JP2826099B2 - Liquid detergent composition for hard surfaces and method for cleaning hard surfaces - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid cleaning composition for hard surfaces for cleaning hard surfaces of automobile bodies and the like, and a method for cleaning hard surfaces. For more information,
The hard surface on which the solid particle stain is present can be directly washed without a preliminary washing with water or the like and with a very small amount of liquid. The present invention relates to a liquid cleaning composition for hard surfaces and a method for cleaning hard surfaces, the surface of which can be cleaned without causing damage due to dirt.

[0002]

2. Description of the Related Art
In order to clean the hard surface where solid particle stains derived from house dust, soil, earth and sand are present, for example, when washing a car body or the like, the hard surface is prevented from being damaged by the solid particle stains. It was necessary to wash other stains while removing solid particle stains with excess water or a detergent solution or after removing them in advance. Also,
There is also a problem that the hard surface is damaged by the wiping material (cloth, paper, nonwoven fabric, sponge, etc.) used at the time of washing. However, in general, it is often impossible to use a large amount of water at a place where a hard surface to be cleaned exists,
Further, even if possible, the use of a large amount of water significantly impaired the workability. This is true for all commercially available hard surface cleaners for this application.

In general, lubrication is used as a method of preventing a hard surface from being damaged by friction between solid particles and a hard surface. In general lubrication, a lubricant is adsorbed on the solid particle surface and the hard surface. By forming a local pressure-resistant lubricating film, scratching is prevented. Therefore, it is necessary to use a lubricant that has a high adsorptive power to both the solid particles and the hard surface that are in contact with each other and that does not break the adsorbed film under the local pressure. For this reason, the molecular structure of the lubricant does not deform under the local pressure due to contact. And the frictional force between the lubricating molecules must be small.

However, in this case, as the amount of lubricant adsorbed on the surface to be cleaned is increased and the ability to prevent scratching is increased, the lubricant itself remains as dirt, which is considered to be advantageous, for example, in preventing scratching. If a manual operation of wiping with a lubricant such as grease is added, the effect of preventing scratching is low and the substance itself remains as dirt, making it impossible to remove dirt. Also, the more enhanced prevention capability damage by hard to destroy the lubricating film in the station pressure, also shear resistance of the lubricant by fibers such as cloth when working wiping with a cloth or the like becomes excessive, wiping of about 0.1 m ² The workability deteriorates to the extent that work is substantially impossible even with washing.

[0005] Accordingly, an object of the present invention is to clean a hard surface on which solid particle dirt is present without pre-cleaning and without using a large amount of water and detergent, thereby making the cleaning process very simple and adding labor. Another object of the present invention is to provide a hard surface cleaning composition and a method for cleaning a hard surface, which can significantly reduce the surface roughness of the surface to be cleaned and can be finished without impairing the appearance of the surface to be cleaned.

[0006]

Accordingly, the present inventors have conducted intensive studies from the viewpoint of wiping and cleaning a hard surface on which solid particle contamination is present without damaging it with a small amount of liquid without preliminary cleaning. Contains specific spherical particles, wiping and cleaning with a composition adjusted to a specific viscosity,
The book has found that it has high performance in preventing scratches during wiping and cleaning of hard surfaces with solid particle stains, has good workability and detergency, and has a tremendous effect in maintaining the beautiful appearance of the surface to be cleaned. The invention has been completed.

That is, the present invention relates to a liquid cleaning composition for hard surfaces, which is applied to a hard surface having solid particle stains and wipes off the stains to clean the hard surface. A washing medium, and (b) spherical particles having an average particle diameter of 0.01 to 15 μm insoluble in the liquid washing medium,
The content of the component (b) in the composition is 0.1 to 30% by weight, and the viscosity at 20 ° C. is 2 to 500 c under uniform stirring.
The present invention provides a liquid detergent composition for hard surfaces, which is characterized by ps.

Further, the present invention provides a liquid lubricating component as a component (c) in addition to the components (a) and (b),
The composition for providing a liquid detergent composition for a hard surface as described above, characterized in that the component and the component (c) are contained so that the blending ratio of the component and the component (c) is (c) / (b) (weight ratio) = 0.01 to 10. It is.

Further, the present invention is characterized in that a surfactant or a polymer dispersant or a mixture thereof is further contained as a component (d) in addition to the components (a), (b) and (c). A liquid cleaning composition for hard surfaces is provided.

Further, the present invention provides the above-mentioned cleaning composition,
A method for cleaning a hard surface, comprising applying to a hard surface on which solid particulate soil is present and wiping the hard surface together with the soil, particularly (a) a liquid cleaning medium; Average particle size insoluble in liquid cleaning medium 0.01 ~
It contains 15 μm spherical particles and (c) a polyorganosiloxane oil which is liquid at 20 ° C., wherein the content of the component (b) in the composition is 0.1 to 30% by weight, and the components (b) and (c) The mixing ratio with the components is (c) / (b) (weight ratio) = 0.01 to 10, and the viscosity at 20 ° C. under uniform stirring is 2 to 500 c.
An object of the present invention is to provide a method for cleaning an automobile body, which comprises applying a liquid detergent composition of ps to an automobile body having solid particle stains without pre-cleaning, and wiping the same together with the stains.

In the present invention, the spherical particles having high motility circulate under the pressure of the hand so as to entrain the solid dirt particles, thereby reducing the contact ratio to the hard surface as the surface to be cleaned to the utmost. (Circulation dilution effect), and a large amount of particles perform free motion in the cleaning liquid to disperse the stress caused by hand, thereby lowering the contact pressure itself at the time of contacting the abrasive particles (contact pressure reduction effect). Expresses the anti-scratch effect.

In the present invention, it is important that the free movement of the particles used is sufficiently performed in order to exhibit a sufficient anti-scratch effect. For that purpose, the viscosity of the system of the liquid cleaning composition of the present invention at 20 ° C. is as low as 2 to 500 cps, and the particles in the cleaning composition of the present invention have little interaction, and It is most important that the shape hardly causes agglomeration, that is, the shape is spherical, and that the average particle size is approximately the same size (0.01 to 15 μm) as the solid particle soil,
At the same time, it is more effective that the surface energy is low.

In order to more effectively realize the anti-scratch effect, the true specific gravity of the spherical particles must be 0.5 to 2 in order to maintain an appropriate contact rate with a hard surface and an appropriate circulation motility in a cleaning solution. .
5 and a moderate value, furthermore, when the pressure at the time of wiping is applied, the particles keep free movement without deforming,
Since the elastic modulus is 10 kg / mm ² or more and the particles do not scratch the surface to be cleaned, the elastic modulus is 1000 kg / m2.
it is effective at m ² or less.

Further, the particles in the cleaning composition of the present invention are:
By adding a liquid lubricating component of solid dirt particles and spherical particles that are not easily adsorbed to the surface to be cleaned, preferably polyorganosiloxane oil, the free movement of the spherical particles, which is the basis of the anti-scratch effect of the present invention, is improved. The anti-scratch effect can be enhanced.

Further, the spherical particles in the present invention pseudo-enlarge the specific surface area of the material used for wiping the dirt, and because the free movement is large for the above-mentioned reasons, only the dirt can be efficiently removed without damaging the surface to be cleaned. Can be removed.

Further, the use of water as the liquid cleaning medium further enhances the anti-scratching and detergency. Since solid particle stains remaining on general hard surfaces are derived from house dust, soil, and soil, the surface of the particle stains is hydrophilic, and the presence of a certain amount of water in the system makes it effective in the cleaning solution. This is because particle dirt can be dispersed.

The free movement of the spherical particles used in the present invention is particularly hindered by high-viscosity oily components caused by oily dirt, such as oxidatively polymerized fats and oils and high-viscosity oily substances derived from exhaust gas. Therefore, it is preferable to add an organic solvent in addition to water as a liquid cleaning medium in order to increase the cleaning power of the surface to be cleaned without hindering the free movement of the particles and without damaging the particles. In addition, when this organic solvent is used in combination with the liquid lubricating component, for example, polyorganosiloxane oil, the viscosity of the liquid lubricating component is reduced, and the mobility of the particles can be further increased. desirable. Furthermore, when a surfactant or a polymer dispersant is blended, the particles are prevented from agglomerating and substantially free movement is ensured, and at the same time, the dispersion of solid particle dirt is promoted, and in terms of both scratch resistance and detergency. preferable.

[0018]

Embodiments of the present invention will be described below in detail.

The cleaning composition of the present invention contains a liquid cleaning medium as the component (a). The liquid cleaning medium in the present invention is a liquid medium having a boiling point of less than 300 ° C. and facilitating desorption of solid particle stains.
Organic solvents of up to 300 ° C. and silicone oils having a boiling point of less than 300 ° C. (one or more of cyclic silicone, volatile dimethyl siloxane, etc.). Among them, water or a mixture of water and an organic solvent is preferable, and a mixture of water and an organic solvent is more preferable. Further, the mixing ratio of the mixture of water and the organic solvent is preferably water: organic solvent (weight ratio) = 5 to 20: 1. The mixture may be in any form such as an emulsification system, a solubilization system, and a separation system.

Examples of the organic solvent used in the present invention include a hydrocarbon solvent having 8 to 20 carbon atoms and an ether solvent represented by the following general formula (III).

CH ₃ (CH ₂ ) _p O (CH ₂ CH ₂ O) _q (C ₃ H ₆
O) _r (CH ₂ ) _s R ₄ (III) (wherein R ₄ represents H, CH ₃ or OH, and p, q, r and s each represent an integer of 0 to 20). Specific examples of the solvent include hydrocarbon solvents such as decane, undecane, dodecane, tridecane, tetradecane, isoparaffin, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl. Examples include ether solvents such as ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol dimethyl ether, and hydrocarbon solvents are particularly preferable.

The cleaning composition of the present invention contains, as the component (b), spherical particles having an average particle diameter of 0.01 to 15 μm, which are insoluble in the liquid cleaning medium. The spherical particles used in the present invention,
It is a concept that includes not only a true sphere but also an ellipsoidal shape, but high sphericity defined below is involved in the mobility and non-aggregation of particles, and a sphericity of 90 or more is preferable .

<Sphericity> An electron micrograph of the solid particles was taken with a scanning electron microscope, and 100 particles in which the particles did not overlap were randomly selected, and the projected image of the particles was a perfect circle or a projected image. Let me draw a circumcircle,
The sphericity of a particle was defined as the number of particles having a shape including the entire contour of the projected image between a concentric circle having a radius of 90% and a circumscribed circle.

The average particle diameter of the spherical particles used in the present invention is from 0.01 to 15 μm, preferably from 0.1 to 10 μm, more preferably from 1 to 5 μm. Average particle size is 0.01 ~ 15μ
Within the range of m, the efficiency is the same as the efficiency based on the number of particles per unit weight and the size of solid particle stains generally existing on the hard surface to be cleaned, and the cleaning efficiency for the solid particle stains is improved. In the present invention, the average particle size of the spherical particles is measured by the following method.

<Measurement Method of Average Particle Size> The particles are completely dispersed by ultrasonic waves in a dispersion medium of water, methanol, and 1% C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₆ H aqueous solution. Then, the particle size is measured with a light diffusion type particle size distribution analyzer (such as HORIBA LA-500). The weight ratio of particles / dispersion medium was determined by adding particles to the dispersion medium until the concentration indication value of the particle size distribution measurement device was displayed as "optimum".

From the obtained particle size, an average particle size on a volume basis is calculated and defined as the average particle size in the present invention. However, when the average particle diameter is a, the maximum value of the measured particle diameter is a + a /
2 or more, or when the minimum value is aa / 2 or less,
Based on the standard deviation δ of the measured particles, a−δ is used to calculate a + δ.
The average particle size on a volume basis is calculated again only for particles having a particle size in the range described above, and is defined as the average particle size in the present invention.

In addition, the specific gravity of the spherical particles of the present invention is set to a true specific gravity of 0.5 in order to satisfy an appropriate contact ratio with a hard surface in a washing solution and an appropriate circulation motility in the washing solution during washing.
Is preferably in the range of ~ 2.5, more preferably
0.5 to 1.5. Similarly, it is preferable that the cohesive force between the particles is low in order to enhance the mobility on the hard surface, and the surface energy of the constituent material of the particles capable of achieving this is
Those having 60 dyne / cm or less are preferred. Here, the surface energy refers to a value measured by the following measuring method.

<Method of Measuring Solid Surface Energy> The surface tension γ is considered to be the sum of a term (γ ^d ) caused by London's dispersion force and a term (γ ^p ) caused by other polar forces. γ = γ ^d + γ ^p (1) Also, by measuring the contact angles of two liquids (distilled water and methylene iodide) for which γ ^d and γ ^p are known, γ ^d and γ ^p Is obtained by calculation.

(B ₁ + C ₁ + a ₁ ) γ ^d γ ^p + c ₁ (b ₁ -a ₁ ) γ ^d + b ₁ (c ₁ -a ₁ ) γ ^p −a ₁ b ₁ c ₁ = 0 (2) (b ₂ + C ₂ + a ₂ ) γ ^d γ ^p + c ₂ (b ₂ -a ₂ ) γ ^d + b ₂ (c ₂ -a ₂ ) γ ^p −a ₂ b ₂ c ₂ = 0… (3) a ₁ = (1/4) γ ₁ (1 + cos θ ₁ ) a ₂ = (1/4) γ ₂ (1 + cos θ ₂ ) b ₁ = γ ₁ ^db ₂ = γ ₂ ^d c ₁ = ^{_{γ 1 p c 2 = γ 2}} p θ 1; contact angle theta ₂ on the solid surface of the distilled water; the surface tension of the contact angle distilled water on a solid surface of methylene iodide _{γ 1 = 72.8dyne / cm γ 1} d = 22.1 dyne / cm γ ₁ ^p = 50.7 dyne / cm ・ Surface tension of methylene iodide γ ₂ = 50.8 dyne / cm γ ₂ ^d = 44.1 dyne / cm γ ₂ ^p = 6.7 dyne / cm (2) and (3) From the formula, the dispersion force component of the surface tension of the solid (γ ^d )
And the polar force component (γ ^p ) are calculated and substituted into the equation (1) to calculate the surface tension of the solid, that is, the surface energy.

In the present invention, the spherical particles do not deform even when pressure is applied at the time of wiping, maintain free movement, provide a sufficient anti-scratch effect, and damage the surface to be cleaned by the particles themselves. Does not occur, its elastic modulus must be
Preferably it is 10 to 1000 kg / mm ² . More preferably
A 50~500kg / mm ^2, more preferably 100 to 300 /
a mm ^2. In the present invention, the elastic modulus is measured by the following method.

<Method of Measuring Elastic Modulus> Using a microcompression tester PCT-200 for powder (manufactured by Shimadzu Corporation), particles 1 were measured.
The compression displacement is measured for each piece, and the value E calculated from the load at the time of deformation of the particle diameter by 10% using the following equation is defined as the elastic modulus of the particles. However, the measurement is performed at 20 to 25 ° C., and the particles to be measured have a particle size of 3 to 10 μm. If the particle size is not in this range, the measurement is performed on particles of the same material having a particle size of 3 to 10 μm, and the elastic modulus of the particle is determined.

F: compressive force (kg) S: amount of compressive deformation (mm) E: compressive elastic modulus of the particles (elastic modulus, kg / mm ² ) R: particle radius (mm)

[0033]

(Equation 1)

As the constituent material for satisfying the above conditions for the spherical particles of the present invention, it is preferable to use one or two or more selected from the group consisting of: Preferred are those selected from, and particularly preferred are those selected from and
Further, the best one is selected from:

Alkyl acrylates and methacrylates (alkyl groups having 1 to 8 carbon atoms), mono- and di-alkyls (alkyl groups having 1 to 5 carbon atoms) itaconates and fumarate, maleic anhydride, vinylidene chloride, styrene, divinylbenzene, Vinyl chloride, vinyl acetate, vinyl acetal, ethylene, propylene, butene, isobutylene, methylpentene, butadiene, vinyltoluene, acrylonitrile, methacrylonitrile,
Acrylamide, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, citraconic acid, crotonic acid, β-acryloyloxypropionic acid, hydroxyalkyl (having 1 to 6 carbon atoms in the alkyl group) acrylate and at least one selected from the group consisting of methacrylates Polymer obtained by polymerizing one kind of ethylenically unsaturated monomer A silicone resin comprising a structural unit represented by the following general formulas (I) and (I ') [for example, Trefil R-925, R
-930, R-935 (manufactured by Toray Dow Corning Co., Ltd.)]

[0036]

Embedded image

(Wherein R ₁ , R ₂ and R ₃ are the same or different and each has an alkyl group having 1 to 100 carbon atoms, an alkoxy group, a hydroxyalkyl group, a hydroxyl group, a siloxy group, a carboxyl group, a carboxyalkyl group, -(2-aminoalkyl) aminoalkyl group, aminoalkyl group, amino group,
Epoxyalkyl group, epoxy group, methylpolyoxyethylene alkyl group, hydroxypolyoxyethylene alkyl group, methylpolyoxyethylene / polyoxypropylene group, hydroxypolyoxyethylene / polyoxypropylene group, alkylpolyoxyethylene group, polyoxyethylene A phenyl group or a fluorinated alkyl group. ) Nylon, polyester, epoxy, amino alkyd, urethane, polyacetal or polycarbonate resin at least one of methyl trialkoxy silane or its partial hydrolysis / condensation product is hydrolyzed / condensed in aqueous solution of ammonia or amines The resulting polyorganosilsesquioxane (for example, Tospearl 103, 105, 108, 120, 130, 1
45, 2000B (manufactured by Toshiba Silicone Co., Ltd.), KMP-590,
KMP-590C (manufactured by Shin-Etsu Chemical Co., Ltd.)] Silica or porous silica It comprises the ethylenically unsaturated monomer described above and the structural units represented by the above general formulas (I) and (I '). Polymer Copolymerized with Silicone Derivative Monomer The above resin, polyorganosilsesquioxane, or silica or porous silica is converted to the ethylenically unsaturated monomer described above and / or the above-mentioned general formula (I) ) And a polymer modified with a silicone derivative monomer comprising the structural unit represented by (I ′) [for example,
Polyorganose sesquioxane / silica / polymers obtained by addition polymerization of acrylic acid, methacrylic acid, trimethylhydroxysiloxane, etc. utilizing silanol groups present on the surface of porous silica] Or a polymer in which a silicone derivative monomer comprising a structural unit represented by the above general formula (I) or (I ′) is incorporated [for example, partial oxidation of a main chain, epoxy group And a polymer obtained by addition polymerization of acrylic acid, methacrylic acid, and trimethylhydroxysiloxane after forming a reaction site by the addition reaction of 0.1 to 30% by weight of the above-mentioned spherical particles.
contains. When the content of the spherical particles is less than 0.1% by weight, the amount of the particles is smaller than that of the solid particle soil generally present on the surface to be cleaned, and the scratch-preventing property, which is the gist of the present invention, is significantly reduced, which is not preferable. . If it exceeds 30% by weight, the particles become excessively large as compared with the liquid mixture, the motility of the particles is impaired, the scratch-preventing property is reduced, and the removal of the particles after washing becomes difficult, and the workability is impaired. Therefore, it is not preferable.

The viscosity of the detergent composition of the present invention should be within the range of 2 to 500 cps at 20 ° C. with uniform stirring in order to enhance the free movement of the spherical particles and more effectively prevent scratches. It is necessary that it is 3 to 100 cps, more preferably 3 to 50 cps. In the present invention, the viscosity is a value measured by the following method.

<Measurement Method of Viscosity> A 100 ml sample was placed in a viscosity measurement beaker (inner diameter φ3.6 cm, height 13 cm).
Immerse in a constant temperature water bath at 20 ° C for 30 minutes or more.
After confirming, cover with wrap or the like and shake vigorously up and down 30 times or more to make the whole uniform. After shaking, 10
Within 60 seconds, turn the No. 1 rotor of type B viscometer (Tokimec Inc.)
After rotating at rpm, the value indicated by the pointer one minute later is defined as the viscosity (cps) in the present invention.

The viscosity of the detergent composition at 20 ° C. is 2 cps.
If the particle size is less than 1, the mobility of the spherical particles is too high, and the wiping material makes it difficult to wipe the spherical particles themselves.As a result, the cleaning power is reduced, and the particles are prevented from moving before dispersing the stress from the hand. The wound effect is reduced. Also, if it is higher than 500 cps, the movement of the spherical particles is inhibited,
Since the diluting effect and the local pressure dispersing effect are reduced and the slidability of the material to be wiped is deteriorated, the force required at the time of work is significantly increased, and further, the force for holding the wiped material is also increased. The normal stress is increased, resulting in accelerated scratching. On the other hand, if it is higher than 500 cps, the wiping property of the composition itself is deteriorated, and the detergency is also reduced in conjunction with the reduction in workability.

When the cleaning composition of the present invention is used by putting it in a spray container, the spray container can be widely used by human power or at home because it can be jetted with a wide jet by discharging from a narrow nozzle. Pressurized gas (10kg / cm
⁽² or less), the composition viscosity is preferably 200 cps or less, preferably 100 cps or less, more preferably 50 cps or less. If it exceeds 200 cps, it becomes virtually impossible to discharge for the above reason.

The cleaning composition of the present invention optionally contains a liquid lubricating component as component (c) in order to further enhance the effect of the cleaning liquid used for cleaning. The liquid lubricating component used in the present invention has a boiling point of 300 ° C. or higher and a viscosity of 500 cps.
The following low-viscosity liquid components are referred to, specifically, silicone oils that are liquid at 20 ° C. and have a boiling point of 300 ° C. or higher, such as polyorganosiloxane oils. The component (c) includes so-called waxes, specifically, vegetable waxes such as carnauba wax and cotton wax; animal waxes such as beeswax and wool wax (lanolin); and minerals such as montan wax and ceresin wax. Wax, solid paraffin, microcrystalline wax,
It does not include petroleum waxes such as polyethylene waxes and their oxidized waxes or synthetic waxes. This is because such waxes rather easily take up dirt and lower the performance as a cleaning agent.

In the present invention, the polyorganosiloxane oil liquid at 20 ° C. used as the component (c) includes those composed of the structural units represented by the above general formulas (I) and (I ′). Wherein the organo group of the polyorganosiloxane oil is an alkyl group having 1 to 80 carbon atoms, an aminoalkyl group, an N- (2-aminoalkyl) aminoalkyl group, a methylpolyoxyethylene alkyl group, an alkoxy group, an epoxyalkyl group, a carboxyalkyl group. Alternatively, those which are at least one group selected from phenyl groups are preferable. In order to increase the mobility of the spherical particles, the viscosity of the polyorganosiloxane oil at 25 ° C.
More preferably, it is 50005000 cps.

Specific examples of the polyorganosiloxane oil used in the present invention include dialkylsiloxane, alkylphenyl silicone, alkyl-modified silicone,
Examples thereof include an alkoxy-modified silicone, a hydroxy-modified silicone, a carboxy-modified silicone, an epoxy-modified silicone, and an amino-modified silicone, and a compound represented by the following general formula (II) is particularly preferable.

[0045]

Embedded image

Wherein n ₁ and n ₂ are 1 to 100, m is 1 to 50
Indicates an integer of 00. These polyorganosiloxane oils are, for example, KF
56, KF-412, KF-413, KF-414, KF50, KF53, KF54, KF56,
KF994, KF995, KF9937, X22-161AS, X22-161A, X22-16
1B, KF8012, KF393, KF859, KF860, KF861, KF867, KF8
69, KF880, KF8002, KF8004, KF8005, KF858, KF864, K
F865, KF868, KF8003, KF-105, X22-163A, X22-163B, X
22-163C, KF-1001, KF101, X22-169AS, X22-169B, KF-1
02, X22-162A, X22-162C, X22-3701E, X22-3710, X22-16
0AS, KF6001, KF6002, KF6003, X22-4015, KF-857, KF86
2, KF8001, X22-3667, X22-3939A (Shin-Etsu Chemical Co., Ltd.)
), TSF-451, TSF4700, TSF4701 (manufactured by Toshiba Silicone Co., Ltd.) and the like, and these can be used.

The content of the component (c) in the cleaning composition of the present invention is such that the weight ratio of the component (b) to the component (c) is (c) / (b) = 0.01 to 10. Is preferable, and a ratio that is 0.1 to 5 is more preferable. Also,
The cleaning composition of the present invention has a boiling point as component (a).
1 to 10% by weight of an organic solvent at 70 to 300 ° C and 50 to 97% by weight of water,
Particularly preferred are those containing 1 to 10% by weight of spherical particles of component (b) and 1 to 10% by weight of polyorganosiloxane oil as component (c).

The cleaning composition of the present invention preferably further contains a surfactant or a polymer dispersant or a mixture thereof as the component (d). That is, the spherical particles alone,
Alternatively, in the state where one or both of a liquid lubricating component such as a polyorganosiloxane oil and / or an organic solvent are added to the spherical particles, water is used by using at least one selected from a surfactant and a polymer dispersant. And emulsification, dispersion or re-dispersion of spherical particles is preferably carried out.

The surfactant content in the detergent composition of the present invention is preferably 0.001 to 5% by weight, more preferably 0.01 to 2% by weight. The content of the polymer dispersant is 0.
It is preferably from 001 to 3% by weight, more preferably from 0.01 to 1% by weight.

The surfactant used in the present invention includes:
Anionic or nonionic surfactants are preferred, specifically, alkyl benzene sulfonate, alkyl sulfonate, polyoxyethylene alkyl ether sulfonate, alkyl polyglycoside, fatty acid salt, alkyl sucrose ester, sorbitan alkyl ester and poly One or more selected from the group consisting of oxyethylene alkyl esters, wherein the average alkyl chain length is 8 to 18 carbon atoms
Are preferred.

The polymer dispersants used in the present invention include alkyl acrylate and methacrylate (alkyl group having 1 to 8 carbon atoms), mono- and di-alkyl (alkyl group having 1 to 5 carbon atoms) itaconate and fumarate, Maleic anhydride, vinylidene chloride, styrene, divinylbenzene, vinyl chloride, vinyl acetate, vinyl acetal, ethylene, propylene, butene, isobutylene, methylpentene, butadiene, vinyltoluene, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid, methacrylic Acid, itaconic acid, fumaric acid, citraconic acid, crotonic acid, β-acryloyloxypropionic acid, hydroxyalkyl (alkyl having 1 to 6 carbon atoms) acrylate and methacrylate, vinylpyrrolidone and Include those obtained by polymerizing a monomer containing at least one ethylenically unsaturated monomer selected from the group consisting of derivatives. The molecular weight of these polymer dispersants is preferably 100,000 to 100,000,
More preferably, 1000 to 50,000, most preferably 3000 to 1
It is ten thousand.

The method for cleaning a hard surface according to the present invention is a method for cleaning the hard surface by applying the above-described cleaning composition to a hard surface having solid particle stains and wiping the hard surface together with the stains. However, a preferred embodiment of the cleaning method of the present invention comprises: (a) a liquid cleaning medium; (b) spherical particles having an average particle diameter of 0.01 to 15 μm insoluble in the liquid cleaning medium; Liquid polyorganosiloxane oil, and the content of the component (b) in the composition is 0.1%.
(C) / (b) (weight ratio) = 0.01 to 10 and the viscosity at 20 ° C. under uniform stirring is 2 to 30% by weight. This is a method of cleaning a car body by applying a liquid detergent composition of 500 cps to a car body having solid particle stains without pre-cleaning and wiping the car body together with the stains.

In the present invention, the method of applying the cleaning composition to the hard surface is not particularly limited, and examples thereof include a method of applying with a wiping material and a method of spraying with a spray.

In the present invention, it has been found that the above-mentioned spherical particles are required to be more than a certain area of the hard surface or a certain ratio to the amount of dirt when the hard surface is washed. 0.05-
The most effective area is 5 g / m ² and the projected area of the spherical particles is 30 to 300% of the surface area of the hard surface, and more preferably 0.2 to ² g / m ² by weight.
It is preferable to perform cleaning within a range of 50 to 200% in m ² and a total projected area. The total projected area was calculated by the following method.

<Method of calculating total projected area> Amount of solid particles incorporated into composition a% Hard surface area to be cleaned bcm ² Amount of composition used for cleaning cg Average projected area per 1 g of particles ^* dcm ² / g When

[0056]

(Equation 2)

* Average projected area dcm ² / g per g of particle
Is determined by the following equation.

When the average particle diameter is ecm and the density of the particles is fg / cm ³

[0059]

(Equation 3)

The pH of the cleaning composition of the present invention is not particularly limited, but is preferably in the range of 3 to 12, more preferably 5 to 10.

The use form of the cleaning composition of the present invention is not particularly limited, but it is preferable to use it in a trigger type sprayer. Further, as the properties of the cleaning composition when sprayed on the surface to be cleaned, various forms such as foam, mist, and liquid are conceivable, and are not limited by the properties, but in terms of workability during cleaning. It is particularly preferred that the composition is in the form of a mist or liquid.

The hard surface to be cleaned by the cleaning method of the present invention is not particularly limited.
Examples include stainless steel, artificial marble, plastics such as acrylic and ABS, and resin-coated or metal-plated surfaces such as metal, wood, and plastic. In particular,
Washing inside and outside walls, floors, tatami mats, ceilings, roofs, etc., kitchen walls, floors, around microwave ovens, ventilation fans, cupboards, chests,
Cleaning of furniture such as tables, desks, chairs, bookshelves, etc., refrigerators, TVs, personal computers, stereos, air conditioners, microwave ovens, washing machines, dryers, lighting equipment, etc. Washing of glass used for furniture doors, car windows, etc., washing of screen doors, washing of toilet floors, walls, doors, toilet seats with a washing function, heating toilet seats, washing dishes, cooking utensils, automobiles, bicycles ,
Suitable for cleaning painted surfaces such as motorcycles and plastic surfaces, cleaning wheels of automobiles, cleaning around exterior entrances, terraces, fences, fences, gates, and other hard surfaces where solid particle contamination exists. .
Furthermore, it is suitable for cleaning the painted surface of a car body, the surface of plastic parts, window glass, and wheels, and particularly suitable for cleaning the body of a car.

In practicing the present invention, various substances can be blended as long as the effects of the present invention are not impaired. Examples of such substances include fragrances, pigments, dyes, fungicides, fungicides, solubilizers, chelating agents, antioxidants, pH adjusters, bleaching agents, thickeners, dispersants, ultraviolet absorbers, etc. Is mentioned.

When the detergent composition of the present invention is used, hard surfaces having solid particle stains such as those derived from house dust / soil and earth and sand can be applied / sprayed or wiped on the target surface without preliminary cleaning. The amount to be used after impregnation is 50 g or less per 1 m ^{2 of} the hard surface. Even when the dirt is wiped off with a cloth / nonwoven fabric / paper / sponge / skin / synthetic leather or a similar wiping material, the hard surface is damaged. Is prevented.

[0065]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Using the spherical particles shown in Table 1 and the compounding ingredients shown in Table 2, cleaning compositions of the present invention and a comparative cleaning composition were prepared. That is, Tables 3 to
The spherical particles according to the present invention shown in Table 1 were blended as the blending component 1 in the blending systems 1 to 42 of the present invention shown in FIG. 6 and the comparative blending systems 1 to 30 to obtain the detergent compositions shown in Tables 7 to 10 (the remainder was water ) Was prepared, and its scratch resistance was evaluated by the following method.
The results are shown in Tables 7 to 10. Tables 11 to 14 show the viscosities at 20 ° C of the cleaning compositions prepared in the same manner.

<Method for Evaluating Scratch-Preventive Performance During Wiping and Washing> Rapeseed oil: carbon black = 9: 1 on a black acrylic plate
The mixture (weight ratio) was applied at 1 g / m ² and dried at 60 ° C. for one month. On this dried acrylic plate, "JIS test dust 7 kinds" (IWAMOTO MINERAL
(Manufactured by CO.) A 0.1% ethanol dispersion is sprayed at 10 g / m ² and dried at 60 ° C. for 24 hours. The various detergent compositions were sprayed thereon so as to be 10 g / m ^2, and wiped and washed with a cotton pile cloth towel with a load of 10 g weight / cm ² until the test dust was completely removed.

The acrylic plate treated with the above detergent composition and the acrylic plate treated only with water had a gloss of 60 ° (J
Using a specular gloss measurement device described in IS Z 8741), and the scratch resistance index was calculated by the following formula.

[0069] (gloss of untreated acrylic plate) = G _I (glossiness when treated with water) = G _W (glossiness when treated with liquid combination) = when the G _t

[0070]

(Equation 4)

[0071]

[Table 1]

Note) * 1: Molar ratio 60/5/20/5/10, molecular weight about 100,000 * 2: Molar ratio 55/5/15/5/10 / crosslinking agent (divinylbenzene) 10 * 3: True The sphericity is measured by taking an electron micrograph of a solid particle with a scanning electron microscope and determining that the particles do not overlap. 1
00 are randomly selected, and the projected image of the particle is drawn as a perfect circle or a circumcircle of the projected image, and the contour of the projected image is defined between a concentric circle having a radius of 90% of the radius of the circumscribed circle and the circumscribed circle. The sphericity of the particles was determined by the number of particles having all the included shapes. The same applies hereinafter.

[0073]

[Table 2]

Note) * 1: Poly (diphenylsiloxane / phenylmethylsiloxane / dimethylsiloxane) represented by the following chemical formula (IV), phenyl group / methyl group ratio = 2/8, refractive index
1.480, viscosity 175cst (25 ℃), Shin-Etsu Chemical Co., Ltd. K
F-54

[0075]

Embedded image

* 2: Poly (N) represented by the following chemical formula (V)
-(2-aminoethyl) aminopropyl methyl siloxane / dimethyl siloxane), amino equivalent 6125 g / mol,
Refractive index 1.403, viscosity 60cst (25 ℃), Shin-Etsu Chemical Co., Ltd.
Made KF-393

[0077]

Embedded image

* 3: Polyethylene polydimethyl siloxane block polymer represented by the following chemical formula (VI), silicone / polyethylene composition ratio = 98/2 (weight fraction), molecular weight about 2,000

[0079]

Embedded image

* 4: Poly (hydroxyalkylmethylsiloxane / dimethylsiloxane) represented by the following chemical formula (VII), viscosity 170 cst (25 ° C.), refractive index 1.412

[0081]

Embedded image

* 5: Dicarboxyethyl polydimethylsiloxane represented by the following chemical formula (VIII), carboxyl equivalent
1500g / mol, refractive index 1.402, viscosity 100cst (25 ℃)

[0083]

Embedded image

* 6: Bis (2,2) represented by the following chemical formula (IX)
3-epoxypropyl) polydimethylsiloxane, epoxy equivalent 2790 g / mol, refractive index 1.409, viscosity 103 cst (25
℃)

[0085]

Embedded image

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

[0089]

[Table 6]

Note) *: In the blending systems of Tables 3 to 6, the balance is water.

[0091]

[Table 7]

[0092]

[Table 8]

[0093]

[Table 9]

[0094]

[Table 10]

[0095]

[Table 11]

[0096]

[Table 12]

[0097]

[Table 13]

[0098]

[Table 14]

Example 2 Using the particles shown in Tables 15 to 17 and the components shown in Table 18, cleaning compositions of the present invention and a comparative cleaning composition were prepared. That is, Table 19 ~
Tables 15 to 15 as the blending components 31 in the blending systems 1 to 37 shown in 20
The cleaning compositions shown in Tables 19 to 20 were prepared by blending the spherical particles according to the present invention shown in FIG. 17 or comparative particles, and the anti-scratch performance was evaluated in the same manner as in Example 1. Table 21-
See Figure 26.

[0100]

[Table 15]

[0101]

[Table 16]

[0102]

[Table 17]

[0103]

[Table 18]

Note: * 1 to * 6 are the same as * 1 to * 6 in Table 2. * 7: Poly (methylpolyoxyethylenepropyl methylsiloxane / dimethylsiloxane) represented by the following chemical formula (X), viscosity 320 cst (25 ° C), refractive index 1.439

[0105]

Embedded image

* 8: Poly (carboxyethylmethylsiloxane / N- (2-aminoethyl) aminopropylmethylsiloxane / dimethylsiloxane) represented by the following chemical formula (XI), 100 cst (25 ° C.)

[0107]

Embedded image

[0108]

[Table 19]

[0109]

[Table 20]

Note) *: In the blending systems of Tables 19 to 20, the balance is water.

[0111]

[Table 21]

[0112]

[Table 22]

[0113]

[Table 23]

[0114]

[Table 24]

[0115]

[Table 25]

[0116]

[Table 26]

Example 3 The cleaning composition shown in Table 28 was prepared by using the spherical particles shown in Table 27 and blending them in the following blending ratio. Table 28 shows the viscosity at 20 ° C. of this detergent composition and the scratch resistance index evaluated by the same method as in Example 1.

<Cleaning composition> Particles 7.0% Dimethylsiloxane (500 cst, 25 ° C.) 5.0% Isoparaffin, boiling point 262 ° C. 10.0% Alkyl glucoside (C _12-14 ) 2.0% Na polyacrylate (molecular weight 3000) 0.5% Ion Exchange water balance

[0119]

[Table 27]

[0120]

[Table 28]

Example 4 The components shown in Table 29 were blended in the proportions shown in Table 29 to prepare the present or comparative cleaning compositions shown in Table 29. Table 29 shows the viscosity at 20 ° C. of the obtained detergent composition, and the evaluation of detergency and workability evaluated by the following methods.

<Evaluation Method for Detergency> The same amount of soil (rapeseed oil / carbon black, seven kinds of JIS test dusts) of the same amount, 10 cm ×
Attach to a 20cm white acrylic plate. Various detergent compositions were sprayed on the mixture so as to be 10 g / m ^2, and a 2 × 5 cm cotton pile towel was folded in two in the longitudinal direction to obtain 10 g weight /
Apply a load of m ² and wipe the entire surface three times evenly. The dirt removal rate at this time was visually determined in five steps based on the following criteria, and this evaluation was repeated five times to calculate the average of the scores, which was used as the detergency rating in the present invention.

1: The stain cannot be removed at all. 2: The area ratio between the stain-removed part and the non-stained part is 1/4 or more. 3: The area ratio between the stain-removed part and the non-stained part is 2 /. 4 or more 4: The area ratio of the portion where the stain is removed to the portion where the stain is not removed is 3/4 or more 5: The stain is completely removed <Workability evaluation method> Sprinkle on an acrylic plate so as to be 10 g / m ² , 40 cm x 40 cm
Cotton piled towels folded in four, height 15
Five female panelists weighing 5 to 165 cm and weighing 45 to 50 kg are required to perform an operation of completely wiping the detergent composition. The workability at this time was evaluated on a five-point scale according to the following evaluation criteria, and the average of five persons was used as the workability score of the present invention.

1: Impossible to completely wipe off 2: Heavier than water wipe 3: Equivalent to water wipe 4: Lighter than water wipe 5: Equivalent to dry wipe

[0125]

[Table 29]

Note) * 1: Methylpolysiloxane network polymer, spherical particles, average particle size 2 μm, elastic modulus 120 kg / mm ² , surface energy 30 dyn / c
m, true specific gravity 1.3, sphericity 95, KMP- manufactured by Shin-Etsu Chemical Co., Ltd.
590 * 2: Poly (aminopropyl methylsiloxane / dimethylsiloxane), Shin-Etsu Chemical Co., Ltd. KF-868 * 3: Kelco, USA, Kelzan

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaki Tosaka 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Laboratory (56) References JP-A-58-154774 (JP, A) JP-A-2-147677 (JP, A) JP-A-9-3407 (JP, A) JP-A-9-3408 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C11D 7/50 C11D 7/22

Claims (15)

(57) [Claims] (A) a liquid cleaning medium; and (b) an insoluble in the liquid cleaning medium having an average particle size of 0.01 to 15 μm and a true specific gravity of 0.5.
For hard surfaces having a content of component (b) in the composition of from 0.1 to 30% by weight and a viscosity at 20 ° C. under uniform stirring of from 2 to 500 cps. A method for cleaning a hard surface, comprising applying a liquid detergent composition to a hard surface on which solid particulate soil is present without preliminary cleaning, and wiping off the soil to clean the hard surface. (A) a liquid cleaning medium, and (b) an insoluble in the liquid cleaning medium, having an average particle size of 0.01 to 15 μm and a true specific gravity of 0.5.
And spherical particles having an elastic modulus of 10 to 1000 kg / mm ² , and the content of the component (b) in the composition is 0.1 to 30% by weight.
And the viscosity at 20 ° C. under uniform stirring is 2 to 2.
Applying a liquid cleaning composition for hard surfaces that is 500 cps to the hard surface where solid particulate soil is present without pre-cleaning,
A method for cleaning a hard surface, comprising cleaning the hard surface by wiping off dirt. And (b) an insoluble in the liquid cleaning medium, having an average particle size of 0.01 to 15 μm and a true specific gravity of 0.5.
~ ^2.5 , a spherical particle having an elastic modulus of 10 to 1000 kg / mm2,
(C) a liquid lubricating component, wherein the content of the component (b) in the composition is 0.1 to 30% by weight;
(C) / (b) (weight ratio) = 0.01-
A viscosity of 10 at 20 ° C. with uniform stirring
A liquid cleaning composition for hard surfaces of ~ 500 cps, wherein the hard surface is cleaned by applying without pre-cleaning to the hard surface where solid particle stains are present, and wiping off the stains. How to clean hard surfaces. 4. A spherical surface particle of 0.05 to 5 g with respect to a hard surface.
/ At a rate in the range of m ² is applied to detergent compositions, cleaning method according to any one of claims 1 to 3. 5. The cleaning composition according to claim 1, wherein the cleaning composition is applied to the hard surface such that the total projected area of all spherical particles with respect to the surface area of the hard surface is in the range of 30 to 300%. The cleaning method described. 6. The cleaning method according to claim 1, wherein a small amount of a cleaning composition of 50 g or less per m ^{2 of} hard surface is applied. (A) a liquid cleaning medium, and (b) an insoluble in the liquid cleaning medium having an average particle size of 0.01 to 15 μm.
m, spherical particles having an average particle diameter of 0.01 to 15 μm having a true specific gravity of 0.5 to 2.5, and the content of the component (b) in the composition is 0.1 to 30.
% By weight and having a viscosity at 20 ° C. of from 2 to 500 cps with uniform stirring.
A liquid detergent composition for hard surfaces used in the cleaning method according to any one of the above. 8. The cleaning composition according to claim 7, wherein the spherical particles have an elastic modulus of 10 to 1000 kg / mm ² . 9. It further comprises (c) a liquid lubricating component,
The compounding ratio of the component (b) and the component (c) is (c) / (b)
The cleaning composition according to claim 7, wherein (weight ratio) = 0.01 to 10. 10. 10. The cleaning composition according to claim 9, wherein the liquid lubricating component (c) is a polyorganosiloxane oil which is liquid at 20 ° C. 11. The method according to claim 7, further comprising (d) a surfactant or a polymer dispersant or a mixture thereof.
The cleaning composition according to any one of the above. 12. The surface energy of the constituent material of the spherical particles is
The cleaning composition according to any one of claims 7 to 11, wherein the cleaning composition is 60 dyn / cm or less. 13. The spherical particles according to the following general formula (I):
And polyorganosilsesquis obtained by hydrolyzing and condensing a methyl trialkoxysilane or its partial hydrolyzate / condensate in an aqueous solution of ammonia or amines. 13. The cleaning composition according to any one of claims 7 to 12, which is oxane. Embedded image (Wherein R ₁ , R ₂ and R ₃ are the same or different and have 1 to 1 carbon atoms)
100 alkyl groups, alkoxy groups, hydroxyalkyl groups, hydroxyl groups, siloxy groups, carboxyl groups, carboxyalkyl groups, N- (2-aminoalkyl) aminoalkyl groups, aminoalkyl groups, amino groups, epoxyalkyl groups, epoxy groups, Methyl polyoxyethylene alkyl group, hydroxy polyoxyethylene alkyl group, methyl polyoxyethylene / polyoxypropylene group, hydroxy polyoxyethylene / polyoxypropylene group, alkyl polyoxyethylene group, polyoxyethylene group, phenyl group or fluorinated Shows an alkyl group. ) 14. The cleaning composition according to claim 7, wherein the liquid cleaning medium of component (a) is water or a mixture of water and an organic solvent. 15. The hard surface is an automobile body.
A cleaning composition according to any one of claims 7 to 14.