JP6910287B2 - Cleaning film forming agent - Google Patents

Description

The present invention relates to a film forming agent for cleaning.

Conventionally, in order to remove stains adhering to a hard surface and clean the hard surface, a combination of a cleaning agent such as water, a surfactant and a solvent and a cleaning tool such as a sponge and a rag has been used. ..
General cleaning tools have many problems from the viewpoint of hygiene, such as accumulation of dirt after repeated use. Moreover, since general cleaning tools have a certain shape, they are often not suitable for cleaning places having fine irregularities or complicated shapes (for example, bathroom door rails, home appliances, etc.). For example, the cleaning tool does not reach the depths of such a place, and it is difficult to completely remove the attached dirt. In addition, since it is difficult to completely wipe off water and detergents after cleaning, they eventually become hotbeds of bacteria and cause recontamination and offensive odors. Therefore, a method that does not require a step of rinsing with water is desired.

Patent Document 1 proposes a method in which an aqueous dispersion composition containing a thermoplastic polymer as a main component is applied to the surface of an object to form a film, and the film is peeled off to remove stains.

Japanese Unexamined Patent Publication No. 50-15362

However, in the composition of Patent Document 1, when it is applied to a place having fine irregularities or a complicated shape (for example, a bathroom door rail, a home electric appliance, etc.), the composition spreads with the passage of time, and a portion where the amount of the composition applied is small is found. It is formed. In such a portion, the composition does not sufficiently penetrate into dirt and the film formed is thin, so that there is a problem that the film is easily torn when the film is peeled off. If the film is torn, the dirt removal effect cannot be sufficiently obtained.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a film-forming agent for cleaning, which is more effective in removing stains.

The present inventors have found that the following cleaning film forming agents can solve the above problems.
That is, the present invention has the following aspects.
[1] Component (A): At least one film-forming polymer selected from the group consisting of (meth) acrylic resin, vinyl acetate resin, vinyl chloride resin, urethane resin, polyvinyl alcohol resin, and polyvinyl acetal resin.
(B) Ingredients: water and
Ingredient (C): An organic solvent having a solubility parameter (SP value) of 12.5 to 18.0, and
Ingredient (D): An organic solvent having a solubility parameter (SP value) of 7.5 to 11.0,
Ingredient (E): Containing a phosphoric acid ester-type surfactant,
A film-forming agent for cleaning having a mass ratio of {(C) component + (D) component} / (E) component of 0.8 to 22.
[2] The cleaning film-forming agent according to [1], wherein the mass ratio represented by the component (C) / component (D) is 0.3 to 10.
[3] The component (D) is a glycol ether solvent represented by the following formula (1), and contains the component (D1) and the component (D2).
In the formula (1), the component (D1) is a glycol ether solvent in which R'is a hydrogen atom or a linear alkyl group having 1 to 8 carbon atoms.
In the formula (1), the component (D2) is a glycol ether solvent in which R'is an acetyl group.
The cleaning film-forming agent according to claim 1 or 2, wherein the mass ratio represented by the component (D1) / component (D2) is 0.2 to 1.
RO- (AO) _n- R'・ ・ ・ (1)
(In the formula (1), R is a linear or branched alkyl group or allyl group having 1 to 8 carbon atoms, and R'is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or It is an acetyl group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents 0.1 to 20 in average number of repetitions.)
[4] The cleaning according to any one of [1] to [3], wherein the content of the component (A) is 20 to 70% by mass with respect to the total mass of the film forming agent for cleaning. Film forming agent.
[5] The cleaning according to any one of [1] to [4], wherein the content of the component (B) is 25 to 75% by mass with respect to the total mass of the film forming agent for cleaning. Film forming agent.
[6] The item according to any one of [1] to [5], wherein the content of the component (C) is 0.1 to 10% by mass with respect to the total mass of the film-forming agent for cleaning. Film forming agent for cleaning.
[7] In any one of [1] to [6], the content of the component (D) is 0.1 to 4.5% by mass with respect to the total mass of the film forming agent for cleaning. The cleaning film forming agent described.
[8] In any one of [1] to [7], the content of the component (E) is 0.1 to 3.0% by mass with respect to the total mass of the film forming agent for cleaning. The cleaning film forming agent described.

According to the present invention, it is possible to provide a film forming agent for cleaning which is more excellent in the stain removing effect.

It is a photographic figure which shows the evaluation method of the dirt removal effect which concerns on this Example.

≪Film forming agent for cleaning≫
The cleaning film forming agent of the present invention contains the following components (A), (B), (C), (D), and (E).

<Ingredient (A)>
The component (A) is at least one film-forming polymer selected from the group consisting of (meth) acrylic resin, vinyl acetate resin, vinyl chloride resin, urethane resin, polyvinyl alcohol resin, and polyvinyl acetal resin.
Here, the "film-forming property" is a property capable of forming a peelable film. For example, a film is formed when a polymer aqueous dispersion or aqueous solution is applied to a thickness of 0.05 to 0.5 mm in a range of 2 cm × 10 cm under atmospheric pressure conditions and left for 48 hours. Is. The film formed in this way is preferably one that can be peeled off by hand or the like.

From the viewpoint of the stain removing effect, as the component (A), a (meth) acrylic resin and a vinyl acetate resin are preferable, and a vinyl acetate resin is more preferable.
The glass transition temperature of the film-forming polymer is preferably 0 to 100 ° C, more preferably 5 to 50 ° C, and even more preferably 10 to 25 ° C.
When the glass transition temperature of the component (A) is equal to or higher than the above lower limit value, a tough film that is hard to break is likely to be formed.
When the glass transition temperature of the component (A) is not more than the above upper limit value, a film is likely to be formed at room temperature.
The glass transition temperature is a value obtained by the plastic transition temperature measuring method specified in JIS-K-7121.

((Meta) acrylic resin)
Examples of the (meth) acrylic resin include (meth) acrylic acid esters (for example, a homopolymer of (meth) acrylic acid ester, a copolymer of (meth) acrylic acid ester); and (meth) acrylic acid ester. Examples thereof include copolymers with ethylenically unsaturated monomers other than (meth) acrylic acid esters. (Meta) acrylic acid ester is a general term for acrylic acid ester and methacrylic acid ester. From the viewpoint of stain removing effect, a copolymer of (meth) acrylic acid esters is preferable.

Examples of (meth) acrylic acid esters include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, -n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and -n-butyl (meth) acrylic acid. , (Meta) isobutyl acrylate, (meth) acrylate-sec-butyl, (meth) hexyl acrylate, (meth) octyl acrylate, (meth) -2-ethylhexyl acrylate, (meth) decyl acrylate, ( Isobornyl acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate, ( Examples thereof include -3-hydroxypropyl (meth) acrylate, -2-hydroxybutyl (meth) acrylate, and -2-hydroxyphenylethyl (meth) acrylate.

The ethylenically unsaturated monomer may have at least one polymerizable vinyl group, and is, for example, an aromatic vinyl compound such as styrene or α-methylstyrene; a heterocyclic vinyl such as vinylpyrrolidone. Compounds; Vinyl halide compounds such as vinyl chloride; Vinyl esters typified by vinyl acetate and vinyl alkanoate; Monoolefins (ethylene, propylene, butylene, isobutylene, etc.); Conjugate diolefins (butadiene, isoprene, chloroprene, etc.) ); Α, β-unsaturated mono or dicarboxylic acid (crotonic acid, itaconic acid, maleic acid, fumaric acid, etc.); vinyl cyanide compound such as acrylonitrile; carbonyl group-containing ethylenically unsaturated monomer such as acrylonitrile and diacetoneacrylamide. Quantum; Examples thereof include sulfonic acid group-containing ethylenically unsaturated monomers such as p-toluenesulfonic acid.

(Vinyl acetate resin)
Examples of the vinyl acetate resin include a homopolymer of vinyl acetate or a copolymer of vinyl acetate and the above ethylenically unsaturated monomer excluding the (meth) acrylic acid ester. An ethylene-vinyl acetate copolymer is preferable from the viewpoint of a stain removing effect.
The copolymerization ratio of vinyl acetate in the ethylene-vinyl acetate copolymer is preferably 25 to 99 mol% with respect to 100 mol% of the constituent units constituting the ethylene-vinyl acetate copolymer. When the copolymerization ratio of vinyl acetate is within the above range, it is possible to form a tough film that is hard to tear even in a complicated shape including an uneven surface.

The gel fraction of the vinyl acetate resin is preferably 20 to 60% by mass. When the gel fraction is within this range, it is possible to form a tough film that is hard to tear even in a complicated shape including an uneven surface.
The gel fraction is, for example, the toluene insoluble content measured as follows. An aqueous dispersion or aqueous solution of vinyl acetate resin is applied onto the substrate and dried to form a film. The dried film is cut into small pieces to prepare a sample, and the mass of this sample (about 0.250 to 0.350 g) is weighed to 1 mg (mass A). Next, 100 ml of toluene is weighed in a flask, the sample is added, and the flask is completely sealed. After allowing to stand at room temperature for 16 ± 2 hours in a completely sealed state, the solution in the flask is stirred with a magnetic stirrer for 1 hour. Then, this solution was subjected to No. 2 Filter with filter paper. The mass of the aluminum plate was measured in advance (mass B), and No. 2 Weigh 20 ml of the filtrate filtered through the filter paper on an aluminum plate. The aluminum dish is dried, the weight after drying (total amount of dried aluminum saliva and filtrate) is weighed to 1 mg (mass C), and the toluene insoluble content (mass%) is calculated by the following formula (2).
Toluene insoluble content (mass%) = 100-[(mass C-mass B) x 5 / mass A] x 100 ... (2)

(Vinyl chloride resin)
Examples of the vinyl chloride resin include a homopolymer of vinyl chloride or a copolymer of vinyl chloride and the above-mentioned ethylenically unsaturated monomer excluding the (meth) acrylic acid ester. Polyvinyl chloride is preferable from the viewpoint of stain removing effect.
Examples of the vinyl chloride resin include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and vinyl chloride-propylene copolymer. , Vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acryloni little copolymer Combined, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer, vinyl chloride-maleic acid ester copolymer Vinyl chloride resins such as coalesced vinyl chloride-acrylonitrile copolymers and vinyl chloride-various vinyl ether copolymers can be used.

(Urethane resin)
The urethane resin is a resin having a urethane bond obtained by reacting a polyol component with a polyisocyanate compound, and examples thereof include polyurethane resin and acrylic urethane resin. As the polyurethane resin, polyester polyol, polyether polyol, and polycarbonate polyol are used alone or in combination as the polyol component, and acrylic polyol is used as the acrylic urethane resin. Polyurethane resin is preferable from the viewpoint of stain removing effect.

Examples of the polyurethane resin include an ether type using a polyether polyol, a polyester type using a polyester polyol, an ester ether type using a polyether polyol and a polyester polyol, and a carbonate type using a polycarbonate polyol.
Among these, the ester type and the ester ether type are preferable, and the ester ether type is more preferable.

(Polyvinyl alcohol resin)
As the polyvinyl alcohol resin, it is preferable to use polyvinyl alcohol having a saponification degree of 65.0 to 99.0 mol% and a polymerization degree of 300 to 4000. Particularly preferably, polyvinyl alcohol having a saponification degree of 85.0 to 99.0 mol% and a degree of polymerization of 500 to 2500 is used.

(Polyvinyl acetal resin)
Examples of the polyvinyl acetal resin include polyvinyl butyral resin and polyvinyl acetal resin. The polyvinyl butyral resin preferably has a hydroxyl group content of 20 to 40 mol%, an acetyl group content of 20 mol%, and a butyralization degree of 55 to 80 mol%. The polyvinyl acetal acetal resin preferably has a degree of acetalization of 5 to 30 mol% and a degree of polymerization of 500 to 4000. A polyvinyl acetal acetal resin is particularly preferable from the viewpoint of cleaning treatment ability.

As the component (A), one type may be used alone or two or more types may be used in combination.
The content of the component (A) is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, based on the total mass of the cleaning film forming agent.
When the content of the component (A) is at least the above lower limit value, the film is less likely to be torn and the dirt removing effect is likely to be improved.
When the content of the component (A) is not more than the above upper limit value, the solubility or dispersibility in the component (B) is improved, and it becomes easy to suppress the formation of agglomerates.

<Ingredient (B)>
The component (B) is water. Distilled water, ion-exchanged water, and ultrapure water can be used as the component (B). Of these, purified water such as distilled water and ion-exchanged water is preferable.
The content of the component (B) is preferably 25 to 75% by mass, more preferably 30 to 60% by mass, based on the total mass of the cleaning film forming agent.
When the content of the component (B) is at least the above lower limit value, the solubility and dispersibility of the component (A) are improved, and it becomes easy to suppress the formation of aggregates of the component (A).
When the content of the component (B) is not more than the above upper limit value, the film is less likely to be torn and the dirt removing effect is likely to be improved.

<Ingredient (C)>
The component (C) is an organic solvent having a solubility parameter (SP value) of 12.5 to 18.0. The component (C) improves the uniformity of the thickness of the film and the ability to penetrate hydrophilic stains.

The solubility parameter (SP value) in the present invention refers to the Hansen solubility parameter, and is an index that serves as a guideline for the solubility of a two-component solution.
The following formula (3) is used as a method for calculating ^{the SP value δ ((cal / cm 3} ) ^1/2 ) of each organic solvent used for the component (C).
δ = ((δd ² + δp ² + δh ² ) /4.2) ^1/2 ... (3)
Here, δd is referred to as a London dispersion force term, δp is referred to as a molecular polarization term, and δh is referred to as a hydrogen bond term.
Moreover, Hansen parameters software (HSPiP ver.4.1.x), or, "HANSEN SOLBILITY PARAMETERS" A User 's Handbook Second Edition values stated in (δd, δp, δh: Units (J / cm ³ ) ^1/2 ) can be calculated.
Further, the SP value when a plurality of organic solvents are used for the component (C) is obtained as a weighted average of the SP values of each organic solvent by the following formula (4).
m = δ1φ1 + δ2φ2 ・ ・ ・ (4)
Here, δ1 and δ2 are SP values of each solvent component, and φ1 and φ2 are volume fractions of each solvent component.

The SP value of the component (C) is 12.5 to 18.0, preferably 13.0 to 17.0, and more preferably 14.5 to 16.5. By setting the SP value of the component (C) within the above range, flexibility is imparted to the film, the film is less likely to crack, and the stain removing effect is improved.
As the component (C), a polyhydric alcohol is preferable, a 2-3-valent alcohol having 2 to 4 carbon atoms is more preferable, and a dihydric alcohol having 2 to 4 carbon atoms is further preferable. Specifically, propylene glycol (SP value = 14.7), dipropylene glycol (SP value = 12.9), triethylene glycol (SP value = 13.4), ethylene glycol (SP value = 16.1). , Glycerin (SP value = 17.6) and the like. Of these, ethylene glycol is particularly preferable.

As the component (C), one type may be used alone or two or more types may be used in combination.
The content of the component (C) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the cleaning film forming agent.
When the content of the component (C) is within the above range, a film having a uniform thickness is formed, the film is less likely to be torn when peeled off, and the stain removing effect is likely to be improved.

<Ingredient (D)>
The component (D) is an organic solvent having a solubility parameter (SP value) of 7.5 to 11.0. The component (D) permeates hydrophobic stains such as mud in contact with the film, dissolves the hydrophobic stains, and improves the stain removing effect.

The SP value of the component (D) is 7.5 to 11.0, preferably 8.0 to 10.5, and more preferably 8.5 to 10.0.
When the SP value of the component (D) is at least the above lower limit value, it is possible to suppress the formation of agglomerates of the component (A), and the film is less likely to break.
When the SP value is not more than the above upper limit value, it is easy to penetrate into hydrophobic stains such as mud, and it is easy to improve the stain removing effect.

As the organic solvent used for the component (D), a glycol ether solvent represented by the following formula (1) is preferable from the viewpoint of the stain removing effect.
RO- (AO) _n- R'・ ・ ・ (1)
In the formula, R is a linear or branched alkyl group or allyl group having 1 to 8 carbon atoms, and R'is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or an acetyl group. , AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents an average number of repetitions of 0.1 to 20.

The component (D) is a glycol ether solvent (hereinafter, also referred to as the component (D1)) in which R'is a hydrogen atom or a linear alkyl group having 1 to 8 carbon atoms in the formula (1), and the formula (1). ), It is preferable to contain a glycol ether solvent in which R'is an acetyl group (hereinafter, also referred to as a component (D2)).

((D1) component)
As the component (D1), diethylene glycol monomethyl ether (SP value = 10.7), triethylene glycol monomethyl ether (SP value = 10.7), ethylene glycol monoisopropyl ether (SP value = 10.9), ethylene glycol mono Butyl ether (SP value = 10.2), diethylene glycol monobutyl ether (SP value = 10.0), triethylene glycol monobutyl ether (SP value = 10.0), ethylene glycol monoisobutyl ether (SP value = 9.1), Ethylene glycol monohexyl ether (SP value = 9.9), diethylene glycol monohexyl ether (SP value = 9.7), diethylene glycol mono2-ethylhexyl ether (SP value = 9.3), ethylene glycol monoallyl ether (SP value) = 10.8), ethylene glycol monophenyl ether (SP value = 10.8), ethylene glycol monobenzyl ether (SP value = 10.9), propylene glycol monomethyl ether (SP value = 10.0), dipropylene glycol Monomethyl ether (SP value = 9.7), tripropylene glycol monomethyl ether (SP value = 9.4), propylene glycol monopropyl ether (SP value = 9.6), dipropylene glycol monopropyl ether (SP value = 9) .8), propylene glycol monobutyl ether (SP value = 9.0), dipropylene glycol monobutyl ether (SP value = 9.6), ethylene glycol dimethyl ether (SP value = 8.6), triethylene glycol dimethyl ether (SP value) = 8.8), diethylene glycol diethyl ether (SP value = 8.7), diethylene glycol dibutyl ether (SP value = 8.3) and the like.

Among them, from the viewpoint of the stain removing effect, monoalkyl glycol ether in which R is a linear or branched alkyl group having 1 to 8 carbon atoms is preferable in the formula (1). Among them, in the above formula (1), R is a linear or branched alkyl group having 4 to 8 carbon atoms, AO is an oxyalkylene group having 2 carbon atoms, R'is a hydrogen atom, and n is 0.1 to 1. A monoalkyl glycol ether of 10 is more preferred.
Among the monoalkyl glycol ethers, diethylene glycol monohexyl ether, diethylene glycol mono2-ethylhexyl ether, diethylene glycol monomethyl ether and ethylene glycol monobutyl ether are preferable, and diethylene glycol monohexyl ether is more preferable.

((D2) component)
As the component (D2), ethylene glycol monomethyl ether acetate (SP value = 10.0), ethylene glycol monoethyl ether acetate (SP value = 9.6), ethylene glycol monobutyl ether acetate (SP value = 8.9), Diethylene glycol monoethyl ether acetate (SP value = 9.4), diethylene glycol monobutyl ether acetate (SP value = 9.0), propylene glycol monomethyl ether acetate (SP value = 9.4), propylene glycol monoethyl ether acetate (SP value) = 9.0), dipropylene glycol monomethyl ether acetate (SP value = 9.2).
Among these, diethylene glycol monobutyl ether acetate is preferable from the viewpoint of stain removing effect and film forming property.

As the component (D), one type may be used alone or two or more types may be used in combination.
The content of the component (D) is preferably 0.1 to 4.5% by mass, more preferably 0.5 to 3.5% by mass, based on the total mass of the cleaning film forming agent.
When the content of the component (D) is at least the above lower limit value, the penetrating power for hydrophobic stains such as mud stains is improved, and the stain removing effect is likely to be improved.
When the content of the component (D) is not more than the above upper limit value, the film is less likely to be torn and the dirt removing effect is likely to be improved.

The component (D) preferably contains both the component (D1) and the component (D2).
The mass ratio represented by the component (D1) / component (D2) (hereinafter, also referred to as D1 / D2) is preferably 0.2 to 1.0, and more preferably 0.3 to 0.6.
When D1 / D2 is at least the above lower limit value, the permeability to dirt is likely to be improved, and the dirt removal effect is likely to be improved.
When D1 / D2 is not more than the above upper limit value, a uniform film is easily formed and the peelability is easily improved.

The total content of the component (D1) and the component (D2) (hereinafter, also referred to as D1 + D2) is preferably 0.1 to 4.5% by mass with respect to the total mass of the film forming agent for cleaning. More preferably, it is 0.5 to 3.5% by mass.
When D1 + D2 is at least the above lower limit value, the penetrating power for hydrophobic stains such as mud stains is improved, and the stain removing effect is likely to be improved.
When the content of D1 + D2 is not more than the above upper limit value, the film is less likely to be torn and the dirt removing effect is likely to be improved.

The mass ratio represented by the component (C) / component (D) (hereinafter, also referred to as C / D) is preferably 0.3 to 10 and more preferably 1 to 4.
When the C / D is at least the above lower limit value, a uniform film is easily formed and the peelability is improved.
When the C / D is not more than the above upper limit value, it is easy to permeate the dirt and the dirt removing effect is easily improved.

The difference between the SP value of the component (C) and the SP value of the component (D) is expressed as (SP value of the component (C))-(SP value of the component (D)), and is 2.0 to 9.5. Is preferable, and 5.5 to 8.0 is more preferable.
When the difference between the SP value of the component (C) and the SP value of the component (D) is within the above range, a uniform film is easily formed, the dirt is easily penetrated, and the dirt removing effect is easily improved.

<Ingredient (E)>
The component (E) is a phosphoric acid ester-type surfactant. The component (E) improves the peelability of the film from the surface to be cleaned and the uniformity of the thickness of the formed film.

As the phosphoric acid ester type surfactant, at least one selected from the group consisting of alkyl phosphates, polyoxyalkylene alkyl ether phosphoric acid esters and salts thereof is preferable, and polyoxyalkylene alkyl ether phosphoric acid esters and salts thereof are preferable. At least one selected from the group consisting of is more preferable.

Examples of the alkyl phosphate ester, polyoxyalkylene alkyl ether phosphoric acid ester, and salts thereof include compounds represented by the following formula (5).
[R ¹ O (A ¹ O) _p ] _q −P (= O) − (OM) _3-q ... (5)
In the formula, R ¹ is an alkyl group having 8 to 20 carbon atoms or an alkenyl group having 8 to 20 carbon atoms, A ¹ O is an oxyalkylene group, and p is the average number of repetitions of the oxyalkylene group, which is 0 or more. , Q is an integer of 1 to 3, and M is a mono, di, trialkyl (2 to 5 carbon atoms) ammonium group in which a hydrogen atom, an alkali metal atom, an ammonium group, or a hydroxyl group may be substituted. ..
When q is 1, the plurality of Ms in the equation may be the same or different.
Examples of the alkali metal atom in M include sodium, potassium and the like.

In the formula (5), when p is 0, it indicates an alkyl phosphate ester or a salt thereof, and when p is a positive number, it indicates a polyoxyalkylene alkyl ether phosphoric acid or a salt thereof.
The alkyl group or alkenyl group of R ¹ preferably has 12 to 15 carbon atoms.
A ¹ O is preferably an oxyethylene (EO) group from the viewpoint of cleaning treatment capacity.
p is preferably 0 to 12, more preferably 3 to 9.
As the compound represented by the formula (5), R ¹ is an alkyl group having 12 to 15 carbon atoms or an alkenyl group having 12 to 15 carbon atoms, p is 3 to 9, q is 1, and M is. A polyoxyethylene alkyl ether phosphoric acid ester in which is a hydrogen atom is particularly preferable.

As the component (E), one type may be used alone or two or more types may be used in combination.
The content of the component (E) is preferably 0.1 to 3.0% by mass, more preferably 0.5 to 2.0% by mass, based on the total mass of the cleaning film forming agent.
When the content of the component (E) is at least the above lower limit value, a sufficient peeling effect can be easily obtained.
When the content of the component (E) is not more than the above upper limit value, a uniform film is easily formed and the peelability is easily improved.

The mass ratio represented by {(C) component + (D) component} / (E) component (hereinafter, also referred to as (C + D) / E) is 0.8 to 22, preferably 1 to 12. .2 to 6 are more preferable.
When (C + D) / E is at least the above lower limit value, sufficient penetrating power for hydrophobic stains such as mud stains can be sufficiently obtained, and the stain removing effect can be easily improved.
When (C + D) / E is not more than the above upper limit value, the component (C) and the component (D) are uniformly dispersed, easily penetrate into dirt, and the dirt removing effect is easily improved.

<Arbitrary ingredient>
The cleaning film forming agent of the present invention may further contain any component other than the above. For example, solubilizers, emulsifiers, alcohols, pH adjusters, metal sequestering agents, plasticizing agents, film-forming aids, disinfectants, antibacterial agents, preservatives, antioxidants, thickeners, inorganic fine particles, UV absorbers. , Bitterants, pigments, pigments, fillers, fragrances and the like.

Examples of the pH adjusting agent include alkaline agents such as sodium hydroxide, potassium hydroxide and alkanolamine (monoethanolamine, diethanolamine, triethanolamine); inorganic acids such as hydrochloric acid and sulfuric acid; citric acid, malic acid, tartrate acid and the like. Organic acids; Examples thereof include acid agents such as paratoluene sulfonic acid, metaxylene sulfonic acid, and benzoic acid.

Examples of the metal sequestering agent include organic carboxylic acids, aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, phosphoric acids and the like.

The dye is not particularly limited, but for example, Red No. 2, Red No. 3, Red No. 225, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Red No. 201, Red No. 213, Red No. 226. , Red 227, Red 230, Red 401, Red 504, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 406, Yellow 407, Orange 206, Orange 207, Orange Examples include 402, Blue 1, Blue 2, Blue 203, Blue 205, Blue 403, Green 3, Green 201, Green 204, Green 205, Green 401, Green 402, and the like. ..
As the dye, one type may be used alone or two or more types may be used in combination.
The content of the dye is not particularly limited, but is preferably 0.1 to 500 ppm, more preferably 0.1 to 100 ppm, further preferably 1 to 50 ppm, and particularly preferably 5 to 30 ppm.
The total content of each component contained in the cleaning film forming agent of the present invention does not exceed 100% by mass.

≪Preparation method of film forming agent for cleaning≫
The cleaning film-forming agent can be prepared by mixing the components (A) to (E) and, if necessary, other components. The mixing order of each component is not particularly limited. For example, it can be prepared by the following procedure.
Add 80% of the total amount of component (B) to a 300 mL beaker and stir with a magnetic stirrer (manufactured by Nisshin Rika: SW-R800, 1200 rpm) to add 5 parts by weight of component (A) / min. To obtain an aqueous solution or an aqueous dispersion of the component (A) by adding the mixture at the rate of You may put it in.)
Next, if necessary, an appropriate amount of a pH adjuster is added to adjust the pH to 7.0, and then the residues of the (C) component, the (D) component, the (E) component, and the (B) component are further added. A cleaning film forming agent is obtained by stirring for 30 minutes.

≪How to use cleaning film forming agent≫
Next, a cleaning treatment method using the cleaning film forming agent of the present invention will be described.
In the cleaning treatment method of the present invention, a cleaning film forming agent is applied to a surface to be cleaned, the cleaning film forming agent is dried to form a film, and the film is formed from the surface to be cleaned. By peeling off, the surface to be cleaned is cleaned.
Here, the cleaning treatment refers to a treatment for removing dirt adhering to the substance surface of the surface to be cleaned. Dirt may broadly refer to substances other than the surface to be cleaned, but the main types of dirt are dust, dirt, etc., and those that have lost water after they have adhered with water. The cleaning treatment capacity broadly refers to the ability to remove stains, but mainly efficiency (amount capable of reducing dirt substances on the surface per hour), particularly one cleaning treatment operation (in the present invention, one coating). It refers to how much dirt can be removed from the surface of the surface to be cleaned by the operation of forming and removing.

The surface to be cleaned includes the surface of a substance existing in various places such as a toilet, a bathroom, a kitchen, a sink, or a living room. In particular, they may have fine gaps or uneven surfaces and can be suitably used for those surfaces. Examples of the material of the surface to be cleaned include plastic, glass, metal, rubber and the like. In particular, the present invention can be suitably used for joints (for example, window sashes) of house members near the outdoors and outdoor house members, which have been difficult to deal with with conventional cleaning agents and appliances. Further, it can be suitably used for the surface of a material to be cleaned, which has many irregularities, is liable to be strongly adhered with mud stains, and is easily deteriorated, such as plastic.

Then, the cleaning film forming agent of the present invention is applied to the surface to be cleaned to which dirt has adhered.
The coating amount is preferably 30 to 300 mg / cm ^2.
The cleaning film forming agent may be applied by applying with a brush, a pen, or the like, or by spraying the cleaning target surface with an aerosol, a spray, or the like.
When the coating is performed by an aerosol, a spray, or the like, a cleaning film-forming agent is filled in a container selected so that the spraying operation can be easily performed. The shape of the container filled with the film-forming agent for cleaning may be a cylinder, a prism, a cone, or the like, and examples of the material include a resin such as plastic or a metal such as a can.
At this time, for the purpose of peeling off the film later, the paper or paper that serves as a handle for the surface to be cleaned before the application of the film-forming agent for cleaning, or the film-forming agent for cleaning in a fluid state after application. A plastic plate may be installed.

Then, a film with a cleaning film forming agent is formed on the surface to be cleaned. The film is a film having a thickness of about 0.05 to 10 mm as a guide in the formed state (described later, in a state where the fluidity is lost). The film can be formed by making the cleaning film-forming agent a solid (a state having no fluidity). In the present invention, the film is formed by drying the cleaning film forming agent. Here, drying is to remove a solvent such as moisture.
As a guideline, the degree of drying, that is, the amount of reducing the water content of the cleaning film forming agent, may be performed until the cleaning film forming agent becomes solid.
When drying, a film-forming agent for natural drying, that is, a cleaning film may be left to evaporate naturally from the surface until a film is formed. Further, a means such as applying wind from a dryer, an electric fan, a ventilation fan, or the like to the cleaning film forming agent may be used in combination. After applying the cleaning film-forming agent, water-absorbing powder may be sprinkled on the coated surface to remove water from the cleaning film-forming agent.

At the stage of applying the cleaning film forming agent to the surface to be cleaned, dirt on the surface of the surface to be cleaned is taken in from the surface to be cleaned to the side of the film forming agent for cleaning, thereby purifying. Dirt is removed from the target surface. Further, even in the process of forming the film, for example, the process of leaving the cleaning film forming agent to dry, dirt is removed from the surface to be cleaned.

Then, the film formed on the surface to be cleaned is peeled off. When peeling off the film, the film of the present invention can be peeled off very easily by pinching the end with a finger or the like. Alternatively, the operation of peeling the film from the surface of the surface to be cleaned may be used in combination with a tool having a sharp tip such as a spatula or a bamboo skewer. Alternatively, when a paper or plastic plate to be the handle is installed, the handle is integrated with the film as the film is formed, so that the handle may be pinched to peel off the film. If the film is hard and difficult to peel off, it may be wiped with water until the film does not flow again, and the softened film may be picked up and peeled off, or peeled off with a tool.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The unit of the blending amount in the table is "mass%", and all the components indicate the net conversion amount.
Blanks in the table indicate that the ingredient is not blended.

<Ingredient (A)>
A1: Ethylene-vinyl acetate copolymer emulsion (Sumika Chemtex Co., Ltd., product name: SUMIKAFLEX S-752, solid content: 50%, glass transition temperature (Tg): 15 ° C.).

<Ingredient (B)>
B1: Water.

<Ingredient (C)>
C1: Ethylene glycol (Kanto Chemical Co., Inc., SP value = 16.1).
C2: Propylene glycol (Kanto Chemical Co., Inc., SP value = 14.7).

<Ingredient (D)>
((D1) component)
D1-1: Diethylene glycol monohexyl ether (Nippon Embroidery Co., Ltd., product name: hexyl diglycol, SP value = 9.7).
D1-2: Diethylene glycol mono2-ethylhexyl ether (Nippon Embroidery Co., Ltd., product name: 2 ethylhexyl diglycol, SP value = 9.3).
D1-3: Diethylene glycol monomethyl ether (Nippon Embroidery Co., Ltd., product name: methyldiglycol, SP value = 10.7).
D1-4: Ethylene glycol monobutyl ether (Nippon Embroidery Co., Ltd., product name: butyl glycol, SP value = 10.2).
D1-5: Diethylene glycol diethyl ether (Nippon Embroidery Co., Ltd., product name: diethyl diglycol, SP value = 8.7).
D1-6: Diethylene glycol dibutyl ether (Nippon Embroidery Co., Ltd., product name: dibutyl diglycol, SP value = 8.3).
((D2) component)
D2: Diethylene glycol monobutyl ether acetate (Kanto Chemical Co., Inc., SP value = 9.0).

<Ingredient (E)>
E1: Polyoxyethylene (9) alkyl ether phosphoric acid ester (Toho Chemical Co., Ltd., product name: Phosphanol (registered trademark) RS610, R ¹ in the above formula (5) is an alkyl group having 12 to 15 carbon atoms, A compound in which the average number of repetitions p is 9, q is 1, and M is a hydrogen atom).

<Examples 1 to 17, Comparative Examples 1 to 3>
A film-forming agent for cleaning having the composition (mass%) shown in Tables 1 to 3 was prepared by the following procedure and evaluated. The results are shown in Tables 1-3.
In Tables 1 to 3, the content of the component (A) is the solid content. "Balance" is an amount in which the total amount of the cleaning film forming agent is 100% by mass.

[Preparation method]
Add 80% of the total amount of component (B) to a 300 mL beaker, add component (A) at a rate of 5 g / min while stirring with a magnetic stirrer (manufactured by Nisshin Rika: SW-R800, 1200 rpm), and further. The mixture was stirred at 25 ° C. for 60 minutes to obtain an aqueous solution or an aqueous dispersion of the component (A).
Next, while stirring the obtained aqueous solution or aqueous dispersion with a magnetic stirrer (manufactured by Nisshin Rika: SW-R800, 1200 rpm), an appropriate amount of a pH adjuster was added as necessary to adjust the pH to 7.0. A mixture of (C) component, (D) component, and (E) component premixed in advance is added at a rate of about 20 g / min, the remaining component (B) is added, and the mixture is further stirred for 30 minutes to create a cleaning agent. 150 g of the composition was obtained.
The premixing of the components (C), (D), and (E) is a mixture of a predetermined amount of each component with a magnetic stirrer (manufactured by Nisshin Rika: SW-R800, 1200 rpm) for 5 minutes. ..

[Evaluation of dirt removal effect]
80 mg of black soil (Marukei Co., Ltd.) was evenly distributed on an aluminum sash rail (width 2 cm x length 4 cm) for general household use to create dust stains.
Next, 500 mg of a film-forming agent for cleaning was spread over an area of ^{8 cm 2} on the sash rail on which dust stains were formed (2000 mg was applied in Reference Example 1). The state of removal of dirt and dirt when the film was peeled off after 24 hours was visually evaluated, and a standard sample prepared separately as shown in FIG. 1 was used as a reference for scoring. Visual evaluation was performed 5 times, and those with a total score of 10 points or more were regarded as acceptable.

As shown in Tables 1 to 3, the cleaning film forming agents of Examples 1 to 17 to which the present invention was applied were excellent in the stain removing effect.
Comparative Example 1 in which (C + D) / E was less than 0.8, Comparative Example 2 in which (C + D) / E was more than 22 and Comparative Example 3 containing no component (E) were all inferior in the stain removing effect. ..
The cleaning film-forming agent of Examples 1 to 17 to which the present invention was applied had a coating amount of 1/4 that of Reference Example 1, but the same stain removing effect as that of Reference Example 1 was obtained. From this, it was found that the cleaning film forming agents of Examples 1 to 17 to which the present invention was applied exerted a stain removing effect with a small coating amount.

Claims (3)

Component (A): At least one film-forming polymer selected from the group consisting of (meth) acrylic resin, vinyl acetate resin, vinyl chloride resin, urethane resin, polyvinyl alcohol resin, and polyvinyl acetal resin, and
(B) Ingredients: water and
Ingredient (C): An organic solvent having a solubility parameter (SP value) of 12.5 to 18.0, and
Ingredient (D): An organic solvent having a solubility parameter (SP value) of 7.5 to 11.0,
Ingredient (E): Containing a phosphoric acid ester-type surfactant,
A film-forming agent for cleaning having a mass ratio of {(C) component + (D) component} / (E) component of 0.8 to 22. The cleaning film-forming agent according to claim 1, wherein the mass ratio represented by the component (C) / component (D) is 0.3 to 10. The component (D) is a glycol ether solvent represented by the following formula (1), and contains the component (D1) and the component (D2).
In the formula (1), the component (D1) is a glycol ether solvent in which R'is a hydrogen atom or a linear alkyl group having 1 to 8 carbon atoms.
In the formula (1), the component (D2) is a glycol ether solvent in which R'is an acetyl group.
The cleaning film-forming agent according to claim 1 or 2, wherein the mass ratio represented by the component (D1) / component (D2) is 0.2 to 1.
RO- (AO) _n- R'・ ・ ・ (1)
(In the formula (1), R is a linear or branched alkyl group or allyl group having 1 to 8 carbon atoms, and R'is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or It is an acetyl group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents 0.1 to 20 in average number of repetitions.)

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