactant hydrotrope %, Preferably 0.4-1.1% by weight (e) 1-10% by weight, preferably 4-6% by weight, hydrogen peroxide.

Minor components : The combination of surfactants in the composition according to the invention gives a thickening effect, but it is also possible to add other thickeners. Gum, especially xanthan gum, is a suitable thickener. Preferred xanthan gums are the Kelzan (RTM) series (available from Kelco Corp). Typical levels of xanthan gum, if present, are between 0.05 and 1% by weight. The viscosity of the resulting composition, measured with a Haake RV2 Rotobiscometer (RTM), is preferably 20 reciprocal seconds.
10-200 mPas with MV1 bob at 25 ° C. shear at 25 ° C. onds).
In the range. More preferably, this viscosity is between 10 and 100 m
Pas.

[0034] Sequestering agents such as ethylenediaminetetraacetic acid, amino-poly-phosphonates (for example, DEQUE manufactured by Monsanto)
Those within the scope of EST ^™ ) and phosphonates, and a wide variety of other polyfunctional organic acids and salts, can also optionally be used. Preferred metal ion complexing agents are dipicolinic acid, ethylenediaminetetraacetic acid (EDTA), and salts thereof, hydroxyethylidene-diphosphonic acid (Dequest 2010), ethylenediamine-tetra (methylene-phosphonic acid) (Dequest 2040), diethylenetriamine-penta ( Methylene-phosphonic acid) (Dequest 2060).

[0035] Optional minor components also include those typically found in cleaning compositions;
Selected from opacifiers, pigments, fragrances, and fluorescent agents.

The preferred level of perfume is 0.05 to 2% by weight. Acid stable fragrances can be obtained from various sources.

Particularly preferred compositions according to the present invention include:

[0038]

[Table 1] A typical product having the above formulation consisting of 3.0% by weight of amine and about 0.56% by weight of SCS is clear, has a specific gravity of 1.040 g / ml, 106 sec ^{- 1} (25C ) Is 120 mPas and 11.7 seconds ⁻¹ (25 ° C.)
Is 300 mPas and pH 0.9 (25 ° C.).

In order that the invention may be better understood, it is exemplified below with reference to the following non-limiting examples.

EXAMPLES Example 1: Antimicrobial Synergy Action Suspension test using a composition of the invention and a comparative composition at a typical in-use dilution (2%) of a composition according to the invention. Was carried out. The following bacterial strains were used for these suspension tests.

Pseudomonas aeruginosa ATCC 15442 Staphylococcus aureus ATCC 6538 Enterococcus faecium DVG 8582 Proteus mirabilis ATCC 14153 EST (DD177. The antibacterial activity was measured.
The total viable count was determined after 5 minutes and 30 minutes contact time using the following solutions and water of standard hardness for controls. Log reduction for water
n) was measured. Viable organisms were determined by culture on nutrients or tryptone-soy agar for 48 hours at 37 ° C. Logarithmic 10-fold reduction (log decim
al reduction) was determined from the number of survivors. Table 1 below shows 5 minutes and 30 minutes.
The result of the contact time in minutes is shown.

The concentrations in this assay, representative of the concentrations found in the toilet after use of the product according to the invention, were as follows: Sulfamic acid: 0.08% by weight Hydrogen peroxide: 0.10% by weight Amine Ethoxylate: 0.06% by weight Etomine S / 12 ™ Table 1 (log kill) The suspension test results show the log kill average (cfu / ml).

CK = complete sterilization NSK = insignificant sterilization

[0044]

[Table 2] Initial counts: Staphylococcus aureus ATCC 6538 6.99 Enterococcus faecium DVG8582 6.99 Pseudomonas aeruginosa ATCC 15442 4.36 Proteus mirabilis ATCC 14153, a trade name of ATCC 14153, and a neutralizer of ATCC 14153. Thus, if the count is zero, this is less than 50 cfu / ml or log 50 =
Equivalent to 1.70 viable organisms. The table shows that the combination of sulfamic acid and amine ethoxylate has improved bactericidal properties against this broad spectrum of bacteria over sulfamic acid itself. In this table, numbers greater than or equal to 3 indicate disinfection behavior, which are underlined.

In particular, sulfamic acid alone (first example) has low antimicrobial properties, which is not significantly improved by the presence of hydrogen peroxide (compare the first two examples). However, a composition containing both sulfamic acid and an amine ethoxylate (compare the two examples below) is almost identical to that of a system further containing hydrogen peroxide (the bottom example). It can be seen that it has a good antibacterial property.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] April 10, 2000 (2000.4.10)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

9. An antimicrobial composition comprising: (a) 1 to 10% by weight of sulfamic acid, (b) 1 to 10% by weight of an ethoxylated amine, (c) 0 to 5% by weight of a nonionic surfactant, (d) 10. The composition according to claims 7 to 9, comprising: 0.05 to 2% by weight of a hydrotrope; and (e) 1 to 6% by weight of hydrogen peroxide.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] April 10, 2000 (2000.4.10)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 1/44 C11D 1/44 1/835 1/835 3/02 3/02 3/39 3/39 7 / 08 7/08 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU , LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, U G, UZ, VN, YU, ZW (72) Inventors Bolzoni, Giusecpe Vincenz o Italy, Casale, I-26841. (72) Inventor Fueturo, Emanuela, Italy, Milan, I-20071, Casal Pusterlengo, Via Lever Jitbus 3, Davisione Label in Austrian, Unilever Italia Etc P. A. Attention (72) Inventor Gali, Marco Italy, 26841 Casparstel Lengo (Rhoday), Via Lever The Tubes 3, Lieber Huaverzier-H.H.C.Innovation Center, Unicever Italy Italy.E.C.P.A.Career (72) Inventors Jyones, Caroline Elizabeth Merseyside El. 62.4 Zet Day, Wirral, Port Sunlight, P.O. Boxes 69, Lieber Brothers Limited Noted (72) Inventor Morris, Ronald Meredith Hungary, Her-1134 Budapest. Senhalmadik, Debye Utu Tour 26-28, Uni Ba-Majiyaruo Rusagu Car F. tape care F-term (reference) 4H003 AC08 AE02 DA05 EA06 EB22 EB24 ED02 EE04 FA28 FA34 4H011 AA02 BA02 BA06 BB07 BB18 BC03 BC04 BC07 BC19 DA13 DD07 DH02 DH03

Claims (6)

[Claims] 1. An alkoxylated fat having 8 to 18 carbon atoms and 1 to 8 alkoxylated units for improving the antibacterial effect of an acidic antibacterial composition containing 0.01 to 15% by weight of sulfamic acid. Use of group 15 amines 0.01 to 15% by weight. 2. (a) 0.01 to 15% by weight of an alkoxylated aliphatic amine having 8 to 20 carbon atoms and 1 to 8 alkoxylated units; (b) 0.01 to 15% by weight of sulfamic acid %; And (c) a source of peroxygen species. 3. An alkoxylated aliphatic amine having the general formula: H (A) _x —N (R) — (A) _y H wherein R is an alkyl or alkenyl containing from 8 to 18 carbon atoms. Group,
A is an ethoxy group, and x and y can be the same or different and are integers from 1 to 4). 4. The composition according to claim 2, wherein the source of the peroxygen species is hydrogen peroxide. 5. An antimicrobial composition comprising: (a) 1 to 10% by weight of sulfamic acid, (b) 1 to 10% by weight of an ethoxylated amine, (c) 0 to 5% by weight of a nonionic surfactant, (d) 5. The composition according to any one of claims 2 to 4, comprising: 0.05 to 2% by weight of a hydrotrope; and (e) 1 to 10% by weight of hydrogen peroxide. 6. (a) 0.01 to 15% by weight of an alkoxylated aliphatic amine having 8 to 20 carbon atoms and 1 to 8 moles of an ethoxylated moiety; and (b) 0.01 to 15% of sulfamic acid. A method for disinfecting a surface, comprising treating the surface with an acidic antimicrobial composition comprising: