JP2871941B2 - Aqueous detergent composition for hard surfaces containing calcium ions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous detergent composition for hard surfaces containing calcium ions which can give an improved feeling of use without deteriorating the storage stability of the composition. The composition is particularly useful in kitchen detergents, and more particularly under soft water conditions.

[0002]

2. Description of the Related Art Anionic surfactants having a short ethylene oxide chain, such as alkyl ethoxy sulfate, alkyl sulfate, alkyl benzene sulfonate, α-olefin sulfonate and alkyl ethoxy carboxylate, are very effective for cleaning hard surfaces. However, it is also known to have a somewhat objectionable "slimy" feel during use. This undesirable attribute is problematic in hard surface detergent compositions, especially kitchen detergent compositions for dishwashing purposes.

[0003] Therefore, there is a considerable need for hard surface detergent compositions, especially for dishwashing purposes, which have a good feel during washing and rinsing as well as good detergency and good storage stability. In the present invention, the definition of good feeling of use is defined as "slimy" or "slimy" when using the composition.
It will most often be described by the word absence or feeling of the "free flowing" kind. "Good feel" is an important attribute for commercial liquid detergent products. A cleaning liquid that is comfortable to use on the hand and on the object to be cleaned allows easy handling of the object to be cleaned and provides good rinsing properties. Such benefits are most noticeable for dishwashing purposes.

Many attempts to improve the usability have been
It has been done using various technologies. These attempts have generally been directed to the use of nonionic surfactants and lather enhancing and solvent type components.
In general, these compositions have sacrificed detergency to obtain an improved feel.

JP-B-46-43550 discloses a liquid detergent composition containing a certain alkylalkyleneoxysulfate and an alkaline earth metal salt of an alkylalkyleneoxycarboxylic acid, which is mild and has good detergency on the skin. Teaching.

[0006] JP 51-125405 discloses the calcium and magnesium salts, and amine oxides of anionic surfactants including alkyl ether sulfates include C _{1 to 5} alkanol and water, amine oxides counter anion surfactant The composition teaches that the weight ratio of active agent is from 1: 100 to 1: 2. Up to about 25% of the anionic surfactant can be a monovalent salt.

US Pat. No. 2,766,212 discloses a composition comprising an alkyl ether alkoxysulfate and a water-soluble polyvalent metal salt of magnesium, calcium, iron or aluminum in an amount of 5 to 50% by weight of the surfactant. Teaching things. The example shows a composition comprising at least 70% of an anionic surfactant in which magnesium and calcium ions aid in detergency.

US Pat. No. 4,681,704 discloses alkaline earth metal salts of anionic surfactants, preferably magnesium salts 10 to 50%, amine oxides 0 to 10%.
It teaches a detergent composition with effective degreasing comprising 5-10%, and 0.5-15% betaine.

[0009] However, the above disclosure uses alkaline earth metals primarily for cleaning benefits and does not disclose or suggest improvements in the usability benefits contributed by calcium ions. In addition, the compositions disclosed above have a high level of divalent ions and therefore will be unstable upon storage according to the definition of the invention, ie, will form undesirable precipitates of calcium. Preferred compositions and examples given in the above disclosure also have high surfactant levels,
Thus, it is believed that the amount of calcium required to reduce or eliminate the "slimy feel" of the composition causes the composition to transition to a phase where calcium readily precipitates.

[0010] Here, it has been found that by using a specific small amount of calcium ions, it is possible to obtain a composition which gives an improved feeling in use without deteriorating the storage stability.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an aqueous detergent composition for a transparent hard surface which has an improved usability during use without deteriorating the storage stability of the composition. is there.

It is another object of the present invention to provide a liquid detergent composition for hard surfaces having good quality balanced with detergency, usability and storage stability.

It is a further object of the present invention to improve the feeling of use of an aqueous detergent composition for hard surfaces or a cleaning solution of an aqueous detergent composition for hard surfaces, wherein calcium ions are added to the aqueous detergent composition for hard surfaces. Is to provide a law.

[0014]

Means for Solving the Problems The present invention provides (1) an anionic surfactant, nonionic surfactant, amphoteric surfactant, and is selected from the group consisting of mixtures thereof, (a) _{C. 10 to} Alkyl ethoxy sulphate having ₁₆ alkyl groups and an average of 1 to 10 moles of ethylene oxide per molecule at least 3% by weight of the composition and at least 20% by weight of the surfactant system, (b) alkyl benzene sulphonate, α-olefin sulphonate,
Other anionic surfactants selected from the group consisting of alkyl ethoxy carboxylate, and mixtures thereof,
(C) 0 to 9% by weight of diethanolamide composition having an alkyl chain of _{C 8} ~20, (d) a surfactant comprising 0-10% by weight of amine oxide compositions having C _{8 ~ 16} alkyl chains An aqueous detergent composition for hard surfaces comprising 3 to 35% by weight of a system and (2) 0.01 to 0.5% by weight of calcium ions, wherein at least 20% by weight of the surfactant system comprises components a, b, c And d. An aqueous detergent composition for hard surfaces giving an improved feeling of use characterized by comprising:

The present invention also relates to a method for improving the feeling of use of an aqueous detergent composition for hard surfaces or a cleaning solution of an aqueous detergent composition for hard surfaces, wherein calcium ions are added to the aqueous detergent composition for hard surfaces. .

The composition does not have an unacceptably slimy feel and is easy to handle during washing and rinsing. The compositions of the present invention have good storage stability, i.e., the compositions are stable under normal use conditions,
More specifically, no precipitation or gel occurs within the temperature range of -5 to 40C. Anionic surfactant The composition of the present invention is selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof, from 15 to 35% by weight of a surfactant system, preferably Contains 20 to 30% by weight. At least 20%, preferably at least 40%, more preferably at least 60% by weight of the surfactant system is the sum of an anionic surfactant, diethanolamide and amine oxide. Of the anionic surfactant, at least 3%, preferably at least 8%, more preferably at least 12% of the composition
Is a C _10-16 alkyl group and an average of 1 to 1 per molecule.
Alkyl ethoxy sulfate having 10 moles, preferably 2 to 5 moles of ethylene oxide.

The anionic surfactant is selected from the above-mentioned alkyl ethoxy sulfates, alkyl sulfates, alkyl benzene sulfonates, α-olefin sulfonates, alkyl ethoxy carboxylates, and mixtures thereof.

Alkyl ethoxy sulfates having _C10-16 alkyl groups and an average of 1-10, preferably 2-5, more preferably 2.5-3.5 mol of ethylene oxide per molecule have high detergency. The effect of giving a bad feeling of use is small. Further, such a composition containing a large amount of alkyl ethoxy sulfate is susceptible to the effect of improving the feeling of use of calcium ions. The average number of moles of ethylene oxide per molecule of alkyl ethoxy sulfate can alter the properties of the surfactant. Here, the alkyl sulfate is treated as an alkyl ethoxy sulfate having 0 mol of ethylene oxide per molecule. In general, it is known that the longer the ethylene oxide chain, the less contributing to the bad feeling of use, but the worse the detergency performance. Only one per molecule
Those having less than moles of average ethylene oxide chains will contribute to a poor feel.

The salt of the anionic surfactant component can be an alkali metal, alkaline earth metal, amine or ammonium salt, preferably a sodium or ammonium salt. The alkaline earth metal salts of these surfactants are known for having good detergency and foaming. Some or all of the calcium ions of the composition can be introduced as the calcium salt of an anionic surfactant. Other Surfactants The compositions of the present invention comprise other anionic, nonionic and amphoteric surfactants as the balance of the surfactant system. These surfactants are formulated into the compositions of the present invention to enhance detergency and to enhance and stabilize foam. The type and amount of other anionic, nonionic and amphoteric surfactants are selected to achieve an optimal balance between detergency, feel and storage stability.

[0020] The composition of the present invention comprises diethanolamide,
A nonionic surfactant such as an amine oxide can be included. 0 to 9, preferably 4 to 7% by weight of diethanolamide and 0 to 10, preferably 2 to 5% by weight of amine oxide are contained in the composition. These two surfactants are known to provide good detergency and good storage stability, but can adversely affect the usability. Using calcium ions to improve the feel during use is particularly useful in compositions comprising diethanolamide and / or amine oxide.

The diethanolamide useful in the present invention has the formula Having (wherein, R ¹ is C _{8 to 20,} preferably selected from alkyl chains of C _{12 to 14).}

The amine oxides useful in the present invention have the formula Having (wherein, R ² is C _{8 to 20,} preferably selected from alkyl chains of C _{12 to 14).} By blending a small amount of calcium ions of calcium, it has been found that balanced benefit of storage stability and feel can be obtained. The effect of adding a small amount of calcium ions to a kitchen detergent is particularly beneficial under soft water conditions where the amount of calcium introduced from tap water is small.

Calcium ions are added to the composition in an amount of 0.01 to
It is added in an amount of 0.5%, preferably 0.1-0.5%, more preferably 0.1-0.3%. At lower calcium levels, no effect on the feel will be observed. At higher calcium levels, storage stability will not be good. That is, calcium ions are
It is known that it precipitates relatively easily under high temperature conditions and thus tends to degrade storage stability when added in large amounts. Calcium ions are further known to contribute to detergency, particularly grease removal. By selecting the amount of calcium within the above range, a composition having all three important benefits, good feel, good grease removal, and good storage stability is obtained.

The compositions of the present invention must have less than 35% total surfactant to avoid precipitation of calcium present in sufficient amounts to improve the feel. If the amount of surfactant is too high, the maximum amount of calcium that can be added without forming a calcium precipitate will not be sufficient to improve the feel of the composition.

The calcium ions can be incorporated into the composition in any convenient manner, so long as the salt containing the calcium ions is soluble in water and does not precipitate under normal use conditions. A preferred method of blending calcium ions is to add calcium ions as a salt selected from the group consisting of chlorides, hydroxides, oxides, acetates, nitrates, formates, and mixtures thereof. Chloride is most preferred.

Alternatively, calcium ions are formulated as counterions to the anionic surfactant, for example by neutralizing the anionic surfactant in acid form with calcium oxide or calcium hydroxide without affecting profit. You can also.

Preferred compositions of the present invention, (1) an anionic surfactant, nonionic surfactant, amphoteric surfactant, and is selected from the group consisting of mixtures thereof, of (a) C _{10 to 16} Alkyl ethoxy sulphate having alkyl groups and an average of 2.5 to 3.5 ethylene oxides per molecule at least 3 of the surfactant systems
5 wt%, 4-7 wt% of diethanolamide composition having an alkyl chain of _{(b) C 8 ~20, (} c) C 8 ~16
Amine oxide having an alkyl chain of 2 to 5
20% to 30% by weight of the surfactant system, including 0.1% to 0.3% by weight of calcium ions, and 0.1% to 1% by weight of magnesium ions. Optional Ingredients The compositions of the present invention can optionally include various ingredients in addition to those already disclosed herein.

[0028] Optional surfactants useful in the compositions of the present invention are monoethanolamide, polyhydroxy fatty acid amide, alkyl polyglucoside, alkyl ethoxylate, and the like.

The optional surfactant monoethanolamide in the present invention has the formula A (wherein, R ³ is C _{8 to 20,} preferably selected from alkyl chains of C _{12 to 14)} a.

In the present invention, the optional surfactant polyhydroxyfatty acid amide is represented by the formula Wherein, R ⁴ is H, C _{1 to 4} hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C _{1 to 4} alkyl, more preferably methyl; R ⁵ is C ₅ Z is _-31 hydrocarbyl, preferably linear _C10-16 alkyl; Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain having at least three hydroxyls directly attached to the chain,
Or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof]. Z will preferably be derived from a reducing sugar in a reductive amination reaction. More preferably, Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.

The alkylpolyglucoside which is an optional surfactant in the present invention has the formula R ⁶ O (C _m H _2m O) _p (glucosyl) _q (where R ⁶ is an alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkyl phenyl, and is selected from the group consisting of mixtures thereof, the alkyl groups are C _{10 to 18,} preferably C _{12 to 14,} m is 2 or 3, preferably 2; p is 0 to about 10, Preferably is 0; q is 1.3 to 10, preferably 1.3 to 3,
Most preferably 1.3 to 2.7).

To prepare these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a glucose source to form a glucoside (linked at position 1). Additional glycosyl units can then be linked between their 1-position and the previous glycosyl unit at positions 2, 3, 4, and / or 6, preferably predominantly at position 2.

Alkyl ethoxylate is an optional surfactant in the present invention. Such alkyl ethoxylates are aliphatic alcohols having 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can be either straight or branched, primary or secondary, and generally has from 8 to 22 carbon atoms. A condensate of an alcohol having an alkyl group having 8 to 20 carbon atoms and 2 to 10 moles of ethylene oxide per mole of alcohol is particularly preferred. Most preferred is a condensate of an alcohol having an alkyl group having 8 to 14 carbon atoms with 6 to 10 moles of ethylene oxide per mole of alcohol.

In the present invention, any amphoteric surfactant has the formula Wherein R ⁷ is a C _7-21 alkyl group or an alkylaryl group, preferably C _9-17 ; R ⁸ is hydrogen or a C _1-6 alkyl group, preferably C _1-3 ;
⁹ C _{1 to 10} alkylene groups, preferably C _{2 to 6,} and most preferably a C _3, each R ¹⁰ is C _{1 to 6} alkyl or hydroxyalkyl group, preferably a C _{1 to 3,} and most preferably methyl or An ethoxylated hydroxyalkyl containing from about 1 to about 10 ethylene oxide units;
R ¹¹ is a betaine having a C _1-6 alkylene group, preferably methyl.

Preferably, from 0.1 to 1% of magnesium ion is incorporated into the composition of the present invention in order to improve the detergency without affecting the good usability and the good storage stability of the composition. You.

The composition of the present invention comprises a hydrotrope selected from the group consisting of cumenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, sodium salts and ammonium salts of sulfosuccinic acid, and mixtures thereof.
It can also contain 8% by weight. Such components are utilized to achieve the desired product phase stability and viscosity.

Other desirable components include solvents, preservatives, dyes, and fragrances.

Solvents useful in the present invention include water and low molecular weight alcohols such as ethanol. Ethanol is also known to reduce the viscosity of the product if needed for the formulation. Solvents other than water are typically
It is present in an amount of 10% by weight.

Preservatives, dyes and fragrances can be formulated into the compositions of the present invention to make the product attractive to consumers,
Will usually prescribe. These components are typically
Each is present in an amount of 1% or less.

Components not preferably incorporated into the composition are those that precipitate upon compounding with calcium ions. Examples are those that include sulfate, carboxylate and fatty acid anions.

[0041]

The following examples are provided to illustrate the compositions of the present invention, but are not intended to be limiting. All percentages and ratios are by weight unless otherwise indicated. Sample Preparation The compositions of the present invention can be prepared by the person skilled in the art by any convenient method. Surfactant in an appropriate amount of water,
Add the lysing agent, calcium salt and, if desired, magnesium salt and mix. The order in which the components are added is not important to the invention. If necessary, add hydrochloric acid to a level suitable for household products.
The pH is adjusted and the viscosity is adjusted by adding alcohol. After adding fragrances, dyes, preservatives and the like as desired, water is added to obtain the desired composition.

The standard product and Examples 1-9 are all prepared by this method. Experiment 1. Usability-500% 6% aqueous solution of standard product and composition of the invention
g is prepared in a 1 liter beaker, and a porcelain crucible is immersed in the aqueous solution. -Simultaneously immerse one hand in the sample aqueous solution and the other hand in the general standard product aqueous solution, and evaluate the difference in sliminess on the crucible on the following scale. -The evaluation is performed by three specialized panels and the average is taken. Evaluation scale 0 = No difference ± 1 = I think there is a difference ± 2 = I know there is a difference ± 3 = I know there is a big difference ± 4 = I know there is a very big difference (+): Sample Good (not slimy) (-): Sample is worse (slimy) For those with higher points as compared to the composition containing the same surfactant system containing no calcium, "the feeling of use was improved." Is determined. 2. Storage stability Put the sample in a 100 ml glass container,
Each is stored for 2 weeks in a constant temperature room set at 0 ° C. The condition of the product after two weeks is evaluated as follows. Transparent and unchanged from before the start of the test-O Precipitation, mist, etc.-X According to Table 1, Examples 1, 3, 4, 7 which are the compositions of the present invention
Indicates that the usability is improved and the storage stability is good.

[0043]

[Table 1]

[0044]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1:75 1:14 1:06 1:22) (73) Patent holder 592043805 ONE PROCTER & GANB LE PLAZA, CINCINNATI I, OHIO , UNITED STATS OF AMERICA (72) Inventor Ryohei Otani 1-5, Kashihara-cho, Ibaraki-shi, Osaka (56) References JP-A-59-36197 (JP, A) JP-A-2-43300 (JP, A) (58) Field surveyed (Int.Cl. ⁶ , DB name) C11D 1/86 C11D 3/04

Claims (12)

(57) [Claims] 1. A (1) anionic surfactants, nonionic surfactants, amphoteric surfactants, and selected from the group consisting of mixtures thereof, the alkyl group and 1 (a) C _{10 to 16}
At least 3% by weight of the alkyl ethoxy sulfate composition having an average of 1 to 10 moles of ethylene oxide per molecule and at least 20% by weight of the surfactant system;
(B) alkylbenzene sulfonates, alpha-olefin sulfonates, alkyl ethoxy carboxylates, and other anionic surfactant selected from the group consisting of mixtures thereof, diethanolamide composition having an alkyl chain of _(c) C ₈ ~20 0 to 9% by weight of (d) C
Aqueous hard surface comprising a surfactant system 3 to 35 wt% and (2) calcium ions 0.01 to 0.5 wt% including 0-10 wt% of the amine oxide compositions with _8-16 alkyl chain An aqueous detergent composition for hard surfaces providing improved usability, characterized in that at least 20% by weight of the surfactant system consists of components a, b, c and d. 2. The composition according to claim 1, comprising 0.1 to 0.5% by weight of calcium ions. 3. The composition according to claim 2, comprising 0.1 to 0.3% by weight of calcium ions. 4. The composition of claim 1, wherein said surfactant system comprises at least 35% by weight of said alkyl ethoxy sulfate.
A composition according to claim 1. 5. The method according to claim 1, wherein the alkyl ethoxy sulfate is 1
The composition of claim 1 having an average of 2 to 5 moles of ethylene oxide per molecule. 6. The method according to claim 1, wherein the alkyl ethoxy sulfate is 1
The composition according to claim 5, having an average of 2.5 to 3.5 moles of ethylene oxide per molecule. 7. The composition according to claim 4, comprising 20-30% of said surfactant system. 8. The composition according to claim 1, wherein the diethanolamide comprises 4 to 7%.
A composition according to any one of claims 1 to 7. 9. The composition according to claim 1, comprising 2 to 5% of the amine oxide. 10. The composition according to claim 1, comprising 0.1 to 1% by weight of magnesium ions. 11. A compound selected from the group consisting of (1) anionic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof, and (a) a _C10-16 alkyl group and a molecule per molecule. average 2.5-3.5 units of at least 35 wt% of the alkyl ethoxysulfate surfactant system with ethylene oxide, 4-7 wt.% of diethanolamide composition having an alkyl chain of _(b) C ₈ ~20,
(C) Amine oxide having a _C8-16 alkyl chain
20-30% by weight of a surfactant system comprising 2-5% by weight of the composition; (2) 0.1-0.3% by weight of calcium ions; and (3) 0.1-1% by weight of magnesium ions. The composition according to any one of claims 1 to 10. 12. Use of an aqueous detergent composition for hard surfaces or a cleaning solution of an aqueous detergent composition for hard surfaces, wherein 0.01 to 0.5% by weight of calcium ions is added to the aqueous detergent composition for hard surfaces. How to improve the feeling.