JPS5927799B2 - Film-type cleaning composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a film-type cleaning composition.

More specifically, the present invention relates to a film-forming type cleaning composition that has excellent cleaning power against denatured oil stains and carbonized stains, and has the excellent characteristics of being easy to handle and being non-hazardous. Neutral kitchen detergents such as those disclosed in Japanese Patent Publication No. 52-38506 are used to clean oil stains such as vegetable oil and animal oil adhering to tableware, but they also adhere to kitchen ventilation fans, gas ranges, etc. Neutral kitchen detergents cannot have a sufficient cleaning effect on denatured oil stains such as sticky oil stains and baked-on oil stains that have been thermally denatured, photodenatured, or oxidized from vegetable oils and animal oils.

For such denatured oil stains,
A strong alkaline household detergent as shown in Publication No. 88 is used. That is, by using a cleaning composition consisting of an alkaline agent such as ammonia, monoethanolamine, and sodium hydroxide, a water-soluble solvent such as Cellosolve and Calpitol, and a surfactant, sticky oil stains and baked-on oil stains can be sufficiently removed. Can be washed. Further, when heat-denatured, photo-denatured, or oxidation-denatured oil stains are further denatured by heating, they become carbonized stains.

This charred dirt includes not only animal and vegetable oils, but also charred protein and carbohydrate foods caused by boiling over and sauces during cooking, and can be found around gas ranges, inside grills, in ovens and open pans, etc. Detracts from the aesthetic appearance and deteriorates the finish of cooked products. To clean such carbonized dirt, abrasives (materials) such as cleansers, soap pads, steel wool, nylon scrubbers, and metal scrubbers, and strong alkaline cleaning agents collectively called oven cleaners are used. However, in the case of abrasives (materials), since they mainly have physical effects, a great deal of effort is required to obtain a sufficient cleaning effect on carbonized dirt. On the other hand, oven cleaners are strongly alkaline and come in an aerosol or liquid form, so they are dangerous if they come into contact with the human body, such as the skin or eyes, or if they come into contact with clothes, painted surfaces, or objects such as metal or plastic. Sufficient care must be taken when using them to avoid damage. Furthermore, when cleaning denatured oil stains or carbonized stains using strong alkaline household detergents, abrasives (materials), or oven cleaners, after cleaning, wipe off the detergent used and the cleaned stains. There remains the tedious task of rinsing. Therefore, the inventors of the present invention have developed a method that has sufficient cleaning power against denatured oil stains and carbonized stains, and also eliminates the troublesome cleanup such as wiping and rinsing the cleaned stains, and the danger and damage to the human body, clothing, and equipment. We have conducted extensive research to develop a cleaning composition that solves these problems, and have developed a film-type cleaning composition that contains a film-forming emulsion or a film-forming polymer solution and an alkaline agent. It has been developed and has already been applied for (see Japanese Patent Application No. 55-115421 and Japanese Unexamined Patent Publication No. 5740600).

However, although the problems of cleanability and workability were solved by the above-mentioned film-type cleaning composition, the storage stability of the cleaning composition itself was not necessarily satisfactory.
That is, film-forming emulsions had the disadvantage of being subjected to dispersion destruction and agglomeration due to the presence of alkali.The inventors of the present invention continued their research to solve this disadvantage, and as a result, they discovered a specific non-conforming emulsion. The present invention was completed by discovering that the above drawbacks could be eliminated by adding an ionic surfactant.

That is, the present invention provides a film-type cleaning composition containing the following (a) to (c) as main components.

(a) Film-forming emulsion (b) Alkaline agent (c) One or more polyether type nonionic compounds selected from the group consisting of compounds represented by the following general formulas (1) and (11) Surfactant [In formula (1), R1 is an alkyl group having 6 to 12 carbon atoms, and p is 30 to 10 on average
It is 0.

[CH3), R3 is an alkyl group having 1 to 4 carbon atoms, m is 1
An integer of ~3, n is an integer of O~2, l is an average of 20 to 10
It is 0. The film-forming emulsion used in the present invention is not particularly limited, but it must be one that does not lose its film-forming ability in the presence of an alkaline agent.

Film-forming emulsions include, for example, ethylene, propylene, isobutylene, butadiene, isoprene, styrene, acrylonitrile, vinyl acetate, vinyl chloride,
Homopolymer emulsions consisting of monomers such as vinylidene chloride, vinylbutylate, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl vinyl ether, butyl vinyl ether, copolymers consisting of these monomers or other monomers Emulsions can be mentioned. Among these, styrene/butadiene copolymer emulsion, polyvinyl chloride emulsion, and methyl methacrylate polymer emulsion are particularly preferred.The viscosity of the emulsion is not particularly limited, but it is preferably 200 cp (20°C) or more in consideration of the applicability to vertical surfaces. Desirably, there is no particular limitation on the upper limit, but in consideration of workability, it is 20,000 cp or less, preferably 100 cp or less.
00cP or less.

Usually, an emulsion having a solid content of 30 to 60% by weight is used. Further, it is desirable that the emulsion has a low film forming temperature.

Although it varies depending on the conditions used, the minimum film forming temperature is 25℃
The temperature is preferably below 15°C. Furthermore, it is desired that the produced film has a certain degree of strength and is desirably easy to peel off after the film has been formed. The amount of emulsion is not particularly limited and is determined in consideration of other ingredients, but is usually 50 to 98.5% by weight, preferably 6% by weight.
It is 0 to 95% by weight.

The alkaline agent that can be used in the present invention is not particularly limited, and any alkaline agent that can be used in detergents can be used.

For example, sodium hydroxide, potassium hydroxide, sodium (or potassium) orthosilicate, sodium (or potassium) metasilicate, sodium (or potassium) phosphate, sodium (or potassium) metaborate, sodium carbonate (
or potassium), or ammonia and amines represented by the following formulas (1) to (3). (In formulas (1) to (3), R,,
R4, R6, R8, R, O. Rl2 is H. CH
3, C2H,, C3H7, or C4H9, and R2, R3, R5, R7, R9, and Rll are each H
．． CH3, C2H5, C3H7, C4H9, C2H4O
H,. Represents any of C3H6OH.

) The amount of the alkaline agent is not particularly limited and varies depending on the type of alkaline agent, but is usually 0.5 to 15% by weight, preferably 1 to 10% by weight.

Particularly preferred are sodium hydroxide and potassium hydroxide. The alkaline agent may be directly dissolved in the emulsion or mixed with a small amount of water. The nonionic surfactant used in the present invention is characterized by the following general formula (1) or It is necessary that the compound is represented by (11).

Even if surfactants other than these are used, the emulsion latex stability of the present invention cannot be obtained. [Formula (1
), R1 is an alkyl group having 6 to 12 carbon atoms, and p is 30 to 100 on average.

] [In formula (n), or (R4 is H or CH3), R3 is an alkyl group having 1 to 4 carbon atoms, m is 1 to
An integer of 3, n is an integer of 0 to 2, l is an average of 20 to 100
It is.

] Generally, an appropriate surfactant is added to emulsion latex during or after emulsion polymerization in order to stabilize the latex particles.

Examples of this type of emulsion stabilizer include anionic surfactants such as fatty acid salts, alkyl sulfates, sulfated oils, alkylbenzene sulfonates, naphthalene sulfonate formalin condensates, phosphate ester salts, and aliphatic amine sulfates. However, nonionic surfactants include polyoxyethylene (5 to 15
mole) alkyl ether, polyoxyethylene (5 to 1
(5 mol) alkyl phenol ether, oxyethylene oxypropylene block polymer, etc., and as amphoteric activators, betaine, sulfobetaine, etc. are used. However, although conventionally used surfactants contribute to the stability of emulsions in the vicinity of neutrality, they have no effect at all in strong alkalis such as those used in the present invention, and the emulsion system is destroyed and aggregation occurs. . On the contrary, the nonionic surfactant represented by the general formula (1) or (11), which is the component (c) according to the present invention, still has an excellent stabilizing effect even in strong alkalis.

General formula (1) or (10) which is the component (c) according to the present invention
Although the mechanism of why the nonionic surfactant represented by the formula has such an excellent stabilizing effect is not necessarily clear, it is probably thought to be as follows. That is,
The compound represented by the general formula (1) or (11) has a lipophilic group containing a benzene ring and a long polyoxyethylene chain, and this lipophilic group containing a benzene ring strengthens its affinity with latex particles. It is believed that the adsorption protective layer formed by the polyoxyethylene chains does not cause phenomena such as aggregation caused by electrolyte addition, and the steric protection effect is significantly improved.

In any case, it can be said that this is a synergistic effect between the lipophilic group containing the benzene ring and the long polyoxyethylene chain. Therefore,
As shown in general formulas () and (n), the ethylene oxide chain (number of moles added) is extremely important. General formula (
For the compound 1), 30 to 100 mol, preferably 60 to 9
0 mol, and 20 to 10 mol for the compound of general formula (11).
The amount is 0 mol, preferably 30 to 80 mol. Specific examples of nonionic surfactants represented by the general formula () include polyoxyethylene (60 mol addition) nonylphenol ether (hereinafter expressed as POE(60) nonylphenol), POE(45 ) nonylphenol, POE(75) dodecylphenol, etc., as specific examples of nonionic surfactants represented by the general formula (I[), POE(50) styrenated phenol, POE
Examples include (80) styrenated phenol, POE (50) dibenzyl phenol, and POE (60) tribenzyl phenol.

The above-mentioned nonionic surfactant can be produced by a conventional method such as a corresponding alkyl phenol styrenated phenol, benzyl phenol, etc., for example, by adding ethylene oxide in the presence of an alkali catalyst. is also easily obtained.

The amount of the nonionic surfactant varies depending on its type and the intended use of the composition, but it is usually used in the range of 0.5 to 10% by weight, preferably 1 to 5% by weight.

The surfactant contained in the film-forming emulsion itself, component (a) used in the present invention, and the nonionic surfactant, component (c), according to the present invention are unrelated to each other. That is, various surfactants such as those mentioned above are used in the production of the emulsion of component (a), but the effect of the nonionic surfactant (component (c)) in the present invention depends on the influence of these surfactants. It is not something that is received. Furthermore, the nonionic surfactant as component (c) of the present invention has poor affinity with the emulsion polymer, and therefore cannot be used in the emulsion polymerization of the emulsion as component (a). Since the film-type cleaning composition of the present invention has the above-mentioned composition, it has excellent cleaning power and workability, as well as excellent chemical and physical stability.

In carrying out the present invention, in order to further enhance the detergency, anionic surfactants, nonionic surfactants other than the component (c) above, and amphoteric surfactants are used to reduce the effect of the present invention. It can be blended arbitrarily within the range.

The blending amount is usually 1 to 10% by weight. These include anionic surfactants such as alkylbenzene sulfonates, alkyl sulfates, alkyl ethoxy sulfates, olefin sulfonates, alkanesulfonates, fatty acid salts, alkyl ethoxy carboxylates, α- Sulfo fatty acid salt, α-sulfo fatty acid ester salt,
Nonionic surfactants include ethylene oxide/propylene oxide protox copolymers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and higher fatty acid alkanolamides. Examples of the amphoteric surfactants include tertiary amine oxide, betaine, sulfobetaine and the like. Particularly preferred is polyoxyethylene alkyl ether. Furthermore, in implementing the present invention, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, ethylene glycol, propylene glycol, methyl Water-soluble solvents such as cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, polyoxypropylene (2.5) monomethyl ether, etc. They may be added as desired within a range that does not impair the effects of the present invention. The blending amount is usually 1 to 10% by weight. In addition, an adhesive such as polyacrylic acid may be added as an optional component to more effectively adsorb and remove decomposed dirt.

Furthermore, builder components such as condensed phosphates, silicates, sulfates, borates, nitrilotriacetates, ethylenediaminetetraacetates, carboxymethylcellulose, polyvinylpyrrolidone, polyacrylates, alginates, thickeners, pigments, Coloring agents, fragrances, bactericidal agents, preservatives, enzymes, plasticizers, and the like may be optionally added to the extent that they do not impair the effects of the present invention. By using the cleaning composition of the present invention, denatured oil stains and carbonized stains can be removed extremely easily.

That is, it is sufficient to simply apply the cleaning composition of the present invention to a surface with denatured oil stains or carbonized stains, leave it for a while, and then peel off the formed film. This makes it possible to remove stubborn stains with extremely little effort, without the need for wiping or rinsing after cleaning.
Furthermore, since the cleaning composition of the present invention has a suitable viscosity, it hardly drips even when applied to vertical surfaces, so it can be applied to vertical surfaces such as ventilation fans without removing it. It also has the advantage of being washable. The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 The compositions shown in Table 1 were examined for detergency, workability, and stability against model carbonized stains.

The results are shown in Table 1. (Model carbonized stain) Two egg yolks (357), broken sugar 107 and soy sauce 107 were stirred well, applied on an iron plate, and heated until the applied material was carbonized.

(Cleaning power test) The cleaning composition shown in Table 1 was applied to a model carbonized stain board,
After standing for 10 hours, the cleaning composition was removed and stain removal was determined.

○: Complete stain removal △: About 50% stain removal x: No stain removal at all (workability) Workability in removing the cleaning composition after leaving it to stand (film peeling, wiping, and rinsing) was evaluated.

○: Extremely easy △: It takes a little time ×: Troublesome.

(Stability) Place in a transparent plastic bottle in a constant temperature room (50℃)
It was stored for 20 days, and the condition after storage was observed and judged.

Example 2 The stability of the compositions shown in Table 2 was investigated in the same manner as in Example 1.

The results are shown in Table 2. Example 3 The compositions shown in Table 3 were examined qualitatively in the same manner as in Example 1.

The results are shown in Table 3. Example 4 The compositions shown in Table 4 were qualitatively examined in the same manner as in Example 1.

Claims (1)

[Scope of Claims] 1. A film-type cleaning composition containing the following (a) to (c) as main components. (a) Film-forming emulsion 50-98.5% by weight
(b) 0.5 to 15% by weight of an alkaline agent (c) One or more polyether-type nonionic interfaces selected from the group consisting of compounds represented by the following general formulas (I) and (II) Activator 0.5-10% by weight ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In formula (I), R
^1 is an alkyl group having 6 to 12 carbon atoms, and p is 30 to 100 on average. ]▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [Formula (II)
Inside, R^2 has ▲ mathematical formulas, chemical formulas, tables, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^4 is H or CH
_3), R^3 is an alkyl group having 1 to 4 carbon atoms, m is 1 to
An integer of 3, n is an integer of 0 to 2, l is an average of 20 to 100
It is. ]. 2. The nonionic surfactant represented by formulas (I) and (II) is polyoxyethylene nonylphenol ether, polyoxyethylene styrenated phenol ether, polyoxyethylene dibenzyl phenol ether or polyoxyethylene tribenzyl phenol ether. A film-type cleaning composition according to claim 1. 3. The film-type cleaning composition according to claim 1 or 2, wherein the alkaline agent is sodium hydroxide or potassium hydroxide.