WO2018003683A1 - Film-forming agent for cleaning and cleaning treatment method in which said agent is used - Google Patents

Abstract

Provided are a film-forming agent for cleaning that easily forms a film on the surface of an object to be cleaned and removes stains and that can remove firmly adhered stains, and a cleaning treatment method in which said agent is used. A film-forming agent for cleaning that contains (A) one or more polymers selected from (meth)acrylic resins, vinyl acetate resins, vinyl chloride resins, urethane resins, polyvinyl alcohol resins, and polyvinyl acetal resins; (B) water; and (C) an organic solvent having a solubility parameter (SP value) of 7.5-11.0, the ratio of (A)/(C) with respect to mass being 30-450. A cleaning treatment method in which said film-forming agent is used.

Description

Cleaning film forming agent and cleaning treatment method using the same

The present invention relates to a film forming agent for cleaning and a cleaning treatment method using the same. This application claims priority based on Japanese Patent Application No. 2016-129920 filed in Japan on June 30, 2016, the contents of which are incorporated herein by reference.

Conventionally, when performing a cleaning process to remove dirt adhering to a container or a human body, a combination of a cleaning agent containing water, a surfactant, or a solvent and a cleaning tool such as a sponge or a cloth is mainly used. It is used.
In the case where the cleaning treatment is performed on a surface with large irregularities or grooves or a surface with a small gap, such as a window glass or an aluminum sash rail, the above combination has been mainly used conventionally. However, since a general cleaning tool has a certain shape, it is often unsuitable for cleaning the surface with the unevenness and the gap. If the cleaning process is forcibly performed, it may be difficult to remove the dirt by pushing the dirt into the back of the gap or crushing the dirt.

On the other hand, for example, Patent Documents 1 and 2 have developed a technique for removing dirt by applying an aqueous solution or dispersion of a film-forming polymer to the dirt surface and peeling the film formed by drying. Has been. These techniques are intended to cope with dirt on a surface with fine irregularities by using an aqueous solution or aqueous dispersion having fluidity at the time of application.

Patent Document 3 discloses a technique of a cleaning film-forming agent containing an aerosol propellant and a film-forming polymer that is soluble under pressure. This film-forming agent for cleaning may contain an organic solvent such as alcohol or glycol ether in order to adjust the solubility and fluidity of the film-forming polymer. This technique uses a gaseous aerosol propellant at a normal temperature, so that the drying speed is fast and a better cleaning treatment capability is obtained.

Patent Document 4 discloses a technique for removing dirt by applying an aqueous dispersion on a dirt surface and peeling off a film formed by drying. This technique is intended to obtain an effect of removing oil stains that are relatively sticky by combining a polymer aqueous dispersion and a glycol solvent.

Japanese Patent Laid-Open No. 10-314688 JP-A-10-95922 JP 2006-16494 A JP 59-189200 A

However, these conventional techniques may not have sufficient cleaning treatment capacity against strong dirt. For example, among the objects to be cleaned, a window sash in a house having many uneven portions is one of the places where dirt is particularly likely to accumulate. Since the sash is open to the outdoors, mud dirt that adheres firmly to the surface to be cleaned is more easily formed than other parts by repeating the cycle of “wetting” and “drying” due to rain or direct sunlight. The techniques of Patent Documents 1 to 3 are intended to remove dust, dust, radioactive substances, or sebum dirt on the skin, which is lightly adhered, and clean up the strong dirt such as mud dirt. In some cases, the processing capacity was not sufficient.

The technique of patent document 4 aims at the removal of the oil dirt with much dirt which adhered comparatively strongly.
However, when used for strong mud dirt adhering to a sash rail having a groove or a window frame, the cleaning treatment capacity may not be sufficient. Furthermore, the film of the technique of Patent Document 4 has a problem that the film is easily torn, and it takes time to perform the peeling operation from the surface of the surface to be cleaned with many grooves, which makes it difficult to perform the cleaning process.

The present invention has been made in view of the circumstances as described above, and it is easy to perform film formation and removal of dirt on the surface to be cleaned, and a film forming agent for cleaning that can remove strongly adhered dirt and It aims at obtaining the cleaning processing method using it.

Specifically, in order to solve the above problems, the present invention has the following aspects.
[1] Component (A): one or more polymers selected from (meth) acrylic resins, vinyl acetate resins, vinyl chloride resins, urethane resins, polyvinyl alcohol resins, and polyvinyl acetal resins;
(B) component: water and
Component (C): an organic solvent having a solubility parameter (SP value) of 7.5 to 11.0,
And a film-forming agent for cleaning having a mass ratio represented by the component (A) / the component (C) of 30 to 450.
[2] The film-forming agent for cleaning according to [1], wherein the component (C) is a glycol ether solvent.
[3] The film-forming agent for cleaning according to [1] or [2], wherein the glass transition temperature (Tg) of the component (A) is 0 to 100 ° C.
[4] Component (D): The film-forming agent for cleaning according to any one of [1] to [3], further containing a chelating agent.
[5] The film-forming agent for cleaning according to [4], wherein the component (D) is a potassium salt.
[6] The film-forming agent for cleaning according to any one of [1] to [5] is applied to the surface to be cleaned, and the film is formed on the surface to be cleaned by the film-forming agent for cleaning. And then cleaning the surface to be cleaned by peeling the film from the surface to be cleaned.
[7] The film-forming agent for cleaning according to any one of [1] to [5], 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. .
[8] The cleaning according to any one of [1] to [5] or [7], wherein the content of the component (B) with respect to the total mass of the film forming agent for cleaning is 25 to 75% by mass. Film-forming agent.
[9] Any one of [1] to [5], wherein the content of the component (C) is 0.1 to 2.5% by mass relative to the total mass of the cleaning film-forming agent, [8] The film-forming agent for cleaning described in [8].

According to the present invention, it is easy to form a film on a surface to be cleaned and to remove dirt, and it is possible to obtain a film forming agent for cleaning that can remove strongly adhered dirt and a cleaning method using the same. .

It is a photograph figure which shows the evaluation method of the cleaning process capability which concerns on a present Example.

Hereinafter, the cleaning film forming agent and the cleaning treatment method using the same according to the embodiment of the present invention will be described with reference to embodiments. However, the present invention is not limited to the following embodiments.

[Embodiment]
The film-forming agent for cleaning of this embodiment contains the following (A) component, (B) component, and (C) component.

[(A) component]
The component (A) is at least one polymer selected from (meth) acrylic resins, vinyl acetate resins, vinyl chloride resins, urethane resins, polyvinyl alcohol resins, and polyvinyl acetal resins.
The polymer used for component (A) has film-forming properties. Here, the film forming property is a property capable of forming a peelable film. For example, when a polymer aqueous dispersion or aqueous solution is applied to a thickness of 0.05 to 0.5 mm in an area of 2 cm × 10 cm under atmospheric pressure conditions and left to stand for 48 hours, a film is formed. Point to. The film thus formed is preferably peelable by hand or the like.

As the polymer having such a film-forming property, a (meth) acrylic resin or a vinyl acetate resin is preferable, and a vinyl acetate resin is particularly preferable. By using these for the film-forming polymer, a high cleaning ability can be obtained.
The polymer used for the component (A) may be a polymer containing only one type of monomer of the above-mentioned type of compound, or a copolymer containing two or more types.

The content of the component (A) is preferably 20 to 70% by mass with respect to the total mass of the film forming agent for cleaning. When it is 20% by mass or more, the coating film is easily broken and the cleaning ability is not lowered. When the content is 70% by mass or less, the solubility or dispersibility in water is reduced, and aggregates are not generated.

The component (A) has a glass transition temperature of preferably 0 to 100 ° C., more preferably 5 to 50 ° C., and particularly preferably 10 to 30 ° C. By setting the glass transition temperature of the component (A) to 0 ° C. or higher, it is easy to form a tough film that does not break, and by setting it to 100 ° C. or lower, it is easy to form a film at room temperature. The glass transition temperature is a value obtained by the plastic transition temperature measurement method specified in JIS-K-7121.

((Meth) acrylic resin)
A (meth) acrylic resin is a polymer having a structural unit based on a (meth) acrylic acid ester. (Meth) acrylic resin is a general term for acrylic resin and methacrylic resin. (Meth) acrylic acid ester is a general term for acrylic acid ester and methacrylic acid ester.

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, Isobutyl (meth) acrylate, (meth) acrylate-sec-butyl, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, (meth ) Isobornyl acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth ) Acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2-hydroxybuty , Or (meth) acrylic acid-2-hydroxyphenyl ethyl.

As the ethylenically unsaturated monomer, any monomer having at least one polymerizable vinyl group may be used. Examples of such ethylenically unsaturated monomers include (meth) acrylic acid esters having a linear, branched, or cyclic alkyl chain, aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl Heterocyclic vinyl compounds such as pyrrolidone, hydroxyalkyl (meth) acrylate, alkylamino (meth) acrylate, vinyl esters such as vinyl acetate and vinyl alkanoate, monoolefins (ethylene, propylene, butylene, isobutylene, etc.) , Cyanidation of conjugated diolefins (butadiene, isoprene, chloroprene, etc.), α, β-unsaturated mono- or dicarboxylic acids (acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc.), acrylonitrile, etc. Vinyl compounds, acrolein and diacetone Carbonyl group-containing ethylenically unsaturated monomers such as acrylamide, or sulfonic acid group-containing ethylenically unsaturated monomers such as p- toluenesulfonic acid.

(Vinyl acetate resin)
Examples of the vinyl acetate resin include a vinyl acetate homopolymer or a copolymer of vinyl acetate and the above ethylenically unsaturated monomer excluding (meth) acrylic acid esters. As the vinyl acetate resin of the present embodiment, an ethylene-vinyl acetate copolymer is preferable from the viewpoint of cleaning treatment ability. When the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 25 to 99 mol%, it is possible to form a tough film that is difficult to break even with complicated shapes including uneven surfaces.

The gel fraction of the vinyl acetate resin is preferably 20 to 60%. When the gel fraction is within this range, it is possible to form a tough film that is difficult to break even with complicated shapes including irregular surfaces.
A gel fraction is a toluene insoluble content measured as follows, for example. An aqueous dispersion or aqueous solution of a vinyl acetate resin is applied onto a substrate and dried to form a film (film). The dried film is finely cut into a sample, and the weight of this sample (about 0.250 to 0.350 g) is weighed to 1 mg (mass A). Next, 100 ml of toluene is weighed into the flask, and the sample is added and 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. Thereafter, this solution was designated Filter through 2 filter papers. In advance, the mass of the aluminum pan was measured (mass B). 2 Weigh 20 ml of the filtrate filtered through filter paper in an aluminum dish. The aluminum dish is dried, the mass after drying (the total amount of the dried aluminum and the filtrate) is weighed to 1 mg (mass C), and the toluene insoluble content (mass%) is calculated by the following formula (1).
Toluene insoluble matter (mass%) = 100 − [(mass C−mass B) × 5 / mass A] × 100 (1)
The above operation is repeated three times (that is, the number of measured n is 3), and the average value thereof is defined as the gel fraction (% by mass) of the vinyl acetate resin.

(Vinyl chloride resin)
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, vinyl chloride-propylene copolymer. Vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, Vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer, Vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile Polymer, or vinyl chloride - can be used vinyl chloride resins such as various vinyl ether copolymers. As the vinyl chloride resin of the present embodiment, polyvinyl chloride is preferable from the viewpoint of the cleaning ability.

(Urethane resin)
The urethane resin is a resin having a urethane bond obtained by a reaction between a polyol component and a polyisocyanate compound. Examples of the urethane resin include polyurethane resin and acrylic urethane resin. Polyester polyol, polyether polyol, and polycarbonate polyol are used alone or in combination as a polyurethane component for the polyurethane resin, and acrylic polyol is used for the acrylic urethane resin. As the urethane resin of the present embodiment, a polyurethane resin is preferable from the viewpoint of the cleaning ability.

Examples of the polyurethane resin include an ether type using polyether polyol, a polyester type using polyester polyol, an ester / ether type using polyether polyol and polyester polyol, or a carbonate type using polycarbonate polyol. Among these, the polyurethane resin of the present embodiment is preferably an ester type and an ester / ether type, and particularly preferably an ester / ether type.

(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. It is particularly preferable to use polyvinyl alcohol having a saponification degree of 85.0 to 99.0 mol% and a polymerization degree of 500 to 2500.

(Polyvinyl acetal resin)
Examples of the polyvinyl acetal resin include polyvinyl butyral resin and polyvinyl acetoacetal 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 acetoacetal resin preferably has an acetalization degree of 5 to 30 mol% and a polymerization degree of 500 to 4000. As the polyvinyl acetal resin of the present embodiment, a polyvinyl acetoacetal resin is particularly preferable from the viewpoint of cleaning ability.

[Component (B)]
The component (B) is water. The component (B) of this embodiment is preferably distilled water, ion exchange water, or ultrapure water. The content of the component (B) in the film-forming agent for cleaning may be appropriately determined from the remaining amount depending on the amount of other components. As an example, the content is preferably 25 to 80% by mass with respect to the total mass of the film forming agent for cleaning. The content of the component (B) is more preferably 25 to 75% by mass.

[Component (C)]
Component (C) is an organic solvent having a solubility parameter (SP value) of 7.5 to 11.0.

The solubility parameter (SP value) in the present invention refers to a Hansen solubility parameter and is an index that serves as a measure of the solubility of a two-component solution.
As a method for calculating the SP value δ ((cal / cm 3) ^1/2 ) of each organic solvent used for the component (C), the following formula (2) was used.
δ = ((δd ² + δp ² + δh ² ) /4.2) ^1/2 (2)
Here, δd is a London dispersion force term, δp is a molecular polarization term, and δh is a hydrogen bond term.
In addition, the values (δd, δp, δh: units (J / cm ³⁾ described in Hansen Solubility Parameter Software (HSPIP ver. 4.1.x) or “HANSEN SOLBILITY PARAMETERS” A User's Handbook Second Edition ) It can be calculated based on ^1/2 ).
Moreover, SP value in the case of using two or more organic solvents for (C) component was calculated | required as a weighted average of SP value of each organic solvent by following formula (3).
m = δ1φ1 + δ2φ2 (3)
Here, δ1 and δ2 are SP values of the respective solvent components, and φ1 and φ2 are volume fractions of the respective solvent components.

The SP value of the organic solvent used for the component (C) is 7.5 to 11.0. When the SP value is 7.5 or more, aggregates of the film-forming polymer are hardly generated. When the SP value is 11.0 or less, a sufficient film forming property can be obtained. The SP value is preferably in the range of 8.5 to 10.5 from the viewpoint of the cleaning ability.

As the organic solvent used as the component (C), a glycol ether solvent represented by the following structural formula (4) is preferable from the viewpoint of the cleaning ability.
RO- (AO) _n -R '(4)
In the formula, R is a linear or branched alkyl group having 1 to 8 carbon atoms or an allyl group, and R ′ is selected from a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, and an acetyl group. Represents a functional group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents an average addition mole number of 0.1 to 20.

From the viewpoint of cleaning ability, the glycol ether solvent has a linear or branched alkyl group having 4 to 8 carbon atoms, AO is an oxyethylene group having 2 carbon atoms, and n is 0.1 to 10 Is preferred. Further, from the viewpoint of film forming property, R ′ is preferably a glycol ether having a hydrogen atom, R ′ is preferably a glycol ether acetate having an acetyl group, and R ′ is more preferably a glycol ether having a hydrogen atom.

Examples of the glycol ether in which R ′ is a hydrogen atom include diethylene glycol monomethyl ether (SP value = 10.7), triethylene glycol monomethyl ether (SP value = 10.7), and ethylene glycol monoisopropyl ether (SP value = 10.9). ), Ethylene glycol monobutyl 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 mono-2-ethylhexyl ether (SP value = 9.3), Ren 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 Examples thereof include monopropyl ether (SP value = 9.8), propylene glycol monobutyl ether (SP value = 9.0), dipropylene glycol monobutyl ether (SP value = 9.6), and the like.

Examples of the dialkyl glycol ether in which R ′ is an alkyl group include ethylene glycol dimethyl ether (SP value = 8.6), triethylene glycol dimethyl ether (SP value = 8.8), diethylene glycol diethyl ether (SP value = 8.7), or Examples include diethylene glycol dibutyl ether (SP value = 8.3).

Examples of glycol ether acetates in which R ′ is an acetyl group include 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 Examples include ether acetate (SP value = 9.0), dipropylene glycol monomethyl ether acetate (SP value = 9.2), and the like.

The content of the component (C) in the film-forming agent for cleaning is preferably 0.1 to 2.5% by mass with respect to the total mass of the film-forming agent for cleaning. When the content of the component (C) is 0.1% by mass or more, when the film forming agent for cleaning is infiltrated into the dirt to remove the dirt, it is for cleaning against dirt such as mud adhering firmly. The penetrating power of the film forming agent can be obtained, and the cleaning treatment ability can be sufficiently obtained. When the content of the component (C) is 2.5% or less, the coating is hardly broken and the cleaning process is preferably performed easily.
In addition, (A), (B), and (C) component which are essential components can be mix | blended in the range with the total of each content not exceeding 100 mass%.

[(D) component]
Component (D) is a chelating agent. (D) The kind of component is not specifically limited, It can select suitably from well-known chelating agents. Specific examples include organic carboxylic acids, aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, and phosphoric acids. Among these, aminocarboxylic acids or phosphonic acids are preferable as the chelating agent, more preferably aminocarboxylic acids, particularly preferably ethylenediaminetetraacetic acid salt or dihydroxyethylglycine salt.

The organic carboxylic acids are compounds having a carboxy group, and the carboxy group may form a salt. The organic carboxylic acids may have only a carboxy group as a functional group, or may have a functional group other than a carboxy group. Examples of organic carboxylic acids having a functional group other than a carboxy group include hydroxycarboxylic acids (salts). Specific examples of organic carboxylic acids include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethyl succinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxy Examples thereof include methyl tartaric acid, citric acid, malic acid, gluconic acid, and salts thereof.

Examples of aminocarboxylic acids include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionic acid, triethylenetetrahexaacetic acid, ethylene glycol dietherdiaminetetraacetic acid, dihydroxyethylglycine , Hydroxyethyliminodiacetic acid, cyclohexane-1,2-diaminetetraacetic acid, methylglycine diacetic acid, or salts thereof.

Examples of phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and its derivatives, 1-hydroxyethane-1,1,2 -Triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid, or a salt thereof.

Examples of the phosphonocarboxylic acids include 2-nosonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, and salts thereof.

Examples of phosphoric acids include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, condensed phosphoric acid such as phytic acid, or salts thereof.

Examples of the salt include alkali metal salts such as sodium or potassium, ammonium salts, monoethanolamine, or alkanolamine salts such as diethanolamine or triethanolamine. Among them, an alkali metal salt is preferable, and a potassium salt is more preferable.
These chelating agents may be used alone or in combination of two or more.

The component (D) is preferably contained as an anhydrous acid in a range of 0.1 to 3.5% by mass with respect to the total mass of the film forming agent for cleaning. According to the content, the cleaning ability is more excellent. The component (D) is particularly preferably contained as an anhydrous acid in the range of 0.1 to 2.5% by mass relative to the total mass of the film-forming agent for cleaning. According to the content, the cleaning ability is particularly excellent.

[Mass ratio represented by (A) component / (C) component]
The mass ratio represented by component (A) / component (C) (hereinafter A / C ratio) is 30 to 450. If the A / C ratio is 30 or more, the coating is hardly broken and the cleaning treatment can be suitably performed. If the A / C ratio is 450 or less, when the cleaning film-forming agent is allowed to penetrate into the dirt to remove the dirt, the cleaning film-forming agent has a penetrating power against dirt such as mud that adheres strongly. As a result, a sufficient cleaning capacity can be obtained. It is preferably 30 to 300, more preferably 30 to 100. By setting the A / C ratio within these ranges, it is possible to obtain a particularly excellent cleaning capability even for dirt such as mud that adheres firmly.

[Optional ingredients]
The cleaning film forming agent of the present invention may further contain optional components other than those described above. For example, solubilizers, emulsifiers, plasticizers, pH adjusters, release improvers, disinfectants, antibacterial agents, antiseptics, antioxidants, thickeners, inorganic fine particles, ultraviolet absorbers, bittering agents, dyes, pigments , Fillers, or fragrances.

Examples of the pH adjuster include alkali agents such as sodium hydroxide, potassium hydroxide, or alkanolamine (monoethanolamine, diethanolamine and triethanolamine); inorganic acids such as hydrochloric acid or sulfuric acid; citric acid, malic acid or tartaric acid Or an acid agent such as paratoluenesulfonic acid, metaxylenesulfonic acid, or benzoic acid.

[Preparation method]
As an example of the method for adjusting the film-forming agent for cleaning according to this embodiment, a part (for example, 50 to 80% by mass) of the component (B) is put into a container such as a beaker and the component (A) is stirred. Are gradually added and stirred to obtain an aqueous solution or dispersion of the polymer compound. Further, a commercially available product in which the component (A) is previously dissolved or dispersed in the component (B) may be directly charged into the container.
Next, after adjusting the pH by adding an appropriate amount of a pH adjusting agent as required, the remainder of (C) component, (D) component, (B) component (water), a peeling improver and the like are further added. By stirring, a film-forming agent for cleaning can be obtained.

[Cleaning method]
Next, a cleaning treatment method using the cleaning film forming agent of this embodiment will be described. In the cleaning treatment method of the present embodiment, a cleaning film forming agent is applied to the surface to be cleaned, the cleaning film forming agent is dried to form a film, and the film is cleaned. The surface to be cleaned is cleaned by peeling from the surface.
Here, the cleaning process refers to a process of removing dirt attached to the material surface of the surface to be cleaned. Dirt may broadly refer to substances other than substances that constitute the surface to be cleaned. Main dirt includes dust, dirt, and the like, and those that have lost moisture after adhering with moisture. The cleaning processing capacity broadly refers to the performance of removing dirt, but is mainly efficient (amount that can reduce the amount of dirt substances on the surface per hour), especially one cleaning processing operation (in this embodiment, cleaning is performed). This refers to how much dirt can be removed from the surface of the surface to be cleaned by an operation of forming and removing a film once on the target surface.

The surface to be cleaned includes surfaces of substances present in various places such as toilets, bathrooms, kitchens, sinks, and living rooms. In particular, these may have fine gaps or uneven surfaces, and these surfaces can be suitably used as surfaces to be cleaned. Examples of the material to be cleaned include plastic, glass, metal, rubber, and the like. Especially this embodiment can be used suitably for the junction part (for example, window sash) of the house member near the outdoors which was difficult to respond with the conventional cleaning agent and instrument, and the house member of the outdoors. These surfaces to be cleaned can be suitably used for the surface of a material having a large number of irregularities, which tends to cause strongly adhered mud stains and the like, and is easily deteriorated such as plastic.

Next, the cleaning film forming agent of the present embodiment is applied to the surface to be cleaned to which dirt has adhered.
The method of applying the cleaning film-forming agent may be performed by applying to the surface to be cleaned by application with a brush or pen, or by aerosol or spray.
When the application is performed by aerosol or spray, the cleaning film forming agent may be filled in a selected container so that the spraying operation can be easily performed. The shape of the container filled with the cleaning film forming agent may be a cylinder, a prism, or a cone, 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 the film later, the paper to be used as a handle with respect to the surface to be cleaned before the application of the film forming agent for cleaning or the film forming agent for cleaning after the application of the coating or A plastic plate may be installed.

Next, a film is formed by the film forming agent for cleaning on the surface to be cleaned. The film is a film having a thickness of about 0.05 to 10 mm as a standard in a formed state (a state in which the film forming agent for cleaning described later has no fluidity). The film can be formed by making the film forming agent for cleaning solid (a state having no fluidity). In this embodiment, the film is formed by drying a cleaning film forming agent. Here, drying is to remove a solvent such as moisture. The amount of drying, that is, the amount by which the water content of the cleaning film-forming agent is reduced may be determined until the cleaning film-forming agent becomes solid as a guide.
When drying, it may be carried out until the film is formed by naturally drying, that is, leaving the film-forming agent for cleaning after installation to evaporate water naturally from the surface. You may use together a means of applying the wind by a dryer, a fan, a ventilation fan, etc. to the film forming agent for cleaning. After applying the cleaning film-forming agent, water may be removed from the cleaning film-forming agent by spraying water-absorbing powder on the applied surface.

In the step of applying the cleaning film forming agent to the surface to be cleaned, the contamination 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. Dirt is removed from the target surface. Further, even in the process of forming the film, for example, in the process of leaving the film forming agent for cleaning to dry, the removal of dirt from the surface to be cleaned is performed.

Next, the film formed on the surface to be cleaned is peeled off. When the film is peeled off, the film of the present embodiment can be very easily performed by pinching the edge with a finger and removing it. Or you may use together the operation which peels off a film | membrane from the surface of the surface to be cleaned using tools with sharp edges, such as a spatula or a bamboo skewer. Or when the paper or plastic board used as the said handle has been installed, since this handle is integrated with the film according to the formation of the film, the film may be removed by pinching the handle. If the film is hard and difficult to peel off, water may be wiped off to the extent that the film does not flow again, and the softened film may be peeled off by hand or removed with a tool.

[Usage method of film forming agent for cleaning]
As a method of using the cleaning film forming agent of the present embodiment, it can be used in the above-described cleaning processing method (use of the cleaning film forming agent as the above-described cleaning processing method). The configuration of at least a part of the conversion processing method can be applied to various methods included in the configuration. For example, the present invention can be applied to a coating method or the like in which the above-described cleaning treatment method is performed on a processing target as a pretreatment for coating the processing target.

Hereinafter, examples will be described in detail.

[Component (A): one or more polymers selected from (meth) acrylic resins, vinyl acetate resins, vinyl chloride resins, urethane resins, polyvinyl alcohol resins, and polyvinyl acetal resins]
A1: Emulsion of acrylic ester copolymer (Showa Denko KK, product name: Polysol (registered trademark) AP604, solid content: 40%, glass transition temperature (Tg): 8 ° C.).
A2: Emulsion of acrylic-styrene copolymer (BASF Japan Ltd., product name: YJ2720Dap, solid content: 48%, glass transition temperature (Tg): 9 ° C.).
A3: Polyvinyl acetate emulsion (Nissin Chemical Industry Co., Ltd., product name: ViniBran (registered trademark) GV6181, solid content 50%, glass transition temperature (Tg): 30 ° C.).
A4: Emulsion of ethylene-vinyl acetate copolymer (Sumika Chemtex Co., Ltd., product name: SUMIKAFLEX S-752, solid content: 50%, glass transition temperature (Tg): 15 ° C.).
A5: Polyvinyl chloride emulsion (Nissin Chemical Industry Co., Ltd., product name: Viniblanc 603EML, solid content 50%, glass transition temperature (Tg): 10 ° C.).
A6: Emulsion of ethylene-vinyl chloride copolymer (Sumika Chemtex Co., Ltd., product name: SE1010, solid content: 50%, glass transition temperature (Tg): 0 ° C.).
A7: Emulsion of polyurethane (Daiichi Kogyo Co., Ltd., product name: Superflex (registered trademark) 150, solid content: 30%, glass transition temperature (Tg): 40 ° C.).
A8: An emulsion of acrylic urethane (Chuo Rika Kogyo Co., Ltd., product name: Rikabond SU-100, solid content: 33.5%, glass transition temperature (Tg): 0 ° C.).
A9: Polyvinyl alcohol (Kuraray Co., Ltd., product name: Kuraray Poval PVA-217).
A10: An aqueous solution of polyvinyl acetal (Sekisui Chemical Co., Ltd., product name: ESREC (registered trademark) KW-10, solid content: 25%, glass transition temperature (Tg): 65 ° C.).

[(B) component: water]
B1: Ion exchange water

[Component (C): an organic solvent having a solubility parameter (SP value) of 7.5 to 11.0]
C1: Diethylene glycol monohexyl ether (Nippon Emulsifier Co., Ltd., product name: hexyl diglycol, SP value = 9.7).
C2: Diethylene glycol mono 2-ethylhexyl ether (Nippon Emulsifier Co., Ltd., product name: 2 ethylhexyl diglycol, SP value = 9.3).
C3: Diethylene glycol monomethyl ether (Nippon Emulsifier Co., Ltd., product name: methyl diglycol, SP value = 10.7).
C4: Ethylene glycol monobutyl ether (Nippon Emulsifier Co., Ltd., product name: butyl glycol, SP value = 10.2).
C5: Diethylene glycol diethyl ether (Nippon Emulsifier Co., Ltd., product name: diethyl diglycol, SP value = 8.7).
C6: Diethylene glycol dibutyl ether (Nippon Emulsifier Co., Ltd., product name: dibutyl diglycol, SP value = 8.3).
C7: Acetone (Wako Pure Chemical Industries, Ltd., SP value = 9.7).
C8: Methyl acetate (Wako Pure Chemical Industries, Ltd., SP value = 9.1).

[(C ′) component: substitution of C component]
C′1: n-hexane (Wako Pure Chemical Industries, Ltd., SP value = 7.3).
C′2: Ethylene glycol monomethyl ether (Nippon Emulsion, BR> Wa Corporation, product name: methyl glycol, SP value = 12.1).

[(D) component: chelating agent]
The content of the component (D) shows the content of the chelating agent as an anhydrous acid in the table of the examples. D1: Dipotassium ethylenediaminetetraacetate (Chillest Co., Ltd., product name: Kirest (registered trademark) 2K-SD)
D2: Disodium ethylenediaminetetraacetic acid (Chillest Co., Ltd., product name: Cylest 2B-SD).
D3: dihydroxyethyl glycine sodium salt (Kyrest Co., Ltd., product name: Kyrest G-50).
D4: Dihydroxyethyl glycine potassium salt (Kyrest Co., Ltd., product name: Kyrest GA adjusted to pH 7 with potassium) was used.
D5: Trisodium citrate (Fuso Chemical Co., Ltd., product name: sodium citrate).

Further, a potassium hydroxide aqueous solution (solid content 25%) or 0.1N sulfuric acid was used as a pH adjuster.

[Methods for preparing Examples 1-27 and Comparative Examples 1-5]
In accordance with the composition (mass%) in Tables 1 to 3, 80% of the total amount of component (B) (water) is charged into a 300 mL beaker and stirred with a magnetic stirrer (Nisshin Rika: SW-R800, 1200 rpm). The component (A) (polymer compound) was added at a rate of 5 parts by weight / minute, and the mixture was stirred at 25 ° C. for 60 minutes to obtain an aqueous solution or aqueous dispersion of the polymer compound. Next, after adding a pH adjuster until the pH becomes 7.0, component (C) (film-forming aid having a solubility parameter (SP value) of 7.5 to 11.0), component (D) By adding the remainder of (chelating agent) and component (B) and stirring for another 30 minutes, a film-forming agent for cleaning was obtained.
“Balance” in the table is an amount such that the total amount of the film forming agent for cleaning is 100% by mass in total.

[Evaluation methods]
(Cleaning capacity)
A general household aluminum sash rail (width 2 cm × length 5 cm) was used as the surface to be cleaned. About 100 mg of black soil (Markei Co., Ltd.) was weighed on the surface to be cleaned, 0.5 g of tap water was added and mixed uniformly with a spatula, and then naturally dried to create mud stains.
Next, an appropriate amount of a film-forming agent for cleaning is formed so that a film having a thickness of 0.1 to 0.3 mm is formed in an area of 10 cm ² on the sash rail on which dirt is formed. After dropping the undiluted solution at room temperature for 24 hours, the state of the film when the film was peeled off and the state of removal of dirt stains were visually evaluated (N = 10) based on the following criteria, and the average score was taken as the evaluation score. . The evaluation method is to binarize the photograph of the rail after peeling the film from above (save in gray scale with Windows application “Paint”) and score it in comparison with a standard sample prepared separately as shown in FIG. did. More than three points were considered acceptable.

(Film peelability)
The film peelability was evaluated according to the following criteria.
○: It can be peeled without tearing the film.
Δ: A part of the film is broken and remains.
X: The film cannot be torn off.

These low-temperature cleaning treatment ability and film peelability are shown in the evaluation results in Tables 1 to 4.

As shown in Table 1, the cleaning power of Example 2 containing the component (D) was further improved compared to Example 1 containing the component (A), the component (B) and the component (C). In Examples 2 and 3, in which the component (C) was replaced with diethylene glycol monohexyl ether of Example 1 and acetone and methyl acetate were used, the cleaning treatment ability was lowered, but it was within the acceptable range. In Examples 5 to 8 in which the content of the component (C) was reduced, the cleaning treatment ability was lowered, but was within the acceptable range. As shown in Table 2, the processing capability was obtained in Example 9 in which the SP value of the component (C) was lower than the most preferable range of 9 to 10, and in Example 12 in which the SP value was higher than the above range. Decreased. In Example 10 in which the SP value is lower than 8.5 to 10.5, which is the preferred range after 9 to 10, and in Example 13 in which the SP value is higher than the above range, the cleaning treatment performance is further reduced. did. However, the cleaning treatment capacities of Examples 5 to 10 were within the acceptable range. In Example 14 using the same component (D) as in Example 2 and Example 16 using dihydroxyethylglycine-K, the same effects as in Example 2 were obtained. In Examples 15, 17 and 18 using other components, the cleaning treatment ability decreased, but was within the acceptable range. Regarding the component (D), the cleaning treatment ability was better when the potassium salt was used than when the sodium salt was used. As shown in Table 3, in Examples 19 to 27 in which different components (A) were used, the detergency of the other components was lower than that of Example 2 but was within the acceptable range. Examples 1-27, which are within the scope of the present embodiment, all showed good results within the acceptable range.

On the other hand, as shown in Table 4, Comparative Example 1 having no (C) component, Comparative Examples 2 and 3 having an A / C ratio outside the range of the present Example, and the SP value of the (C) component are In Comparative Examples 4 and 5 using those outside the scope of the present application, the cleaning treatment ability did not satisfy the acceptance criteria. In Comparative Examples 4 and 5, there was little penetration of the cleaning film-forming agent into the soil components, and the ability to remove the soil components could not be sufficiently exhibited.
From the above results, it has been clarified that the cleaning film-forming agent of the present embodiment exhibits good cleaning ability at low temperatures.

Claims (6)

(A) component: one or more polymers selected from (meth) acrylic resins, vinyl acetate resins, vinyl chloride resins, urethane resins, polyvinyl alcohol resins, and polyvinyl acetal resins;
(B) component: water and
Component (C): an organic solvent having a solubility parameter (SP value) of 7.5 to 11.0,
And a film-forming agent for cleaning having a mass ratio represented by the component (A) / the component (C) of 30 to 450. The film-forming agent for cleaning according to claim 1, wherein the component (C) is a glycol ether solvent. The film-forming agent for cleaning according to claim 1 or 2, wherein the glass transition temperature (Tg) of the component (A) is 0 to 100 ° C. Component (D): The film-forming agent for cleaning according to any one of claims 1 to 3, further comprising a chelating agent. The film-forming agent for cleaning according to claim 4, wherein the component (D) is a potassium salt. Applying the cleaning film-forming agent according to any one of claims 1 to 5 to a surface to be cleaned, forming a film on the surface to be cleaned with the film-forming agent for cleaning, Next, a cleaning method for cleaning the surface to be cleaned by peeling the film from the surface to be cleaned.

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