JPH05239500A - Improvement to hard surface cleaner - Google Patents

Abstract

PURPOSE: To mask volatile amine odor and prevent corroding in the empty space of a filled can by filling a surfactant, a liquid phase corrosion inhibitor, and a volatile amine in a metal can.

CONSTITUTION: A composition comprising 0.1-10 wt.% nonionic surfactant having 3-12 HLB, 0.1-10 wt.% liquid phase corrosion inhibitor, 100-750 ppm volatile amine, and 0.1-10 wt.% solvent is regulated to pH 11-13 by adding an alkali. The composition and a propellant are filled in a metal can.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a foamable hard surface cleaning agent and a method for producing the cleaning agent in a packaging form.

[0002]

It is known to include a foamable hard surface cleaner in a metal can together with a propellant for dispensing the cleaner through a valve. Such cleaning agents are usually detergents (to provide cleaning action), solvents (to facilitate cleaning), EDTA (to help remove limescale: limescale / iron stains), etc. Of a sequestering agent for metal ions and a fragrance. The pH of such compositions is alkaline. Known commercial compositions are sprayed onto hard surfaces (such as bathroom and kitchen surfaces) to help remove limestone, soap deposits and other soils. Other metals (eg,
Aluminum or the like) may be used, but the can is conveniently formed from a tin-plated steel plate.

It is well known that corrosion can occur both on the inner surface of the can, in the areas in which the can can come into contact with the liquid phase and especially in the areas in which the can can come into contact with the gas phase (ie the head fill space of the can). Is. Corrosion in the filled volume is believed to occur due to the presence of water vapor in the propellant in the filled volume.
Corrosion not only weakens the can, but also discolors the contents of the can severely, so some used cans must be discarded. Discarding cans wastes resources such as surfactants and other substances into the ecosystem, wasting resources.

In known compositions, high pH and alkaline silicates are used to prevent corrosion in the areas of the can that come into contact with the liquid phase. It is believed that corrosion can be prevented by forming a protective film on the inner surface of the can. For conventional tin-plated steel cans, this layer is believed to form a layer of tin oxide on the inside surface of the can, but the detailed composition of this layer is unknown.

In the specification of the present invention, the components incorporated into the liquid phase which inhibit the corrosion of the portion of the can that contacts the liquid phase are:
It is called a liquid phase corrosion inhibitor.

Even with the inclusion of liquid phase corrosion inhibitors (eg, alkaline silicates), corrosion can occur in areas of the can that are in contact with the gas phase,
It can occur especially around the dome-shaped portion of the top of the can, the top portion of any sidewall seals and valve fittings. This second form of corrosion also weakens the can and severely discolors the contents of the can.

A further problem with corrosion is that the active metal ion sequestrant is lost because the metal ions are released into the composition. Since the sequestrant plays an important role in the lime scale removal action of the composition, if the sequestrant is compromised, the performance will correspondingly decrease.

The incorporation of volatile amines in such compositions, preferably primary or secondary amines or ammonia, in order to prevent corrosion in these parts of the can which are in contact with the gas phase, is It is known. As used herein, unless otherwise stated, ammonia is considered an amine.

Ammonia is known to have a characteristic, persistent and unpleasant odor and requires high levels of strong perfume to be incorporated into the composition. Previous compositions used accurately measured ammonia at levels up to and above 1000 ppm. The odor of ammonia is significant at levels above about 700-750 ppm. The odor rating of hard surface cleaners on the market indicates that it is the pronounced and characteristic offensive odor of ammonia. Assuming that the known threshold is that ammonia can be detected by the human nose, it is believed that these conventional products have ammonia levels above 750 ppm.

The number of accurately measured ammonia levels in products on the market is probably due to the loss of vapor when opening the can for inspection and the adsorption of ammonia on the inner surface of the can.
It is expected to be measured lower than the actual value.

[0011]

As mentioned above, it can be understood that the addition of ammonia to the formulation of the contents of a can to prevent the corrosion that occurs in the filling empty space of the can. However, while it is desirable to retain an acceptable aroma in the product while preventing vapor phase corrosion, known corrosion protection methods must incorporate unacceptably high levels of ammonia.

[0012]

SUMMARY OF THE INVENTION The present inventors have been able to provide adequate corrosion protection in can fill volumes at levels less than ammonia used in the prior art, and the odor of ammonia is essentially acceptable. It has been demonstrated that ammonia levels can be achieved that are or can be effectively masked by perfume.

Ammonia levels in the compositions disclosed herein of greater than about 100 ppm, and preferably greater than 190 ppm provide good corrosion protection in fill voids. In a typical composition when ammonia is included at levels of about 700-750 ppm or less,
Depending on the particular perfume composition used, the odor of ammonia is not unpleasant.

It is also desirable not to use EDTA as a sequestrant. EDTA is non-biodegradable and has been criticized for its ability to sequester and dissolve heavy metal ions (eg, cadmium and mercury) from river sludge and sediments. Surprisingly, the inventors have determined that modifying the sequestration system offers the advantage of reducing any negative effects of sequestering agents in the biosphere while reducing can corrosion.

Accordingly, the present invention provides a stable, packaged, foamable hard surface cleaning composition in which a composition comprising a surfactant, a liquid phase corrosion inhibitor, and 100 to 750 ppm of a volatile amine is packaged in a metal can. Provide things.

In the present invention, acceptable storage stability is considered to have been achieved if after storage for 6 weeks at ambient temperature no part of the inner surface of the can is corroded at all.

Usually, the composition further comprises a fragrance.

For a typical perfume composition, the odor is very acceptable when the amine is ammonia. Alternatively, the amine may be selected from the group consisting of volatile mono-, di- and trialkanolamines, amino-alcohols and mixtures thereof. Of the amines, ammonia is preferred because it reduces the tendency for unwanted compounds (eg, nitrosamines) to form.

The ammonia level is preferably 400 to 750 ppm, more preferably 400 to 600 ppm. Best results are obtained when the ammonia level is about 450-570 ppm. Lower levels of ammonia are usually preferred so that any residual odor can be masked by low levels of mild perfume.

Suitable liquid phase corrosion inhibitors include alkaline silicates. Substitutes may be used provided they are effective in the pH of the liquid phase and the metal used for the walls of the can. The preferred level of liquid phase corrosion inhibitor is 0.1 to 10% by weight.

Lower levels of ammonia also reduce corrosion protection in those areas of the can that come into contact with the gas phase. In the liquid phase, the combination of aqueous alkali, alkaline silicates or other liquid phase corrosion inhibitors with ammonia provides effective corrosion protection at lower levels than in the gas phase. Thus, the composition of the present invention preferably comprises at least two corrosion inhibitors, one more volatile and effective in the gas phase, the other less volatile and effective in the liquid phase.

The composition preferably further comprises a sequestering agent. EDTA is known as a suitable sequestering agent, but sequestering agents other than EDTA are preferred for the above reasons.

Suitable sequestrants are selected from polycarboxylic acids, polyacrylates, phosphonates and their salts. The sequestering agent is preferably a polycarboxylic acid or salt thereof. More preferably, the sequestrant is citric acid or citric acid in combination with one or more acids selected from adipic acid, succinic acid, glutaric acid or salts thereof. Most preferably, the sequestrant is citric acid alone or a salt thereof.

When EDTA is added, the formation of a protective film on a tin-plated steel can is performed by so-called tin removal (de-t) on the inner surface of the can.
innig) is a feature. With the addition of citrate, there is much less corrosion, but tin removal on the inner surface of the can is not clear.

In conventional cans, the overcoat does not extend to the top or dome area of the can. Ensuring that the protective effect extends to the inner surface of the can could substantially reduce can corrosion and product discoloration, if not completely prevented during the life of a typical commercial can.

We have turned the can over after filling, holding the can in the inverted position for a period of time long enough for the protective film to form in the upper region of the can, and then fully covering the lower region of the can with the protective film. It was confirmed that the entire inner surface of the can can be protected by returning the can to the normal state so as to form.

Other operating methods (eg rolling a can,
Shaking) can also be used. A problem in operation is that the entire inner surface of the can must be coated with the contents immediately after filling. It is believed that this treatment ensures that the protective layer is formed over the entire inner surface of the can.

Therefore, another aspect of the present invention is
(A) A can is filled with a composition consisting of a liquid component consisting of a liquid phase corrosion inhibitor and a normal gas component consisting of a propellant and a volatile amine, (b) the can is sealed, and (c) the inside of the can. A method of packaging a foam hard surface cleaner comprising the steps of storing the can in at least two orientations so that the entire surface is treated with the liquid phase component.

For cans that have been treated by this "inversion method" or repositioned in other directions during storage, when the can is unfolded for inspection, the characteristic double-striped pattern on the internal metal surface of the can. (Banding) is found. In the case where the can is simply inverted, this double stripe pattern takes the form of first and second reference lines on the inner surface of the can, each reference line defining the first and second inner volume of the can. In the first and second planes, respectively, and the volume of one section defined by the first plane is arranged to be equal to the volume of the other section defined by the other plane. There is.

Re-orientation proce
For tin-plated cans over ss), a characteristic dull film is also seen to be spread over the entire inner surface of the can. In conventional cans, the overcoat does not extend to the top of the can or the dome area, and these areas retain the brightness of the tin-plated steel plate. If the protective layer tightly covers the inner surface of the can, the corrosion and product discoloration of the can could be significantly reduced, even though it may not be completely prevented during the life of a typical commercial can.

The apparent appearance of the film and stripes varies depending on the can used and the type of sequestrant used. When EDTA is added as a sequestering agent, a striped pattern is noticeable,
The inner surface of the can is quite dull. When citrate is blended as a sequestering agent, stripes are slightly visible and the inner surface remains bright. Whether citric acid or EDTA is used as a sequestrant, the surface can be adequately protected to prevent corrosion during the life of the product.

In view of the above described aspects of the present invention, it may be possible to produce a package-stable, low ammonia product which is odor acceptable and does not suffer from packaging corrosion problems that may occur at low ammonia levels. Can be found.

While the various aspects of the present invention are uniform in that conventional low ammonia formulations were desired, in practice,
The formulation could not be packaged in stable form.

In a preferred embodiment of the present invention, the cleaning composition comprises at least ammonia, a surfactant, a solvent, a sequestering agent, an alkali and a fragrance.

The surfactant is conveniently incorporated in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight. The surfactant is H
Nonionics with a LB of 3 to 20, preferably 12 to 16, are suitable. Alcohol ethoxylates have been found to be particularly suitable as surfactants.

The solvent is preferably one capable of dissolving the non-polar species and may be miscible or immiscible with the aqueous solution. Such a solvent is 0.1 to 10% by weight, preferably 1 to 10% by weight.
It is preferably compounded at a level of 5% by weight. The solvent preferably has a solubility of 1% or more in water. It has been found that glycol ethers, preferably butyl carbitol and alcohols, preferably isopropyl alcohol, are suitable.

Sequestering agents for metals such as calcium and magnesium are preferably incorporated at levels of 0.1 to 8% by weight, more preferably 0.5 to 6% by weight. As mentioned above, trisodium citrate is the preferred sequestrant.

Suitable alkalis include buffering agents which buffer at alkaline pH. Suitable buffers are preferably formulated to raise the pH of the composition to a pH above 10. The pH of the composition is preferably 11-13. Alkaline silicates that function as liquid phase corrosion inhibitors and buffer at pH 11-12 are preferred. Alternatively, the buffer system is phosphate,
It is preferably composed of carbonates and borates. This does not preclude the use of non-buffering agents to raise the pH (ie sodium hydroxide). Alkaline silicates are also believed to have a stabilizing effect on the formulations of the present invention.

A typical composition is (a) 100 ammonia.
~ 750ppm, (b) citric acid or its salt 0.75-10%,
It is composed of (c) 0.05 to 10% of alkaline silicate and (d) 0.10 to 10% of surfactant.

Alternatively, the composition comprises (a) ammonia 10
0 to 750 ppm, (b) aminopolycarboxylic acid 0.1 to 5%,
(C) 0.05-10% alkaline silicate, and (d) 0.1-10% surfactant.

The propellant is preferably blended at 3 to 20%. Although halogenated propellants may be used, it is preferred to use "ozone friendly" propellants such as air, carbon dioxide, nitrogen and its oxides, volatile hydrocarbons or mixtures thereof.

A mixture of butane and propane has been found to be particularly suitable.

[0043]

EXAMPLES Examples are provided by way of reference for a further understanding of the invention.

A foamable hard surface cleaner was prepared with the composition given in Table 1.

[0045]

[Table 1]

The alkaline silicate used was Crystal-12.
0A (trademark: Crosfields, Warrington).

The method of packaging the foamable hard surface cleaner is as follows:
(A) Mixed under air and divided into 200 ml aliquots,
A tin-plated steel can was filled with a composition consisting of ammonia, a sequestering agent, a solvent, a buffer solution, a liquid phase corrosion inhibitor, a fragrance and a surfactant, and (b) a cooled propellant was placed in the can. The process comprises the steps of sealing the can and then (c) storing the can in the inverted orientation for 48 hours after filling and then in the "normal" orientation so that the entire inner surface of the can is treated with the liquid phase corrosion inhibitor. Was there.

After storage for 6 weeks at ambient temperature, the cans were opened and the inner surface was inspected.

At a level of 1000 ppm ammonia, corrosion was very well protected in the presence of EDTA (1.3%) both with and without the method of the invention, but the odor of ammonia generated from the product was Was unacceptably uncomfortable. The odor and corrosion results for both control and inverted cans are summarized in Table 2 below.

[0050]

[Table 2]

It can be seen that 190-700 ppm of ammonia provided very good corrosion protection. These examples constitute examples of the invention, but the examples with 0 and 1000 ppm ammonia are comparative examples.

The cleaning performance was compared with pre-stained plastic sheets. This sheet was made by spraying a thin layer of a solvent in which calcium stearate was dispersed onto a sheet molded from an acrylic plastic of the type used to make baths. Before applying calcium stearate,
The sheet was cleaned with a branded dishwashing solution and rinsed thoroughly with water. Dimensions 30 cm x 2 using a solution of 15 g calcium stearate in 500 g isopropyl alcohol.
About 1 gram of calcium stearate was placed on a 0 cm sheet. During the cleaning performance test, a small amount of carbon black was added for easy viewing. 50 sheets after dirt
Heated at ℃ for 18 hours.

The performance test consists of applying the hard surface cleaning composition to a pre-soaked sheet. Four hollow,
Clear glass cylinder with open ends (5 cm / each height)
5 cm diameter) was placed on the dirty surface of the sheet. The composition was sprayed into the upper open end of each cylinder for 2 seconds so that the cylinder was half filled with foam. A passive washing operation was performed for 5 minutes. The cylinder was then removed from the sheet and the sheet was rinsed for 10 seconds with cold running water (15 ° C.) of French hardness 12. The water flow rate was set to 2 liters / minute before rinsing. The sheets were left to dry in air at room temperature (which takes 1-2 hours) and then repeated 3 replicates of each composition for at least 3 using the scale described in Table 3.
It was evaluated by a human trained panel.

[0054]

[Table 3]

The results of the panelists and replicates were averaged to determine the overall percentage for each composition.

Comparative tests were carried out with the sequestrants given in Table 4. Results standardized 1.3% EDTA as 100% efficacy. The standardized numbers are the performance of all compositions in the performance tests described above, using the grades in Table 3 averaged over the replicates.

For comparison, the affinity of some sequestrants for calcium is given as the logarithm of the binding constant between the sequestrant and the calcium and sequestrant at a fixed concentration of calcium. Be done. It is believed that these numbers represent relative calcium binding capacity rather than absolute values.

[0058]

[Table 4]

Dequest, Sokalan and Trilon are registered trademarks.

From Table 4 it can be seen that the effectiveness of the sequestrants is not solely related to their calcium binding capacity: the Dequest 2016 / 2060s / 2000 affinity of the sequestrants for calcium is relevant to the wash test. It has not changed as much as their effectiveness in. That is, Dequest 20
Although 60s seems to have the highest affinity for calcium on a theoretical basis, Dequest 2016 forms a more effective cleaning composition from experimental results, although the affinity is clearly lower.

When both ammonia and EDTA are blended,
The formation of a protective film on a tin-plated steel can is characterized by so-called removal of tin on the inner surface of the can. When the citrate was formulated in combination with ammonia and silicate, tin removal on the inner surface of the can was not significant, but corrosion was significantly reduced.
Surprisingly, citric acid worked much better than Sokalan DCS, a combination of adipic acid, succinic acid and glutaric acid.

When adding ammonia and citrate without adding silicate, tin removal was significant.

Various modifications may be made to the embodiments of the present invention without departing from the scope of the present invention. For example, I mentioned that cans need propellants to disperse the contents,
This does not exclude the use of pump-dispersing lids.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display location C11D 3:08) (72) Inventor Ronald Melades Morris Merseyside El 49, England 3. A. Kyu, Wilal Graceby, Patstow Road 15 (72) Inventor Raymond Jean-Barreer France, 59237 Berlangan, Ciyuman-Giorgyu-Carpentier, La Tremoiseie (No address)

Claims (15)

[Claims] 1. A stable, packaged, foamed hard surface cleaning composition containing a surfactant, a liquid phase corrosion inhibitor, and 100-750 ppm of a volatile amine and packaged in a metal can. 2. The composition according to claim 1, wherein the liquid phase corrosion inhibitor is an alkaline silicate. 3. The composition according to claim 1, further comprising a fragrance. 4. The composition according to claim 1, wherein the volatile amine is ammonia. 5. The composition according to any one of claims 1 to 4, which has a pH of 11 to 13. 6. 190 to 750 ppm, preferably 400 to 750 ppm,
The composition according to any one of claims 1 to 5, which further preferably contains 450 to 570 ppm of ammonia. 7. The composition according to claim 1, wherein the metal can contains a propellant gas. 8. The first and second reference lines are on the inner surface of the can and each reference line is in a first plane and a second plane that divides the inner volume of the can into first and second portions. The composition of claim 1, wherein the arrangement is such that the volume of one portion bounded by the first plane is equal to the volume of the other portion bounded by the other plane. 9. A can is filled with a composition comprising (a) a liquid component comprising a liquid phase corrosion inhibitor and a normal gas component comprising a propellant and a volatile amine, and (b) the can is sealed, and c)
So that the entire inner surface of the can is treated with a liquid phase corrosion inhibitor,
A method of packaging a foam hard surface cleaner comprising the steps of storing a can in at least two directions. 10. A composition comprising 100 to 750 ppm of ammonia, an effective amount of a liquid phase corrosion inhibitor, 0.1 to 10% by weight of a surfactant, 0.1 to 8% by weight of a sequestering agent, and a fragrance. 7. The composition according to any one of items 6 to 6. 11. Composition according to claim 1, characterized in that the sequestering agent is selected from polycarboxylic acids, polyacrylates, phosphonates, salts thereof and mixtures thereof. object. 12. The composition according to claim 11, wherein the sequestering agent is a polycarboxylic acid or a salt thereof. 13. The composition according to claim 12, wherein the sequestering agent is citric acid or a salt thereof. 14. (a) 100 to 750 ppm of ammonia,
(B) Citric acid or its salt 0.75-10%, (c) Alkaline silicate 0.05-10%, and (d) Surfactant 0.1-10%.
14. The composition of claim 13, which consists of 15. (a) 100 to 750 ppm of ammonia,
The composition according to claim 10, which comprises (b) 0.1 to 5% aminopolycarboxylic acid, (c) 0.05 to 10% alkaline silicate, and (d) 0.10 to 10% surfactant.