JP2006016583A - Liquid cleanser composition and cleansing method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a packed cleanser composition having enough storage stability to store for a long period a mass-produced cleanser solution in small portions doubling as having such film peelableness as to continuously peel film with its adhesion to the surface of a structure being controllable, and to provide a cleansing method using the composition. <P>SOLUTION: The liquid cleanser composition comprises a polyvinyl alcohol as film-forming material, a plasticizer imparting the film with flexibility, a water-based solvent, a filler insoluble to the solvent and a dispersion stabilizer for stabilizing the filler in the solvent. The cleansing method comprises coating the surface of a structure with this composition in the form of thin film, drying the thus formed coating film to form dry film on the surface of the structure, then peeling the dry film off the surface of the structure as continuous film to remove stains on the surface of the structure together with the dry film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a pack-type cleaning composition excellent in film peelability and storage stability and a cleaning method using the same.

  A pack type that forms a film on the surface of the surface to be cleaned by applying a liquid cleaning agent to the surface to be cleaned and drying it, and then strips the film after drying to remove the dirt on the surface to be cleaned. Cleaners are well known. The cleaning method using this pack-type cleaner is a combination of a normal cleaning method with detergent and mechanical action such as a brush. It is expected to be applied to easily painted surfaces.

As a pack type cleaner using polyvinyl alcohol (hereinafter also referred to as PVA) as a film forming material, a PVA aqueous solution or emulsion having a specific polymerization degree, saponification degree and viscosity is applied to the surface of a structure (see Patent Document 1). In addition, there is known a method in which a colorant is mixed in a pasty solution in which a polymer for forming a peelable adhesive film is dissolved in a solvent, a mixed solution is prepared, and the mixture is applied to a wall surface (see Patent Document 2). Patent Document 2 exemplifies opaque particles such as calcium carbonate, sawdust, fibers, sand, pebbles, metal pieces, fly ash, plant strips, and plastic strips as colorants.
Japanese Patent No. 3107030 Japanese Patent No. 2980230

In order to develop an effective and simple cleaning method for the cushion floor that has been embossed so that the dirt on the recesses is not easily removed by a normal cleaning method, the present inventors have studied a pack type cleaner and have reached the present invention. It was.
First, a PVA aqueous solution added with a plasticizer was prepared and applied to the cushion floor (see Comparative Example 1 described later). Although this PVA aqueous solution was not so different from the coating liquid described in Patent Document 1 and its configuration, it is not easy to peel off the film from the cushion floor, and even if peeled, the film strength is not sufficient. There was a problem that the film of the concave part with a thick film remained on the cushion floor side, so that a so-called slipping phenomenon easily occurred and it was unexpectedly difficult to peel off as a continuous film.

Therefore, in order to solve the above-mentioned problem of the PVA aqueous solution that weakens the adhesion of the film to the cushion floor surface and increases the film strength, a PVA aqueous solution further added with a filler corresponding to the colorant described in Patent Document 2 is prepared. Thus, the investigation was continued (see Comparative Examples 2 and 3 described later).
By this filler addition formulation, the adhesion of the film to the cushion floor surface can be adjusted. In addition, the film strength has been surprisingly improved, and the phenomenon of omission has been improved, thereby solving the above problems. However, it has been found that the PVA aqueous solution to which this filler is added has a new problem of lack of storage stability. In other words, if the prepared PVA aqueous solution is stored, the added filler will be separated from the solvent and settled in less than a day, depending on the composition of the solution, and redispersed at the cleaning site. It turned out to be extremely difficult.

  If the pack type cleaner solution is adjusted at the cleaning site and it is immediately applied, the storage stability of the cleaner solution will not be a problem, but for small-scale cleaning work such as a household cushion floor, such on-site adjustment and installation are not possible. There is a limit, and the cleaner solution is required to have a certain storage stability, that is, a property that maintains the property and dispersion state during the preparation of the solution for a certain period or more. The inventors of the present application set forth the harsh storage conditions of a storage temperature of 40 ° C. and stable for at least 2 weeks, and further studied to realize the storage stability.

  The present invention is intended to solve the problems that have not been solved with such conventional pack type cleaners, and is capable of adjusting the adhesion of the film to the construction surface and improving the film strength caused by the addition of the filler. An object of the present invention is to provide a pack-type cleaner that also enjoys storage stability of a cleaner solution and a cleaning method using the same.

As a result of intensive investigations on methods for improving the storage stability of a pack-type cleaner solution to which a filler has been added, the present inventors have found that the use of a dispersion stabilizer, particularly an alkali metal salt of carboxymethylcellulose and xanthan gum, is extremely important. The knowledge that it is effective was obtained, and the present invention was achieved.
That is, the liquid detergent composition of the present invention comprises polyvinyl alcohol as a film forming material, a plasticizer that imparts flexibility to the film, a solvent mainly composed of water, a filler insoluble in the solvent, and a filler in the solvent. In addition, the cleaning method of the present invention is formed by applying the liquid cleaning composition in the form of a thin film on the structure surface. The coating film is dried to form a dry film on the surface of the structure, and then the dry film is peeled off from the structure surface as a continuous film to remove the dirt on the surface of the structure by entanglement with the dry film. It is a cleaning method.

  The liquid detergent composition of the present invention has excellent film peelability as a pack type cleaner. Therefore, the dry film can be peeled off from the structure surface as a continuous film, and the peeling work is extremely simple. In addition, it has excellent storage stability, and can be stored and stored for a long time by subdividing a large amount of detergent solution prepared at the factory, and it can be used for small-scale cleaning work such as cushion floors in homes and stores. Open.

BEST MODE FOR CARRYING OUT THE INVENTION

First, the liquid detergent composition of the present invention will be described.
The liquid detergent composition of the present invention is insoluble in polyvinyl alcohol (A) as a film-forming material, a plasticizer (B) that imparts flexibility to the film, a solvent (C) mainly composed of water, and a solvent (C). Filler (D), dispersion stabilizer (E) for stabilizing dispersion of filler (D) in solvent (C), and nonionic surfactant (F) added as necessary ).

  As PVA (A) which is a film forming material, it is preferable to use partially saponified PVA having a saponification degree of less than 90%. On the other hand, completely saponified PVA having a saponification degree of 90% or more is a preferable film forming material in that the film strength is strong, but it is inferior in dispersion stability of the filler (D) such as calcium carbonate, and is used as it. Is also preferably used as a mixture with partially saponified PVA. Furthermore, in terms of the degree of polymerization of PVA (A), the average degree of polymerization is about 1700 to 2400 higher than the low degree of polymerization having an average degree of polymerization of 300 to 700 and the medium degree of polymerization having an average degree of polymerization of 1000 to 1500. The product is preferable because of high film strength and elongation.

  The content of PVA (A) in the liquid detergent composition is preferably 4 to 10% by weight, more preferably 5 to 8% by weight. When the content of PVA (A) is less than 4% by weight, it is difficult to obtain a film strength sufficient to continuously peel the formed dry film, and when it exceeds 10% by weight, a filler (D) is added. The viscosity of the PVA solution becomes too high, so that it becomes difficult to obtain the dispersion stabilizing effect by the dispersion stabilizer (E).

  The plasticizer (B) is selected from those that give flexibility and strength to the dry film of PVA (A). Specific examples include glycols such as glycerin and propylene glycol, and butyl carbitol. Among these, glycerin is particularly preferable. The content of the plasticizer (B) in the liquid detergent composition is preferably 1 to 12% by weight, more preferably 2 to 6% by weight. If the content of the plasticizer (B) is less than 1% by weight, the flexibility of the dry film is not yet sufficient, and if it exceeds 12% by weight, the bleed of the plasticizer (B) from the film becomes severe and the film peels off. Sex worsens.

  As the solvent (C), water, particularly deionized water is preferably used, and when it is desired to shorten the drying time of the coating film, an aqueous solution to which an aliphatic lower alcohol, particularly ethyl alcohol is added, is used as the solvent (C). It can also be used.

The filler (D) is selected from those that are insoluble in the solvent (C) and can adjust the adhesion of the dry film to the coated surface by adding it to the liquid detergent composition. Specific examples include clay, calcium carbonate, dolomite, titanium oxide, talc, kaolin, gypsum, diatomaceous earth, aerosil, carbon fiber short fibers, cinnabar sand, fly ash, etc. Among them, they are easily dispersed in a PVA solution. Calcium carbonate, dolomite and aerosil are particularly preferred fillers (D).
Furthermore, the present inventors were able to confirm an unexpected and desirable result that a strong film strength can be obtained even with a small amount of PVA as a result of an increase in the thickness of the film due to the effect of increasing the filler (D). .

  The content of the filler (D) in the liquid detergent composition is preferably 3 to 15% by weight, more preferably 5 to 10% by weight. If the content of the filler (D) is less than 3% by weight, the adhesion of the dry film to the coated surface cannot be adjusted sufficiently, and if it exceeds 15% by weight, the fluidity and storage stability of the liquid detergent composition It becomes difficult to store for a long time in addition to applying it to the structure surface with a predetermined uniform thickness.

  The dispersion stabilizer (E) is used to stabilize the dispersion of the filler (D) in the solution. Specific examples include alkali metal salts, xanthan gum, and gum arabic of carbooxymethyl cellulose (hereinafter also referred to as CMC). CMC alkali metal salts, particularly CMC sodium salts, and polysaccharides produced by fermentation of microorganisms. Xanthan gum is a particularly preferred dispersion stabilizer (E). The content of the dispersion stabilizer (E) in the liquid detergent composition is preferably 0.05 to 5% by weight, more preferably 0.1 to 1% by weight.

  The use of a liquid detergent composition to which a surfactant (F) is added is effective for the surface of a structure with severe oil stains. The surfactant (F) is selected from those having a hydrophilic / lipophilic balance (HLB) of 7 or more, preferably 8 or more, and may be either a nonionic surfactant or an anionic surfactant. As nonionic surfactants, sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monocaprate, deglyceryl monolaurate, hexaglycerin monolaurate, decaglyceryl monooleate, tetraglycerin monooleate and the like. Mono fatty acid esters, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monooleate, modified silicone emulsions, and the like, and anionic surfactants include ammonium lauryl sulfate and sodium dodecylbenzene sulfonate. It is. The content of the surfactant (F) is preferably 0.5 to 5% by weight of the liquid detergent composition.

Next, the cleaning method of the present invention will be described.
In the cleaning method of the present invention, the liquid detergent composition is applied to the surface of the structure in a thin film form, and the formed coating film is dried to form a dry film on the surface of the structure. Is peeled off from the surface of the structure as a continuous film, whereby the dirt on the surface of the structure is entangled in the dry film and removed.

The liquid detergent composition is applied to the surface of the structure by spreading (leveling) the liquid detergent composition taken out from the container on the application surface with a uniform thickness using a developing tool such as a brush, a trowel, a roller, or a spatula. Can be done. If this leveling is not uniform, unevenness in the thickness of the dry film, which is a thin film, will occur and cause film rupture when it is peeled off from the surface of the structure. Liquidity is required.
The coating amount of the liquid detergent composition is appropriately selected according to the state of the structure such as the degree of soiling, the surface material, and the degree of unevenness, but the strength and economy required for the dry film at the time of peeling. In consideration of the above, it is preferable to apply the liquid detergent composition so that the thickness of the dry film is usually 0.05 to 0.5 mm, particularly 0.1 to 0.3 mm.

  The coating film can be dried by natural drying, drying with wind using a fan, warm air drying, infrared irradiation drying, or the like. The drying time in the case of natural drying is usually about several hours to 48 hours.

  According to a particularly preferred embodiment of the present invention, the edge of the dried film is naturally peeled off as the coating film is dried, and if the peeled part is picked and peeled off with a finger, the whole film can be easily formed as a continuous film. Can be peeled off. Moreover, in the case where natural peeling has not been achieved, it can be peeled in the same manner by rolling up the edge of the dry film using a tool such as a spatula. In addition, before applying the liquid cleaning composition, a masking tape is laid in advance on one end of the surface of the structure, and the tape can be used as a picking allowance by applying the tape including the tape. This method using a masking tape has the advantage that the dry film can be easily peeled off and unnecessary structural parts need not be applied.

Since all or most of the raw materials including PVA constituting the liquid detergent composition according to the present invention can be used for food additives and cosmetics, they are harmless even if they adhere to the skin. It is harmless to the human body unless an extreme amount is consumed.
Accordingly, the peeled and recovered dried film can be incinerated as long as there is not much, depending on the content of the dirt.

  As described above, the present invention was made as a result of studying the cleaning method for the embossed cushion floor, but the object of cleaning according to the present invention is limited to the cushion floor. It covers not only things but p-tiles, flooring materials such as flooring, glass, wood, walls, painted surfaces, etc. in general.

  After charging 827 g of deionized water with a water temperature of 15 to 25 ° C. into a heating vessel with a stirrer having a capacity of 1.5 liters, 30 g of glycerin and 60 g of calcium carbonate (heavy product) are added and stirring is started at 600 rpm for 1 minute. did. Subsequently, the container heating apparatus was started, and 80 g of PVA (1) (Kuraray PVA-224, saponification degree 88%, high polymerization degree product) 80 g was slowly divided into several times in the course of temperature increase. The solution was charged and kept at a liquid temperature of 75 ° C. for 15 minutes to completely dissolve the PVA. After the holding time had elapsed, heating was stopped and cooling was started, and 3 g of xanthan gum (Rhodia Japan's Rhodigel 200) was added when the liquid temperature dropped to 65 ° C. or lower. And stirring was stopped when liquid temperature became 30 degrees C or less, and 1 kg of liquid cleaning composition was obtained.

About half of the resulting liquid detergent composition is applied to an embossed cushion floor laid in the office building of the office, and the remaining half of the volume is used for fluidity and peelability tests. Each glass bottle was sealed and allowed to stand in a 1 liter transparent glass bottle and subjected to a storage stability test at 40 ° C. for 2 weeks.
The amount of the liquid detergent composition applied to the cushion floor was about 1 kg per 1 m ² of the floor area, and the peelability test was performed on the dried film after 24 hours from the application. An example of the film thickness measured with a micrometer for the dried film peeled from the cushion floor was 0.16 mm at the embossed convex part and 0.32 mm at the concave part.

  The fluidity, peelability and storage stability of the liquid detergent composition of Example 1 were all good. Further, as in the other examples, in this example, it was confirmed that the film peeling surface of the cushion floor was clean as compared with the surroundings, and the dirt was removed.

The amount of deionized water charged was 837 g, the amounts of PVA (1) and calcium carbonate were changed to 50 g and 80 g, respectively, and 3 g of CMC sodium salt (hereinafter also referred to as CMC / Na) was used instead of xanthan gum. Was carried out in the same manner as in Example 1 to obtain 1 kg of a liquid detergent composition.
The liquid detergent composition obtained had good fluidity, peelability and storage stability.

A liquid cleaning composition 1 kg was obtained in the same manner as in Example 2 except that 30 g of propylene glycol (hereinafter also referred to as PG) was used instead of glycerin.
The liquid detergent composition obtained had good fluidity, peelability and storage stability.

A liquid detergent composition was prepared in the same manner as in Example 2 except that the amount of deionized water charged was 847 g, the amount of PVA (1) was changed to 60 g, and 60 g of dolomite was used instead of calcium carbonate. 1 kg was obtained.
The liquid detergent composition obtained had good fluidity, peelability and storage stability.

The amount of deionized water charged was 827 g, the amount of calcium carbonate charged was changed to 90 g, and instead of PVA (1), PVA (2) (Kuraray PVA-220, saponification degree 88%, high polymerization degree product) Except using 50g, it carried out like Example 2 and obtained 1 kg of liquid cleaning composition.
The liquid detergent composition obtained had good fluidity, peelability and storage stability.

A liquid detergent composition of 1 kg was carried out in the same manner as in Example 5 except that the amount of deionized water charged was 757 g and the amounts of PVA (2), glycerin and calcium carbonate were changed to 60 g, 100 g and 80 g, respectively. Got.
Both the fluidity and storage stability of the obtained liquid detergent composition were good, and the peelability was slightly good.

A liquid detergent composition 1 kg was obtained in the same manner as in Example 6 except that the amount of deionized water charged was 837 g and the amount of glycerin was changed to 20 g.
The liquid detergent composition obtained had good fluidity, peelability and storage stability.

The amount of deionized water charged was 796 g, and the amounts of calcium carbonate and xanthan gum were changed to 70 g and 4 g, respectively. Instead of PVA (1), PVA (3) (Denka B-17, saponification degree 87-89) %, High polymerization degree product) 60 g and PVA (4) (Kuraray PVA-CST, saponification degree 96%, high polymerization degree product) 40 g was used in the same manner as in Example 1 except that a liquid was used. 1 kg of a cleaning composition was obtained.
The liquid detergent composition obtained had good fluidity, peelability and storage stability.

A liquid detergent composition was prepared in the same manner as in Example 2 except that the amount of deionized water charged was 808 g and the amounts of PVA (1), glycerin and CMC · Na were changed to 60 g, 50 g and 2 g, respectively. 1 kg was obtained.
The liquid detergent composition obtained had good fluidity, peelability and storage stability.
Furthermore, when the same cleaning agent was applied to a cushion floor soiled with oil installed in the factory and tested, the cleaning agent solution was repelled at the oil-stained location, and no film was formed over the entire surface.

The amount of deionized water charged was 798 g, and 10 g of decaglycerol monolaurate (ML-750, HLB 14.8, a non-ionic surfactant) was newly added at the same timing as glycerol and calcium carbonate. Except for this, the same procedure as in Example 9 was carried out to obtain 1 kg of a liquid detergent composition. And the fluidity | liquidity and peelability test were done using the cushion floor soiled with the oil laid in the factory.
The liquid detergent composition obtained had good fluidity, peelability and storage stability.

A liquid detergent composition of 1 kg was obtained in the same manner as in Example 10 except that 10 g of polyoxyethylene sorbitan monooleate (OT-221, HLB 15 manufactured by NOF Corporation) was used instead of decaglycerin monolaurate. It was.
The liquid detergent composition obtained had good fluidity, peelability and storage stability.

Comparative Example 1

The amount of deionized water charged was 890 g, 60 g PVA (3) was used instead of PVA (1), and except that calcium carbonate and CMC Na were not added, the same as in Example 9, 1 kg of a liquid detergent composition was obtained.
Although the fluidity and storage stability of the obtained liquid detergent composition were good, the peelability was poor.

Comparative Example 2

Deionized water was charged to 810 g, PVA (1) was used instead of PVA (3) 60 g, and CMC / Na was not added. 1 kg of composition was obtained.
The liquid detergent composition obtained had good fluidity and peelability, but poor storage stability.

Comparative Example 3

A liquid detergent composition 1 kg was obtained in the same manner as in Comparative Example 2 except that the amount of deionized water charged was 720 g and the amount of PVA (3) charged was changed to 150 g.
In this example, whether the storage stability, which is a problem of Comparative Example 2, is improved by increasing the amount of PVA added and increasing the solution viscosity, is examined. As a result, the peelability of the liquid detergent composition was good, but the fluidity was poor, and the storage stability was gelled, which was also bad. This is considered to indicate that the dispersion of the filler cannot be stabilized simply by increasing the viscosity of the solution.

  The results of Examples 1-7 are shown in Table 1, and the results of Examples 8-11 and Comparative Examples 1-3 are shown in Table 2. In addition, the number in a table | surface is a ratio (weight%) of each component in a composition.

In the fluidity test, it was evaluated whether the liquid detergent composition has fluidity that can be applied with a uniform thickness as long as it is visible on the cushion floor. Brush, trowel, (indicated by ○ in Table 1 and 2) if good detergent at a rate of about 1kg per floor area 1 m ² can be expanded with a uniform thickness on the cushion floor using the deployment tool such as a roller, from the container If it is not easy to remove the cleaning agent or it is not easy to spread evenly on the cushion floor, it is defective (indicated by the same x). It was determined and evaluated (indicated by Δ).

  In the peel test, you can pinch the edge of the dry film with your finger to start peeling from the cushion floor, or the dry film will remain on the cushion floor side due to the cut of the dry film or embossed recesses in the middle Two points, which can be peeled off as a single continuous film with no omission, were used as evaluation points. It is easy to start peeling and is good if it can be peeled as a continuous film (indicated by ○ in Tables 1 and 2). A tool such as a spatula was required to start peeling, but somewhat good if it can be peeled as a continuous film (indicated by Δ) ), It was judged and evaluated that it was not easy to start peeling even if a tool was used, and if it could not be peeled off as a continuous film due to cutting or removal of the film, it was judged as defective (indicated by x).

  The storage stability test was conducted at a temperature setting higher than the normal storage temperature for the purpose of an accelerated test. As the temperature increases, the solution viscosity decreases, which is a severe condition for storage stability where sedimentation of the filler is a problem. The liquid detergent composition is sealed in a transparent glass bottle, stored at 40 ° C., and after 2 weeks, no precipitate of the filler is seen at the bottom of the glass bottle, or even if it is seen, it can be easily dispersed. It was judged and evaluated as good (indicated by ○ in Tables 1 and 2), and poor (indicated by ×) if it was difficult to disperse the precipitate by hand stirring.

Claims (7)

  Polyvinyl alcohol (A) as a film forming material, a plasticizer (B) for imparting flexibility to the film, a solvent (C) mainly composed of water, and a filler (D) insoluble in the solvent (C) A liquid detergent composition comprising a dispersion stabilizer (E) for stabilizing the dispersion of the filler (D) in the solvent (C).   The liquid detergent composition according to claim 1, further comprising a surfactant (F).   The liquid detergent composition according to claim 1 or 2, wherein the dispersion stabilizer (E) is an alkali metal salt of carbooxymethyl cellulose and / or xanthan gum.   The polyvinyl alcohol (A) is a partially saponified polyvinyl alcohol having a saponification degree of less than 90%, or a mixture of the partially saponified polyvinyl alcohol and a fully saponified polyvinyl alcohol having a saponification degree of 90% or more. Liquid detergent composition.   The liquid detergent composition according to claim 4, wherein the plasticizer (B) is glycerin and the filler (D) is calcium carbonate and / or dolomite.   The composition ratio in the liquid detergent composition is 4 to 10% by weight of polyvinyl alcohol (A), 1 to 12% by weight of plasticizer (B), 3 to 15% by weight of filler (D), and dispersion stabilizer (E The liquid detergent composition according to claim 1 or 5, which is 0.05 to 5% by weight.   The cleaning composition according to any one of claims 1 to 6 is applied to the surface of the structure in a thin film, and the formed film is dried to form a dry film on the surface of the structure, followed by drying. A cleaning method in which the film is peeled off from the surface of the structure as a continuous film, whereby dirt on the surface of the structure is entangled with the dry film.