JP3126682B2 - Cleaning agent impregnated articles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article impregnated with a detergent, and more particularly, to an article impregnated with a detergent that wipes off dirt lightly and does not leave uneven wiping after wiping.

[0002]

2. Description of the Related Art As a method for cleaning hard surfaces such as glass and automobile bodies, a liquid cleaning agent containing a surfactant and an alkali agent is sprayed on the hard surface. After spraying, the cleaning agent is generally wiped off with a wet cloth and further wiped dry with a dry cloth. In this method, after the dry wiping, the cleaning agent, the dirt component, the lint, and the like are left on the hard surface as dry wiping unevenness. Had become.

Further, as a lens cloth for eyeglasses, a lens cloth made of ultrafine fibers is known. This cloth removes dirt by taking in dirt components between ultrafine fibers without using a cleaning agent. Accordingly, although there is a cleaning effect on dirt components such as oils such as sebum adhering to the lens surface, a cleaning effect on dirt components firmly adhering to the surface cannot be expected. Further, since the cloth is composed of ultrafine fibers, the cloth has a high coefficient of friction with the surface and requires a large force when wiping. Therefore, the cloth is not suitable for lightly wiping a large surface such as a window glass.

[0004] Accordingly, an object of the present invention is to provide a detergent-impregnated article in which dirt is lightly wiped, and unevenness in wiping does not remain after wiping. It is a further object of the present invention to provide a detergent-impregnated article that can easily wipe a large area of dirt.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors, the above object can be achieved by a detergent-impregnated article in which a substrate is impregnated with a detergent containing a specific amount of spherical particles having a specific particle size. I found that.

The present invention has been made based on the above-mentioned findings, and is intended to reduce spherical particles having an average particle size of 0.01 to 15 μm to 0.1 to 15 μm.
A substrate impregnated with a detergent containing 30% by weight and having a viscosity of 2 to 500 mPa · s at 20 ° C. under uniform stirring of the spherical particles. By providing the above, the above object has been achieved.

Another object of the present invention is to provide a method for cleaning a hard surface, comprising cleaning the hard surface using the above-mentioned cleaning agent-impregnated article.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the spherical particles contained in the cleaning agent, those capable of polishing and removing dirt components on a wiping surface are used. More specifically, the dirt components on the surface to be cleaned are used as the spherical particles. And an agent having an action of mixing the dirt component and floating the powder from the surface to be cleaned.

In particular, the above-mentioned spherical particles include the following (1):
It is preferable that one or more components selected from the group consisting of (2), (3), (4) and (5) are used as constituent components.

(1) Alkyl acrylates and methacrylates having 1 to 8 carbon atoms, mono- and dialkyl (alkyl groups having 1 to 5 carbon atoms) itaconate and fumarate, maleic anhydride, vinylidene chloride, styrene, divinylbenzene, vinyl chloride, Vinyl acetate, vinyl acetal, ethylene, propylene, butene, butylene, methylpentene, butadiene, vinyltoluene, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, citraconic acid, crotonic acid, β-acrylic Roxypropionic acid,
Polymers obtained by polymerizing monomers containing at least one ethylenically unsaturated monomer selected from the group consisting of hydroxyalkyl (alkyl groups having 1 to 6 carbon atoms) acrylates and methacrylates, or polymer blends containing the polymers .

(2) A silicone derivative (silicone rubber) having at least one group selected from structural units represented by the following general formula (I) or (I ').

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(3) A resin of at least one of nylon, polyester, epoxy, amino alkyd, urethane, polyacetal and polycarbonate.

(4) Polyorganosilsesquioxane (silicone resin) obtained by hydrolyzing and condensing methyltrialkoxysilane or its partial hydrolyzate / condensate in an aqueous solution of ammonia or amines.

(5) Silica or porous silica, sodium silicate glass, soda-lime glass powder, aluminosilicate, silicon carbide, layered silicate, quartz sand, aluminum oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium phosphate, oxide One or more water-insoluble inorganic substances of chromium, emery, dolomite, mica powder, quartzite, diatomaceous earth, kaolinite, halloysite, montmorillonite, illite, vermiculite, hectorite, bentonite, chitin powder, chitosan powder or hydroxyapatite.

Of the polymers or polymer blends included in the group (1), those preferably used are polymers obtained by polymerizing monomers containing ethylenically unsaturated monomers such as methacrylate, styrene, ethylene and propylene. And more preferably used are polymers obtained by polymerizing monomers containing an ethylenically unsaturated monomer such as methacrylate and styrene. Specific examples of the polymer include polyethylene, polystyrene, polyvinyl chloride, acrylic acid ester / acrylic acid / methacrylic acid ester / methacrylic acid / styrene copolymer, and cross-linked polymethacrylic acid ester.

Of the silicone derivatives included in the group (2), those preferably used include polydimethylsiloxane (silicone rubber) having a high polymerization degree.

Among the resins included in the group (3), those preferably used are polyester, polycarbonate, polyacetal, urethane and the like.

The polyorganosilsesquioxanes included in the group (4) are also particularly preferably used as the spherical particles in the present invention.

Among the water-insoluble inorganic substances included in the group (5), those preferably used are silica or porous silica, soda-lime glass powder, diatomaceous earth, kaolinite,
Montmorillonite, hectorite and bentonite.

Among the above components, it is particularly preferable to use those contained in the above groups (2) and (4).

In particular, when a polymer contained in the group (1) is used as the spherical particles, the polymer is
Ethylenically unsaturated monomers listed in the group of (1),
That is, it is preferable that the polymerizable monomer is obtained by emulsion polymerization or suspension polymerization in order to efficiently prepare spherical particles.

The spherical particles must have an average primary particle size of 0.01 to 15 μm in view of wiping and spreading properties, releasability of dirt components, and ease of wiping the wiping surface. 10 μm, preferably 1 to 5 μm
m is more preferable. The average particle size is a value measured by a laser diffraction / scattering type particle size distribution analyzer (LA910: manufactured by HORIBA, Ltd.). Further, the spherical particles may have a true specific gravity of 0.5 to 2.5 from the viewpoint of preventing the spherical particles from being separated within the substrate after the substrate is impregnated with the cleaning agent. Preferably, 0.5
More preferably from 1.5 to 1.5, and even more preferably from 1.0 to 1.5. In particular, the spherical particles have an average particle size of 1 to 5 μm and a true specific gravity of 0.5 to 1.5.
It is preferable to satisfy all of the wiping property, the wiping property, and the stability of the cleaning agent in the substrate.

The spherical particles preferably have a pencil hardness of 6B to 9H, more preferably H to 8H, from the viewpoint of preventing scratches on general hard surfaces. The spherical particles have a surface energy of the main component,
80 mN / m when the main component alone is measured in a planar state
The following are preferred in terms of the wiping spreadability, the wiping property, the operability, and the release property from the inside of the base material of the detergent-impregnated article. The surface energy is more preferably 50 mN / m or less, and even more preferably 30 mN / m or less. There is no particular limitation on the lower limit of the surface energy. The “main component” means a component having the highest proportion (weight% basis) among the components constituting the spherical particles. In particular, the main component preferably accounts for 50% by weight or more of the components constituting the spherical particles. The method for measuring the surface energy will be described in detail in Examples described later.

The performance of the spherical particles is improved as they are closer to a true sphere, and it is most preferable that all of them are true spheres in order to achieve the effects of the present invention.
Either the above particles have a projected image of a perfect circle, or when a circumscribed circle of the projected image is drawn, the radius of the circumscribed circle is 90%.
%, The effect of the present invention can be sufficiently exerted as long as the concentric circle having a radius of% and the circumscribed circle have a shape including the entire contour of the projected image. The method for measuring the shape of the spherical particles will be described in detail in Examples described later.

The above-mentioned spherical particles are contained in the above-mentioned detergent in an amount of 0.1 to 0.1%.
30% by weight is contained. If the content of the spherical particles is less than 0.1% by weight, sufficient detergency cannot be obtained and 30% by weight.
If it exceeds 300, it is difficult to stably impregnate the substrate, and the wiping property at the time of wiping is deteriorated, so that it may remain on the hard surface. The above-mentioned spherical particles are contained in the above-mentioned detergent preferably in an amount of 1 to 10% by weight, more preferably 2 to 5% by weight.

The above detergent has a viscosity at 20 ° C. of 2 to 500 mPa.
-It is s. If the viscosity is less than 2 mPa · s, the viscosity is too low to hold the cleaning agent in the substrate, and when cleaning a vertical surface such as a window glass, the cleaning agent drips downward. It falls down, which is not preferable for operation. On the other hand, if the viscosity exceeds 500 mPa · s, it is difficult to impregnate the substrate itself, and even if impregnated, the detergent does not easily come out of the substrate when washing. The viscosity is preferably from 10 to 100 mPa · s, and more preferably from 30 to 60 mPa · s.

The above-mentioned cleaning agent contains the above-mentioned spherical particles as an essential component, and it is preferable to use water as a medium from the viewpoints of wiping and spreading properties on the surface to be cleaned, handling properties, and impregnation into the substrate. Water is preferably blended in an amount of 100 to 10,000 parts by weight, more preferably 500 to 5,000 parts by weight, and more preferably 1,000 to 4,000 parts by weight, based on 100 parts by weight of the spherical particles. More preferably, it is blended. If the amount of water is less than 100 parts by weight with respect to 100 parts by weight of the spherical particles, the spherical particles may not be uniformly applied to the surface to be cleaned, and may be 10,000.
If the amount exceeds the weight part, it may not be possible to apply a sufficient amount of the spherical particles for cleaning to the surface to be cleaned.

Next, various optional components that can be blended with the above-mentioned cleaning agent will be described. The cleaning agent preferably contains a protective film forming component, particularly a polyorganosiloxane, from the viewpoint that a coating (protective film) can be formed on the surface to be cleaned and the antifouling property of the surface to be cleaned can be enhanced. The polyorganosiloxane is preferably blended in an amount of 1 to 200 parts by weight, more preferably 2 to 100 parts by weight, and more preferably 5 to 50 parts by weight, based on 100 parts by weight of the spherical particles. More preferred. If the amount of the polyorganosiloxane is less than 1 part by weight based on 100 parts by weight of the spherical particles, a sufficient protective film is not formed on the surface to be cleaned when the detergent-impregnated article is used, and sufficient antifouling property is obtained. May not be expressed, 200
If the amount exceeds the weight part, excess polyorganosiloxane may remain on the surface to be cleaned and glare may occur.

As the above-mentioned polyorganosiloxane, it is preferable to use a polyorganosiloxane having a static friction coefficient of 0.1 to 1.0 on the surface to be cleaned after wiping (more preferably 0.1 to 0.5). Examples of such polyorganosiloxanes include silicone oils such as dimethylpolysiloxane and methylhydrogenpolysiloxane, fluorinated silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, alcohol-modified silicone oil, and alkyl-modified silicone oil. There are organically modified silicone oils and the like. These polyorganosiloxanes can be used alone or in combination of two or more.

In particular, the polyorganosiloxane is a liquid at ordinary temperature (20 ° C.) and has the general formula (I)
Alternatively, it is preferable to use a compound having at least one group selected from the structural units represented by (I ′), because the wiping property and the ability to form a protective film are more excellent. Particularly, when the organo group in the polyorganosiloxane is phenyl, It is preferable to use one or more groups selected from a group and an alkyl group having 1 to 80 carbon atoms because the above performance is particularly excellent.

The most preferred polyorganosiloxane is
It is represented by the following general formula (II).

[0032]

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In the general formula (II), n1 and n2 are preferably each independently an integer of 0 to 50, and m is preferably an integer of 1 to 1,000.

It is preferable that the above-mentioned cleaning agent contains an organic solvent having a boiling point of 70 to 300 ° C. from the viewpoint of the cleaning performance against oily stains, the spreadability and the wiping property. The organic solvent is preferably incorporated in an amount of 0.05 to 60% by weight, more preferably 0.1 to 30% by weight.

The type of the organic solvent is not particularly limited as long as it has the above-mentioned boiling point.
Paraffin, kerosene, petroleum benzine, xylene, n-
Hexane, cyclohexane and the like can be used. These organic solvents can be used alone or in combination of two or more.

In particular, as the organic solvent, the following general formula (II)
The use of the compound represented by I) is preferable because the cleaning performance against oily dirt, the spreading property and the wiping property are further improved.

[0037]

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In the above general formula (III), p, q, r and s
Is preferably independently an integer of 0 to 50. Among the organic solvents represented by the general formula (III), n-paraffin is particularly preferably used.

When the detergent contains the organic solvent, the detergent comprises 0.1 to 20% by weight of the spherical particles, 0.01 to 20% by weight of the polyorganosiloxane, and 0.05 to 20% by weight of the organic solvent. It is preferred that it consists of 60% by weight and the balance water.

It is also preferable that the above-mentioned detergent further contains at least one selected from a surfactant and a polymer dispersant from the viewpoints of the blending stability of the detergent and the washing performance. The surfactant and the polymer dispersant are each 0.005 to 10% by weight.
It is preferably added, more preferably 0.01 to 5% by weight, more preferably 0.02 to 1% by weight.

As the above-mentioned surfactant, conventionally known various surfactants (anionic, cationic, nonionic, amphoteric surfactant) can be used without any particular limitation. These surfactants can be used alone or in combination of two or more.

The surfactants preferably used include:
Alkyl (straight or branched chain having a carbon chain length of 8 to 18) benzene sulfonate, polyoxyethylene (average addition mole number 0.5 to 10) alkyl (straight or branched chain having a carbon chain length of 8 to 22) ether Sulfate, alkyl (carbon chain length 8-18
Straight or branched chain) sulfates, fatty acids (carbon chain length of 8 to 22)
Linear or branched) salts, polyoxyethylene (average addition mole number 0.5 to 10) alkyl (linear or branched chain having a carbon chain length of 8 to 22) ether carboxylate, alkyl (carbon chain length of 8 to 10) 22 straight-chain or branched-chain) sulfonates, alkyl (straight-chain or branched-chain having a carbon chain length of 8 to 22) glycoside (average degree of sugar condensation: 1.0 to 10.0), fatty acid (carbon chain length of 8 to 22) Linear or branched chains) glycerides, sorbitan fatty acid (linear or branched chains having a carbon chain length of 8 to 22) esters,
One or more selected from the group consisting of alkyl (linear or branched chain having a carbon chain length of 8 to 18) trimethylammonium salt and alkyl (linear or branched chain having a carbon chain length of 8 to 18) dimethylbenzylammonium salt No.
In these surfactants, in the case of an anionic surfactant, the counter ion is an alkali metal, an alkaline earth metal, ammonium, or an alkanolamine having 1 to 3 carbon atoms, and a cationic surfactant is used. In the above case, the counter ion is a halogen atom or an alkyl sulfate residue having 1 to 6 carbon atoms.

Among these surfactants, it is particularly preferable to use an alkyl glycoside such as dodecyl glycoside, since it is difficult to form uneven wiping on a hard surface.

It is particularly preferable that these surfactants have an average alkyl chain length in the molecule of from 8 to 18 carbon atoms from the viewpoint of blending stability and cleaning performance.

On the other hand, as the above-mentioned polymer dispersant, those which increase the dispersibility of the dirt component in the washing process and lower the re-contamination property of the dirt component are used.
8, alkyl acrylates and methacrylates, mono and dialkyl (alkyl groups having 1 to 5 carbon atoms) itaconate and fumarate, maleic anhydride, vinylidene chloride, styrene, divinylbenzene, vinyl chloride, vinyl acetate, vinyl acetal, ethylene, propylene,
Butene, butylene, methylpentene, butadiene, vinyltoluene, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, citraconic acid, crotonic acid, beta-acryloxypropionic acid, hydroxyalkyl (carbon of alkyl group Formulas 1 to 6) Use of a polymer dispersant obtained by polymerizing monomers containing at least one ethylenically unsaturated monomer selected from the group consisting of acrylates and methacrylates, vinylpyrrolidone and derivatives thereof. It is also preferable from the viewpoint of the blending stability of the polymer dispersant itself. These polymer dispersants can be used alone or in combination of two or more.

Other optional components that can be added to the above-mentioned detergent include, for example, an alkali agent for improving the detergency of the detergent-impregnated article of the present invention, a lubricant for enhancing the lubricity, and a lubricant in the detergent. Examples include a thickening stabilizer for improving the dispersibility of each component, a drying accelerator (for example, ethanol, etc.), an antifungal agent for fungicide of a detergent, a fragrance and a pigment. These components are preferably contained in the above-mentioned detergent in an amount of 5 to 5%.
0% by weight, more preferably 10 to 30% by weight.

The detergent is preferably impregnated with 50 to 5,000% by weight, more preferably 100 to 3,000% by weight, based on the weight of the substrate under no load. If the impregnation amount of the cleaning agent is less than 50% by weight, only the required amount of the cleaning agent can be applied to the surface to be cleaned. If the amount exceeds 5,000% by weight, a cleaning agent in a necessary amount or more is applied to the surface to be cleaned.

As the substrate used in the cleaning agent-impregnated article of the present invention, a substrate which can be impregnated with the cleaning agent, has a sufficient strength at the time of use, and does not generate scraps is used. In particular, it is preferable to use a substrate that can be impregnated with the above-described amount of the detergent under no load. Examples of such a substrate include a fibrous structure composed of a fibrous material, such as various types of paper, nonwoven fabric, woven fabric, and knitted fabric. Examples of the fibrous material constituting these fiber structures include cellulosic fibers, modified cellulosic fibers, synthetic fibers, and mixtures of two or more of these. Examples of the cellulosic fibers include wood-based pulp and cotton,
Natural fibers such as hemp and cellulosic chemical fibers such as tencel, viscose rayon and acetate are exemplified. on the other hand,
Examples of the synthetic fibers include polyolefin fibers such as polyethylene and polypropylene, polyester fibers such as polyethylene terephthalate, polyamide fibers such as nylon, polyacrylonitrile fibers, polyvinyl alcohol fibers, and at least two kinds of these synthetic fibers. And fibers obtained by mixing at least two of these synthetic fibers.

Also, a flexible porous structure such as a plastic foam (for example, a sponge-like structure) can be used as the base. In this case, examples of the shape of the porous structure include a sheet shape, a column shape, and a rectangular parallelepiped, but are not limited thereto. The porous structure has a cell diameter larger than the average particle diameter of the spherical particles,
This is preferable because the spherical particles can be easily taken into the porous structure and can be sufficiently supplied to the surface to be cleaned.
The porous structure has a cell number of 10 to 100.
Cells / 2.5 cm (that is, the number of cells crossed when a 2.5 cm straight line is drawn on an arbitrary portion of the porous structure is 10 to 100), particularly 30 to 50 cells / 2.5 cm. This is preferable from the viewpoints of impregnation of the above-mentioned cleaning agent, release and application of an appropriate amount of the cleaning agent to the surface to be cleaned, and the like.

Examples of the material constituting the porous structure include a cellulosic resin, a synthetic resin, and a mixture of two or more thereof. Examples of the cellulose-based resin include viscose rayon and acetate.
On the other hand, examples of the synthetic resin include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, polyamide resins such as nylon, polyacrylonitrile resins, polyvinyl alcohol resins, urethane resins, and the like. .

In particular, from the viewpoint of the impregnation of the above-mentioned detergent into the substrate, and the usability and operability of the article impregnated with the detergent, the substrate may be made of paper, nonwoven fabric, woven fabric, knitted fabric or plastic foam. It is preferable to use a flexible porous structure (sponge-like structure).

Further, as the substrate, a nonwoven fabric aggregate formed by fiber entanglement of a fiber web on one or both surfaces of the mesh sheet is formed on the mesh sheet together with the entanglement between the constituent fibers. It is also preferable to use a sheet integrated in an entangled state.

The above-mentioned substrate is preferred in view of the impregnation property of the above-mentioned cleaning agent into the substrate and the capacity for impregnating the required amount of the cleaning agent.
Preferably it has a basis weight of 15~400g / m ^2, and still more preferably from 25~300g / m ^2.
Further, the substrate preferably has a thickness under a load of 0.5 g / cm ^{2 of} 0.5 to 5 mm, and more preferably 1 to 3 mm, from the viewpoint of the operability and the feeling of use of the detergent-impregnated article. More preferred.

The detergent impregnated articles of the present invention are particularly effective for cleaning hard surfaces. That is, when the cleaning agent-impregnated article of the present invention is used for cleaning hard surfaces such as glass, automobile bodies, mirrors, tiles, and furniture, the hard surfaces do not remain even after dry wiping. Time and effort such as wiping can be saved. More specifically, a method for cleaning a hard surface using the cleaning agent-impregnated article of the present invention includes:
Cleaning floors, tatami mats, ceilings, roofs, etc., wall / floor / door /
Cleaning of bathroom equipment such as bathtub / washbasin etc., cleaning of kitchen wall / floor / sink area / range area / ventilation fan, cleaning of cupboards, chests, tables, desks, chairs, bookshelves and other furniture, refrigerator Cleaning of appliances such as televisions, personal computers, stereos, air conditioners, microwave ovens, washing machines, dryers, lighting equipment, cleaning of windows used in houses, doors, furniture doors, automobile windows, etc. , Screen door cleaning, toilet floors, walls, doors, toilet bowls, toilet seats, etc., cleaning dishes, cooking utensils, cleaning painted and plastic surfaces of automobiles, bicycles, motorcycles, etc., cleaning automobile wheels, exterior It is effective for cleaning around entrances, terraces, fences, fences, gates, and other hard surfaces.

Since the detergent-impregnated article of the present invention is impregnated with the above-mentioned detergent, the coefficient of dynamic friction at the time of application of the detergent (when used) is small, and the surface to be cleaned can be lightly wiped. Further, the coefficient of kinetic friction at the time of wiping with a wiping sheet (dry wiping sheet) after the dirt on the surface to be cleaned is raised by the cleaning agent-impregnated article of the present invention is reduced, and the surface to be cleaned can be lightly wiped. it can. Therefore, a large area of dirt can be easily wiped off. The coefficient of kinetic friction when the surface to be cleaned is wiped dry with a wiping sheet after the surface of the surface to be cleaned is lifted up by the cleaning agent-impregnated article of the present invention is preferably 0.5 or less, and more preferably 0.5 or less. 4 or less. In order to set the value of the dynamic friction coefficient within such a preferable range, for example, the solid abrasive particles and the protective film forming component in the cleaning agent, and the type and concentration of the lubricant or the cleaning base material as necessary, And the amount of impregnation of the cleaning agent may be adjusted. The details of the method of measuring the coefficient of dynamic friction will be described in Examples described later. Further, as the wiping sheet, for example, a sheet similar to the above-described base can be used.

Further, after the dirt on the surface to be cleaned is lifted up by the cleaning agent-impregnated article of the present invention, the dirt is wiped off with a wiping sheet or the like, and the surface to be cleaned is cleaned (that is, after the dry wiping). The coefficient of static friction of the surface to be cleaned)
Due to the action of the protective film-forming component, particularly the protective film formed by the above-mentioned polyorganosiloxane, the size becomes extremely small. That is, when the polyorganosiloxane is blended, the static friction coefficient of the cleaned surface to be cleaned is preferably 0.1 to 1.0, and more preferably 0.1 to 0.1.
It becomes 5. As a result, the coefficient of kinetic friction at the time of wiping the cleaned surface to be cleaned again with a wiping sheet or the like is reduced as necessary, and the surface to be cleaned can be wiped lighter. In order to make the value of the coefficient of static friction fall within such a preferable range, for example, the type and concentration of the protective film forming component mixed in the cleaning agent and the impregnation amount of the cleaning agent may be adjusted. The details of the method of measuring the coefficient of static friction will be described later in Examples.

Furthermore, when the cleaning agent-impregnated article of the present invention is used, dirt comes up only by gently wiping the surface to be cleaned. Therefore, the cleaning agent-impregnated article and / or wiping sheet of the present invention is shown in FIG. Head part 2 in cleaning tool 1 as shown
, It is possible to easily clean the surface to be cleaned which is usually located at a high place where wiping is difficult. The cleaning tool 1 shown in FIG. 1 has a flat head portion 2 on which the cleaning agent-impregnated article (particularly a sheet-like article) 10 of the present invention can be mounted, and is connected to the head section 2 via a universal joint 3. The cleaning agent-impregnated article 10 of the present invention, which is constituted by a rod-shaped handle 4, is fixed by a plurality of flexible pieces 5 forming radial slits provided on the head 2.

Next, a cleaning method using the cleaning agent-impregnated article of the present invention will be described with reference to FIG. 2 taking the cleaning of the glass surface as an example. Here, FIG. 2 is a schematic diagram illustrating a method of cleaning a glass surface using a detergent-impregnated sheet as one embodiment of the detergent-impregnated article of the present invention. The greatest feature of the cleaning agent-impregnated article of the present invention is that the surface of glass can be cleaned by the cleaning agent-impregnated article alone without using a large amount of water and a liquid such as a cleaning agent other than the impregnated cleaning agent. . That is, when cleaning the glass, as shown in FIG. 2A, the surface 21 to be cleaned of the glass 20 is directly wiped with the cleaning agent-impregnated article 10 of the present invention, and the impregnated cleaning agent is applied to the surface to be cleaned. Apply. As a result, as shown in FIG. 2 (b), the dirt component 22 present on the surface 21 to be cleaned is mixed with the spherical particles 23 in the cleaning agent and floats up, and is formed on the surface 21 to be cleaned in powder form. It comes free. Although not shown in the figure, the oily dirt is mixed with a cleaning base such as n-paraffin in the cleaning agent formulated as necessary, floats up, and is released on the surface 21 to be cleaned. . When the above-mentioned polyorganosiloxane is blended in the above-mentioned cleaning agent, the above-mentioned polyorganosiloxane coats the surface 21 to be cleaned. Next, as shown in FIG. 2 (c), the dirt component 22 released in the powdery state is dry-wiped using a wiping sheet 26 such as paper or non-woven fabric such as a dry cloth, tissue paper, and kitchen paper. (After about 30 seconds to 5 minutes). In this case, since the dirt component is in a powdery form, it can be easily wiped off, and no wiping unevenness remains. When the polyorganosiloxane is mixed in the cleaning agent, the protective film 25 remains on the surface 21 to be cleaned. And the next cleaning can be done easily.

[0059]

The following examples illustrate the effectiveness of the detergent impregnated articles of the present invention. However, the present invention is not limited to such an embodiment. In the following examples,%
Means% by weight unless otherwise specified.

Example 1 Formulation of Detergent A detergent was prepared by mixing the following components in the following proportions.・ Spherical or amorphous particles (see Tables 1 to 4) 3% ・ Dimethylpolysiloxane (protective film forming component) 0.5% ・ n-paraffin (boiling point: 227 ° C.) (washing substrate) 2% ・ Dodecyl glucoside 0.50% (nonionic surfactant, glucose condensation degree 1.35) ・ Xanthan gum (dispersant) 0.13% ・ Ethanol (drying accelerator) 20% ・ Ion-exchanged water balance The spherical or amorphous particles shown in FIG. 4 were used. In the spherical particles shown in Tables 1 to 4, 90% or more of the particles in number percent had a perfectly circular projected image. The projected images and surface energies of the spherical and amorphous particles were measured by the following methods.

<Method of Measuring Projected Images of Spherical and Amorphous Particles> Stereo microscope [Hiscope KA-2200;
The projected image of the particles was measured using an image analyzer (TV Image Processor EXCEL TVIP-4100; manufactured by Nippon Avionics Co., Ltd.) equipped with [Hyrox].

<Method of Measuring Surface Energy of Spherical and Amorphous Particles> Each particle sample (freeze-dried product in the case of an emulsion) was subjected to a tableting machine at 300 to 1,000 kg / kg.
The tablet was pressed at ² cm ² to prepare a tablet having a substantially mirror-finished surface, and the surface energy of the particles was measured by measuring the contact angles of water and diiodomethane on the surface.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

Production of Cleaning Impregnated Articles Dry type pulp sheet made of Havix having a basis weight of 55 g / m ² and a thickness of 0.9 mm under a load of 0.5 g / cm ² (pulp fibers that have been defibrated and laminated with a binder). (Which were bonded and formed into a sheet) were immersed in the above-mentioned cleaning agent. After the detergent was sufficiently impregnated, the dry pulp sheet was pulled up, and excess detergent was removed using a mangle to obtain a detergent-impregnated article. The amount of the detergent impregnated in the obtained detergent impregnated article was 3 to the weight of the dry pulp sheet.
It was 00-500%. In order to examine the cleaning performance of the obtained detergent-impregnated article, a glass for evaluation (a flat and transparent soda-lime plate glass which has been sufficiently washed beforehand in a clean state) was placed on a northern place where rainwater does not directly hit for three months. After standing, the surface of the glass for evaluation was wiped with the detergent-impregnated article, and after drying, the surface was wiped dry with kitchen paper (manufactured by Havix, the above-mentioned dry pulp sheet). The coefficient of kinetic friction when the surface was wiped dry with the kitchen paper was measured by the following method. In addition, the state of uneven wiping of the surface after wiping with the kitchen paper was evaluated according to the following criteria, and the coefficient of static friction of the surface after wiping was measured by the following method. Furthermore, the antifouling property of the surface after the dry wiping was evaluated by the following method. The results are shown in Tables 5 to 8.

<Measurement of Dynamic Friction Coefficient> A detergent was uniformly applied (3 g / m ² ) to the surface of the evaluation glass left under the above conditions for three months using the detergent impregnated article. After being dried (after about 3 minutes), a kitchen paper (made of Havix, dry pulp sheet) having a diameter of 6 cm was placed, and the kitchen paper was rotated at a speed of 3 under a load of 1.3 kg.
The dynamic friction coefficient was determined by the following equation (1) by measuring the force F applied when the actuator was moved horizontally in cm / sec. If the coefficient of dynamic friction at the time of wiping is 0.4 or more, wiping becomes extremely heavy and difficult. Dynamic friction coefficient = F (kg weight) /1.3 (kg weight) (1) <Evaluation of uneven wiping> Utilizing the phenomenon that uneven wiping causes a decrease in the glossiness of the surface to be cleaned, and The wiping unevenness was evaluated by measuring the glossiness of the surface to be cleaned with a Minolta glossmeter 9M-268 at a measurement angle of 85 °. The higher the value of gloss, the more
This means that there is little wiping unevenness, and when it is 110 or less, wiping unevenness can be visually recognized. The gloss before leaving (that is, the clean surface) was 115. <Measurement of static friction coefficient> Static friction coefficient measuring machine (Shinto Kagaku,
HEIDON Tribogear Muse TYPE 94
Kitchen paper (manufactured by Havix, dry pulp sheet) was attached to the measuring section of (i), and the coefficient of static friction of the surface to be washed after washing was measured. Each measurement is the average of n = 5. still,
The static friction coefficient after leaving the glass for evaluation for 3 months under the above conditions was 1.45, and the static friction coefficient before leaving (that is, the clean surface) was 0.52. However, since the coefficient of static friction slightly changes depending on the weather during standing and the surface condition of the glass, the above numerical value is a guide. <Evaluation of antifouling property> After leaving the above-mentioned glass for evaluation for 3 months under the above-mentioned conditions, the surface of the glass for evaluation is wiped with the detergent-impregnated article, and the glass is further washed with kitchen paper (manufactured by Havix, dry pulp sheet). The surface cleaning agent is wiped off to prepare an evaluation surface. Next, the static friction coefficient A of the surface of the glass for evaluation immediately after preparation of the surface for evaluation is measured according to the above method. After the measurement, the glass for evaluation is left again under the above conditions, and the static friction coefficient B of the surface of the glass for evaluation after three months is measured according to the above method. Separately, a control glass similar to the above-mentioned evaluation glass is left under the above-mentioned conditions for three months, and then the surface of the control glass is sufficiently washed and cleaned to prepare a control surface. Next, the static friction coefficient C (≒ 0.52) of the control glass immediately after preparing the control surface is measured according to the above method. After the measurement, the control glass was allowed to stand again under the above conditions, and the static friction coefficient D of the control glass surface after three months had passed.
(≒ 1.45) is measured according to the above method. From the obtained values of A, B, C and D, the degree of contamination was calculated by the following equation (2). When the degree of contamination is preferably 30% or less, and more preferably 20% or less, it indicates that the antifouling property is visually exhibited.

[0069]

(Equation 1)

[0070]

[Table 5]

[0071]

[Table 6]

[0072]

[Table 7]

[0073]

[Table 8]

Example 2 Silicone resin (average particle diameter 3 μm, surface energy 30 mN / m, true specific gravity 1.3, number percent 90)
% Or more of particles have a perfect circular projected image), and a cleaning agent was prepared in the same manner as in Example 1 except that polyorganosiloxane shown in Table 9 was used. After that,
A detergent-impregnated article was obtained in the same manner as in Example 1. The same measurement and evaluation as in Example 1 were performed on the obtained detergent-impregnated article. Table 9 shows the results.

[0075]

[Table 9]

[Example 3] Silicone resin (average particle size 3 µm, surface energy 30 mN / m, true specific gravity 1.3, true sphere) was used as the spherical particles in Example 1, and the organic solvents shown in Table 10 were used. Example 1 except for using
A detergent was prepared in the same manner as described above. Thereafter, a detergent-impregnated article was obtained in the same manner as in Example 1. The same measurement and evaluation as in Example 1 were performed on the obtained detergent-impregnated article.
Table 10 shows the results.

[0077]

[Table 10]

Comparative Examples 1 and 2 In the cleaning agent of Example 1, except that spherical or irregular particles were not used (Comparative Example 1) and dimethylpolysiloxane was not used (Comparative Example 2). A cleaning agent was prepared in the same manner as in Example 1. After that, a detergent-impregnated article was obtained in the same manner as in Example 1. The same measurement and evaluation as in Example 1 were performed on the obtained detergent-impregnated article. Table 11 shows the results.

Comparative Example 3 A liquid cleaning agent for glass wiping [glass mypet (trade name) manufactured by Kao Corporation) was used in Example 1.
The same amount of glass was sprayed on the same surface as in Example ² (spray amount: 6 g / m ² ). After the spray surface was wiped off with a wet cloth, it was wiped dry with kitchen paper (made by Havix, dry pulp sheet). The state of uneven wiping on the glass surface after wiping with the kitchen paper was evaluated in the same manner as in Example 1, and the static friction coefficient and antifouling property of the glass surface were measured and evaluated in the same manner as in Example 1. Table 11 shows the results.

[0080]

[Table 11]

As is clear from the results shown in Tables 5 to 11, the cleaning agent-impregnated article of the present invention in which the substrate was impregnated with a cleaning agent containing spherical particles having a specific average particle size at a specific concentration was used. When the glass surface is washed, the coefficient of kinetic friction at the time of wiping (dry wiping) is smaller than that of the case where the detergent-impregnated articles of Comparative Examples 1 and 2 are used, and it can be seen that there is no wiping unevenness after the wiping. The coefficient of static friction after dry wiping is determined by the effect of the protective film on the clean surface (0.5%).
It turns out that it becomes smaller than 2). Furthermore, it is understood that the antifouling property after washing is excellent. In addition, when the glass surface is cleaned using a conventional liquid cleaner for wiping glass (Comparative Example 3), considerable wiping unevenness is left as compared with the cleaning agent-impregnated article of the present invention, and other various performances are inferior.

[0082]

According to the cleaning agent-impregnated article of the present invention, dirt can be wiped off lightly without using water, and there is no unevenness in wiping after wiping, so that the next cleaning work can be omitted. Further, according to the cleaning agent-impregnated article of the present invention, a large area of dirt can be easily wiped off.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a cleaning tool equipped with a cleaning agent-impregnated article of the present invention.

FIG. 2 is a schematic view illustrating a method for cleaning a glass surface using the cleaning agent-impregnated article of the present invention.

[Explanation of Signs] 1 Cleaning tool 2 Head part 4 Handle 10 Detergent impregnated article 20 Glass 21 Surface to be cleaned 22 Soil component 23 Spherical particle 24 Polyorganosiloxane 25 Protective film 26 Wiping sheet

Continuation of the front page (56) References JP-A-7-252454 (JP, A) JP-A-6-17356 (JP, A) JP-A-58-7496 (JP, A) JP-A-61-108700 (JP) U.S. Pat. No. 4,212,759 (US, A) European Patent Application Publication 100195 (EP, A2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 17/04 A47L 13/17

Claims (17)

(57) [Claims] 1. A composition containing 0.1 to 30% by weight of spherical particles having an average particle size of 0.01 to 15 μm, and having a viscosity at 20 ° C. of 2 to 500 m under uniform stirring of the spherical particles.
A detergent-impregnated article comprising a substrate impregnated with a detergent having a Pa · s. 2. The spherical particles have an average particle size of 0.1 to 10.
The cleaning impregnated article according to claim 1, which has a size of μm. 3. The true specific gravity of the spherical particles is 0.5 to 2.5.
The cleaning agent-impregnated article according to claim 1 or 2, wherein 4. The surface energy of the main component of the spherical particles is 80 mN when the main component alone is measured in a planar state.
The detergent-impregnated article according to any one of claims 1 to 3, which is not more than / m. 5. The method according to claim 5, wherein the spherical particles are 90% by number.
% Or more of the particles have a projected image of a perfect circle, or when a circumcircle of the projected image is drawn, 9% of the radius of the circumscribed circle
The shape which includes all the contours of the projected image between a concentric circle having a radius of 0% and the circumscribed circle.
5. The cleaning agent-impregnated article according to any one of 4. 6. The spherical particles according to the following (1), (2),
The detergent-impregnated article according to any one of claims 1 to 5, comprising one or more components selected from the group consisting of (3), (4) and (5). (1) Alkyl acrylates and methacrylates having 1 to 8 carbon atoms, mono- and dialkyl (alkyl groups having 1 carbon atom
~ 5) itaconate and fumarate, maleic anhydride, vinylidene chloride, styrene, divinylbenzene, vinyl chloride, vinyl acetate, vinyl acetal, ethylene, propylene, butene, butylene, methylpentene, butadiene, vinyltoluene, acrylonitrile,
Methacrylonitrile, acrylamide, acrylic acid,
Methacrylic acid, itaconic acid, fumaric acid, citraconic acid,
Obtained by polymerizing monomers containing at least one ethylenically unsaturated monomer selected from the group consisting of crotonic acid, β-acryloxypropionic acid, hydroxyalkyl (alkyl group having 1 to 6 carbon atoms) acrylate and methacrylate. A polymer or a polymer blend containing the polymer. (2) A silicone derivative having at least one group selected from the structural units represented by the following general formula (I) or (I '). Embedded image (3) One or more resins of nylon, polyester, epoxy, amino alkyd, urethane, polyacetal or polycarbonate. (4) Polyorganosilsesquioxane obtained by hydrolyzing and condensing methyltrialkoxysilane or a partial hydrolyzate / condensate thereof in an aqueous solution of ammonia or amines. (5) Silica or porous silica, sodium silicate glass, soda-lime glass powder, aluminosilicate, silicon carbide, layered silicate, quartz sand, aluminum oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium phosphate, chromium oxide, emery , Dolomite, mica powder, silica, diatomaceous earth, kaolinite, halloysite, montmorillonite, illite, vermiculite, hectorite, bentonite, chitin powder, chitosan powder or hydroxyapatite. 7. The spherical particles according to claim 1, wherein the spherical particles are obtained by emulsion polymerization or suspension polymerization of a polymerizable monomer.
7. The detergent-impregnated article according to any of 6. 8. The method according to claim 1, wherein said cleaning agent contains 1 to 200 parts by weight of polyorganosiloxane and 100 to 10,000 parts by weight of water based on 100 parts by weight of said spherical particles. A cleaning agent-impregnated article according to any one of the above. 9. The cleaning according to claim 8, wherein the polyorganosiloxane is liquid at normal temperature and has at least one group selected from the structural units represented by the general formula (I) or (I ′). Agent impregnated articles. 10. The detergent-impregnated article according to claim 8, wherein the polyorganosiloxane is represented by the following general formula (II). Embedded image 11. The cleaning agent according to claim 1, wherein the spherical particles are 0.1 to 2 particles.
0% by weight, 0.01 to 20% of the above polyorganosiloxane
Organic solvent having a boiling point of 70 to 300 ° C.
The detergent-impregnated article according to any one of claims 1 to 10, comprising% by weight and the balance being water. 12. The cleaning impregnated article according to claim 11, wherein the organic solvent is represented by the following general formula (III). Embedded image 13. The cleaning agent according to claim 1, further comprising at least one selected from a surfactant and a polymer dispersant.
13. The cleaning agent-impregnated article according to any of the above items 12. 14. The detergent-impregnated article according to claim 1, wherein the substrate comprises a flexible porous structure such as paper, nonwoven fabric, woven fabric, knitted fabric, and plastic foam. 15. The detergent-impregnated article according to claim 1, wherein the substrate can be impregnated with 50 to 5,000% by weight of a detergent under no load based on the weight of the substrate. . 16. The detergent-impregnated article according to claim 1, which is for a hard surface. 17. A method for cleaning a hard surface, comprising using the cleaning agent-impregnated article according to claim 1 to clean a hard surface.