JP2001520259A - Alkoxylated amines and their use in cleaning compositions - Google Patents

Abstract

  (57) [Summary] The invention relates to an alkoxyl having from 8 to 18 carbon atoms and from 1 to 8 moles of an ethoxylated moiety, wherein the molar ratio of saturated to unsaturated aliphatic residues is from 40:60 to 80:20. Providing a fluorinated aliphatic amine. The invention also relates to (a) 8-18 carbon atoms and 1-8 moles of an ethoxylated moiety, wherein the molar ratio of saturated aliphatic residues to unsaturated aliphatic residues is 40: 60-80: 20. A cleaning composition comprising 0.01 to 15% by weight of an alkoxylated aliphatic amine having the formula: and (b) 0.01 to 15% by weight of an anionic surfactant. The cleaning compositions containing amines show improved viscosity stability on storage. In the presence of an anionic surfactant at low pH, lime scale deposition on surfaces treated with this composition is delayed.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates to acidic cleaning compositions, particularly to 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 remain on the inclined surface, for example, inside a 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.

[0003] GB 1443244 relates to acidic detergents and descaling agents containing ethoxylated tertiary amines as thickeners. Of these amines, etomien (ET
HOMEEN) S12 (N, N-dihydroxyethyl-oleylamine) is mentioned as an example. The composition also contains a mineral acid and an acid selected from the acid salts of strong inorganic acids, such as sulfamic acid. A fungicide is an additional optional ingredient.

[0004] FR 2459830 discloses a composition comprising a non-ethoxylated amine and an ethoxylated amine together with a sulfamic acid. The composition also comprises a disinfectant (
disinfectants).

[0005] 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 and formalin is disclosed as a fungicide that improves the antimicrobial action of these acids.

[0006] EP-B-02276501 is a thickened aqueous cleaning composition, comprising p
Weak acids with K> 2 (of which sulfamic acid is mentioned as an example) 0
. 1 to 50% by weight, 0.1 to 20% by weight of an amine which may contain 2% by weight of oleyl-bis- (2-hydroxyethyl) -amine, and hydrotrope (sodium xylene sulfonate are mentioned as examples. ) Discloses compositions comprising from 0.01% to 5% by weight. The disinfectant is optional.

[0007] EP-A-0314232 relates to a composition having a viscosity increase upon dilution, wherein the thickened liquid detergent composition comprises amine oxides, amines (eg etomine S12), betaines. Or a quaternary ammonium compound, and a hydrotrope (sodium xylene sulfonate). The specification also states that amine oxides and quaternary ammonium compounds are known to have life-destructive properties, and furthermore that a bactericide containing an organic peracid is optional. These compositions may be of acidic, neutral, or alkaline pH.

[0008] One problem with known compositions is that the viscosity of the composition drifts over time,
Especially when the product is stored.

BRIEF DESCRIPTION OF THE INVENTION We have discovered that certain mixtures of both saturated and unsaturated alkoxylated aliphatic amines in the presence of anionic surfactants have improved upon storage. It was confirmed to exhibit viscosity stability. Surprisingly, we have found that by adding an anionic sulfonate surfactant hydrotrope to these formulations,
It has been discovered that the surface energy of surfaces treated with this composition has been reduced and has the additional effect of delaying subsequent deposition of lime scale.

DETAILED DESCRIPTION OF THE INVENTION According to a first aspect of the present invention, the molar ratio of saturated aliphatic residues to unsaturated aliphatic residues is from 40:60 to 80:20, from 8 to 18 Provided are alkoxylated aliphatic amines having from 1 to 8 moles of ethoxylated moieties.

According to a second aspect of the present invention, (a) the molar ratio of the saturated aliphatic residue to the unsaturated aliphatic residue is from 40:60 to 80:20.
0.01 to 15% by weight of an alkoxylated aliphatic amine having 8 to 18 carbon atoms and 1 to 8 moles of ethoxylated moieties, and (b) 0.01 to 15% by weight of an anionic surfactant And a cleaning composition comprising:

According to a third aspect of the present invention, there is provided a method for delaying lime scale adhesion to a surface, comprising: (a) a molar ratio of saturated aliphatic residues to unsaturated aliphatic residues of 40: 60-80: 20
0.01 to 15% by weight of an alkoxylated aliphatic amine having 8 to 18 carbon atoms and 1 to 8 moles of ethoxylated moieties, and (b) 0.01 to 15% by weight of an anionic surfactant %, Wherein the surface is treated with a cleaning composition having a pH of less than 1.

Amine : Typically, the alkoxylated aliphatic amine is an ethoxylated tertiary amine of the general formula: H (A) _x -N (R)-(A) _y H where R is An alkyl or alkenyl group containing from 8 to 18 carbon atoms, A is an ethoxy or propoxy group, x and y may be the same or different and are integers from 1 to 3.

A preferred material is an ethoxylated amine wherein A is —OCH ₂ CH ₂ —.

Preferably, x and y are both 1. In a preferred embodiment of the present invention, R is mixed group of mixed saturated and unsaturated C ₁₄ -C ₁₈ alkyl, most preferably the fatty acid residue that most corresponds to the oleic acid, and / or stearic acid Comes from.

Preferably, the molar ratio of saturated fatty acids to unsaturated fatty acids is between 50:50 and 66:33.

A particularly suitable alkoxylated aliphatic amine is the material known as ETHOMEEN BTB / 12 ^™ , available from Akzo. B
TB / 12 is a 65% mixture of oleyl derivative with well-cured tallow-derived material.
It is considered to be a mixture at a ratio of / 35. Such admixtures are prepared by synthesis using appropriate ratios of admixed starting materials, or by mixing an alkoxylated aliphatic amine such as ETHOMEEN HT12 ^™ (Akzo) with an unsaturated material such as ETHOMEEN S12. Can be obtained by: ETHOMEEN S12 ^™ (Akzo) is N, N- (dihydroxyethyl) -oleylamine.

In an embodiment of the present invention as a cleaning product, the preferred level of alkoxylated aliphatic amine is 1-10% by weight for product and 2% for product.
Levels of ６6% by weight are particularly preferred.

[0019]Anionic surfactant  In a particularly preferred embodiment of the present invention, the alkoxylated aliphatic amine is
Present with nonionic surfactants. Preferably the levels of these substances are
Are such that they interact to thicken the composition.

[0020] Suitable anionic surfactants include sulfonate hydrotropes.
Preferred surfactants include salts of alkylarylsulfonates, such as toluenesulfonate, cumenesulfonate, or xylenesulfonate, especially alkali metal salts. A particularly preferred anionic surfactant is sodium cumene sulfonate. A suitable material is ELTESOL SC40 ^™ (
Albright and Wilson
n)). Typical levels of anionic surfactant are 0% for the product.
. It is 0.5 to 2% by weight.

[0021] Preferably, the formulation containing the alkylaryl sulfonate is formulated at a pH of 1 or less. While not wishing to limit the invention with reference to working theory, below pH 1, ethoxylated amines behave as cationic surfactants and interact with alkylaryl sulfonates to form water-insoluble gels, Is believed to adhere as a monolayer on the surface. It is believed that this monolayer lowers the surface energy of the surface and delays 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., at a Haake RV2 rotoviscomet.
er) (registered trademark) and 50 mPas-10 as measured using MV1 Bob.
00 mPas.

Acids : Typically, the cleaning compositions embodying the present invention comprise from 0.01 to 15% by weight of a lime-scalable acid, preferably an organic acid, and more preferably a sulfamic acid. I have. In such embodiments, typical levels of acid (e.g., aminosulfonic acid) are 1-10% by weight for the product and 2-10% for the product.
A level of 6% is particularly preferred.

The pH of the composition according to the invention preferably has a pH <2.0, more preferably a pH <1.0.

Peroxygen Source : A preferred embodiment of the present invention is a cleaning and / or sanitary composition comprising a peroxygen compound.

[0027] If a typical source of peroxygen species is present, this 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 from 1 to 10% by weight of the product, from 3 to
A level of 8% is particularly preferred.

Nonionic surfactant : Preferred compositions according to the present invention further comprise a nonionic surfactant.

[0030] Suitable nonionic surfactants include alkoxylated alcohols, preferably ethoxylated alcohols. Suitable non-ionic detersive active compounds are broadly described as compounds formed by the condensation of an alkylene oxide group, which is actually hydrophilic, with an organic hydrophobic compound, which may actually be aliphatic or alkylaromatic. be able to.

The length of a hydrophilic or polyoxyalkylene group condensed with a specific hydrophobic group is
It can easily be adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Preferred alkoxylated alcohols are selected from the group comprising ethoxylated alcohols of the general formula: R _1- (OCH ₂ CH ₂ ) _m -OH

Here, R ₁ is a straight-chain or branched-chain C ₈ -C ₁₈ alkyl or hydroxyalkyl, and m is 1-14 on average. Ethoxylated alcohols suitable for use in the present invention include LIAL 1 commercially available from DAC.
11.10 EO ™. Typical levels of non-ionic surfactants in the products according to the invention are 0-5%.

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

Minor components : The combination of surfactants in the composition according to the invention gives a thickening action, but it is also possible to add other thickeners. Gum, especially xanthan gum, is a suitable thickener. Preferred xanthan gums are the Kelzan ^™ series (available from Kelco Corp). Typical levels of xanthan gum are 0.05-1% by weight. When measured in a Haake RV2 Lotto viscometer, the viscosity of the resulting composition is preferably 20 ^- using MV1 bob at 25 ° C. In ^a second shear is in the range of 10～200MPas. More preferably, the viscosity is between 10 and 100 mPas under the above conditions.
It is.

[0036] Sequestering agents such as ethylenediaminetetraacetic acid, amino-polyphosphonates (eg, Dequest manufactured by Monsanto)
ST ^TM) of a certain thing range) and phosphonates, and a wide variety of other polyfunctional (poly-functional) organic acids and salts, can also be used arbitrarily. Preferred metal ion complexing agents are dipicolinic acid, ethylenediaminetetraacetic acid (EDTA), and salts thereof, hydroxyethylidene-diphosphonic acid (Dequest 2010), ethylenediamine-tetra (methylenephosphonic acid) (Dequest 2040), diethylene-triamine-pentane (Methylene phosphonic acid) (
Dequest 2060).

The optional minor components also include those typically found in cleaning compositions and are selected from opacifiers, pigments, fragrances, and fluorescent agents.

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

Particularly preferred compositions according to the present invention include:

[0040]

[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 preferably clear and has a specific gravity of 1.040 g / ml, 1
The initial viscosity at 06 sec ^-1 (25 ° C.) was 120 mPas, and 11.7 sec ^-1 (
The initial viscosity at 25 ° C) is 300-600 mPas, and the pH is 0.9 (25 ° C).
It is.

In order that the invention may be better understood, the invention will be illustrated below with reference to the following non-limiting examples and the accompanying drawings.

EXAMPLES Example 1 Viscosity Stability A composition was prepared as follows.

[0044]

[Table 2]

To demonstrate the interaction of the ethoxylated amine with the anionic surfactant,
The other components were each under-dosed and over-dosed by +/- 10%. 11.
Initial viscosity at 7 sec- ¹ shear 500 m. The results for Pas are shown in Table 1 below.

[0046]

[Table 3]

From the foregoing, it can be seen that the maximum viscosity modification occurs when the relative levels of the anionic surfactant and the ethoxylated amine are varied, and that variations in the levels of the other components have little effect. I understand.

As indicated by the numbers in Table 2 below, the ethoxylated amine / anionic surfactant molar ratio can be modified to provide thickening in the viscosity range. Similarly, end products similar to those described above could be used.

[0049]

[Table 4]

A composition having a viscosity of 50 mPas to 1000 mPas (molar ratio: 3 to 3.5)
Was a flowable composition suitable for use as a toilet cleaner. Compositions with lower viscosities were too thin to stay on sloped surfaces, while higher viscosities could not be easily dispensed. Compositions having a viscosity of from 200 to 700 mPas were particularly suitable for this purpose.

[0051] Compositions in the above class of ranges have been prepared with varying degrees of saturation in ethoxylated amines. The materials used were: 'S12' N, N-dihydroxyethyl-oleylamine (ETHOM
EEN S12), 'HT12' fully cured N, N-dihydroxyethyl-tallowylamine (ETHOMEEN HT12), '50 / 50 'equal weight mixture of' S12 'and' HT12 ', and '66 / 33' A mixture of "HT12" and "S12" in a 66:33 weight ratio (similar to BTB12).

The effect of storage on viscosity is shown in FIGS.

FIG. 1 shows the viscosities (mPas) of the substances according to the invention and the comparative example at 11.7 s ⁻¹ , measured using a Haake RV2 Rotoviscometer and MV1 Bob after storage at room temperature. It can be seen that the viscosity of the "HT12" sample increased over time until the product became a non-flowable gel. The viscosity of the "S12" sample decreased, and thus the product was sometimes too thin to be retained on the inclined surface. The viscosities of these products, including mixtures of hardened and unhardened tallow, remained within acceptable ranges on storage.

FIG. 2 shows the viscosities (mPas) of the substances according to the invention and the comparative example at 106 sec ⁻¹ , measured using a Haake RV2 Rotoviscometer and MV1 Bob after storage at room temperature. It can be seen that the viscosity of the "HT12" sample first decreased and then increased. The viscosity of the "S12" sample was reduced and thus the product was sometimes too thin to be retained on the inclined surface. The viscosity of the product, including the mixture of cured and uncured materials, remained within acceptable ranges on storage.

FIG. 3 shows that after storage at 37 ° C., the Haake RV2 rotobiscometer and MV1
Figure 3 shows the viscosity (mPas) of the material according to the invention and the comparative example at 106 sec- ¹ measured using Bob. It can be seen that the viscosity of the "HT12" sample also decreased first, and then increased. The viscosity of the "S12" sample was reduced and thus the product was sometimes too thin to be retained on the inclined surface. The viscosity of the product, including the mixture of cured and uncured materials, remained within acceptable ranges on storage.

FIG. 4 shows that after storage at 37 ° C., the Haake RV2 rotobiscometer and MV1
FIG. 4 shows the viscosity (mPas) of the substances according to the invention and the comparative example at 11.7 s ⁻¹ , measured with Bob. It can be seen that the viscosity of the "HT12" sample also increased. The viscosity of the "S12" sample was reduced and thus the product was sometimes too thin to be retained on the inclined surface. The viscosity of the product, including the mixture of cured and uncured materials, remained within acceptable ranges on storage.

Example 2: Prevention of lime scale Flow of carbon dioxide overnight in tap water containing both calcite and dolomite (plus
h) By doing so, hard water of ６０60 degrees French was prepared. Several pairs of tiles were washed with the detergent composition and ethanol and rinsed with tap water. One tile was treated with the composition according to the invention (from example 1). The contact time was 20 minutes. The tile was then rinsed with water. Hard water was then dropped on the tiles for 24 hours, with one drop falling on each tile every 5 minutes. The results for the treated and untreated tiles were compared visually using a panel of 10 people and scored on a scale of 0 = no lime scale and 5 = more skin forming tiles. The results are shown in Table 3 below. Furthermore, the lime scale is
Titrated after dissolution in dilute HCl. The titration results are shown in Table 3 below in mg of calcium carbonate per tile. Examples are replicates (replica)
ate) Implemented as A, B, and C.

[0058]

[Table 5]

From these results, the treatment of this tile is not negligible for the degree of lime scale deposited on the tile, either chemically measured in this test or when looking at the surface (measurable). ) You can see the effect.

[Brief description of the drawings]

FIG. 1 shows the viscosities (mPas) of substances according to the invention and comparative examples at 11.7 s ⁻¹ , measured using a Haake RV2 Rotoviscometer and MV1 Bob after storage at room temperature.

FIG. 2 shows the Haake RV2 Rotoviscometer® after storage at room temperature.
2 shows the viscosities (mPas) of the substances according to the invention and the comparative example at 106 sec ⁻¹ , measured using a MV1 bob.

FIG. 3 shows that after storage at 37 ° C., the Haake RV2 rotobiscometer and MV1
Figure 3 shows the viscosity (mPas) of the material according to the invention and the comparative example at 106 sec- ¹ measured using Bob.

FIG. 4 shows that after storage at 37 ° C., the Haake RV2 rotobiscometer and MV1
FIG. 4 shows the viscosity (mPas) of the substances according to the invention and the comparative example at 11.7 s ⁻¹ , measured with Bob.

[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 Continuation of front page (81) Designated country 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, UG, US, UZ, VN, YU, ZW (72) Inventors Bolzoni, Giusetupe Vincenz Italy Italy, Casale, E26841 Casa Lupus Terlengo (Rhoday), Via Reaver Gitbus 3 / Ar, Reaver Development Center, Unilever Italy Etc. P.A. Attention (72) Inventor Fueturo, Emanuela Italy, Milan, I -20071 · Casal Pusterlengo, Via Lieber Gibbs 3, Davis Ione Label Indonesia, Unilever Italy (72) Inventor Gully, Marco Italy, Milan, I-20071 Casal Pusterlengo, Via Lever Jibbs 3, Davis Ione Label Indialiale, Unilever Italy (72) Inventors Morris, Ronald Meredith, Hungary, Ha-1134 Budapest, Teisenhalmadik, Debye Uztua 26-28, Unilever Magical Lusag Kaef. F term (reference) 4H003 AB18 AC08 AC13 AE02 BA12 DA05 EA06 EB22 EB24 ED02 EE04 FA16 FA28 FA30 FA34

Claims (14)

[Claims] 1. The molar ratio of saturated aliphatic residues to unsaturated aliphatic residues is from 40:60.
80:20 alkoxylated aliphatic amine having 8-18 carbon atoms and 1-8 moles of ethoxylated moieties. (A) a molar ratio of saturated aliphatic residue to unsaturated aliphatic residue of 40:
From 0.01 to 15% by weight of an alkoxylated aliphatic amine having from 8 to 18 carbon atoms and from 1 to 8 mol of ethoxylated moieties, from 60 to 80:20, and (b) anionic surfactant 0 0.11 to 15% by weight. 3. An alkoxylated aliphatic amine having the general formula: H (A) _x —N (R) — (A) _y H wherein R is an alkyl or alkenyl group containing from 8 to 18 carbon atoms. Wherein A is an ethoxy or propoxy group and x and y are the same or different and are integers from 1 to 3). object. 4. The composition according to claim 3, wherein A is —OCH ₂ CH ₂ —. 5. The composition according to claim 3, wherein x and y are both 1. 6. The composition according to claim 3, wherein R is a mixed group of saturated and unsaturated C ₁₄ -C ₁₈ alkyl. 7. The composition according to claim 1, wherein the molar ratio of saturated fatty acid to unsaturated fatty acid in the alkoxylated aliphatic amine is from 50:50 to 66:33. 8. The composition according to claim 2, wherein the pH of the composition is less than 1.0. 9. The molar ratio of the ethoxylated amine to the anionic surfactant is:
3. The composition according to claim 2, wherein the composition is between 3 and 3.5, more preferably between 3.25 and 3.5. 10. 50 mPas to 1000 mP as measured with a Haake RV2 rotoviscometer and MV1 bob at 11.7 sec- ¹ shear and 25 ° C.
3. The composition according to claim 2, having a viscosity of as. 11. The composition according to claim 2, comprising 0.01 to 15% by weight of a lime-scalable acid. 12. The composition according to claim 2, further comprising a peroxygen compound. 13. (a) 1 to 10% by weight, preferably 3 to 5% by weight of sulfamic acid
(B) 1 to 10% by weight of ethoxylated amine, preferably 2 to 5% by weight, (c) 0 to 5% by weight of nonionic surfactant, preferably 0.05 to 1% by weight, (d) A) anionic surfactant hydrotrope, 0.05 to 2% by weight, preferably 0.4 to 1.1% by weight, (e) hydrogen peroxide 1 to 10% by weight, preferably 4 to 6% by weight. The composition of claim 2, wherein the composition is: 14. A method for delaying the deposition of lime scale on a surface, the method comprising:
14. A method comprising treating the surface with a cleaning composition according to any of claims 8 to 13, wherein the composition is below pH 1 and (a) saturated aliphatic residues versus unsaturated. The molar ratio of the aliphatic residue is 40:60 to 80:20.
0.01 to 15% by weight of an alkoxylated aliphatic amine having 8 to 18 carbon atoms and 1 to 8 moles of an ethoxylated moiety, and (b) 0.01 to 15% by weight of an anionic surfactant. % And the method containing.