JP2826097B2 - Liquid cleaning composition in spray container - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an improved and novel
Particularly, the present invention relates to a liquid cleaning composition in a spray container suitable for cleaning hard surfaces. More specifically, it is a cleaning composition containing water-insoluble spherical particles, sprayed from a spray-type container to the surface to be cleaned in the form of foam, mist, or fine droplets. The present invention relates to a liquid detergent composition in a spray-type container which can maintain good spray characteristics even when used for a long time without causing any problem.

[0002]

2. Description of the Related Art In a liquid detergent, a water-insoluble particle such as an abrasive or a opaque agent such as a synthetic resin emulsion is blended for the purpose of enhancing the detergency. Techniques for giving a good liquid feeling and enhancing palatability are already known, and such products are widely distributed. In such a solid-dispersed liquid detergent composition, it is common practice to stabilize the dispersion of solid particles by increasing the viscosity of the detergent composition and maintain a uniform dispersion state.

On the other hand, in recent years, in consideration of user's convenience, those in a spray type container in which a cleaning liquid can be directly applied to a wide range of a surface to be cleaned have been widely used. In the case of the cleaning composition in a spray-type container, when the water-insoluble particles are contained in the cleaning composition for the above-described purpose, it is impossible to spray when the viscosity of the cleaning composition is high, and the viscosity is low. If it is low, spraying is possible, but there is a problem that the spray nozzles are often clogged during use and spraying becomes impossible. It is conceivable to increase the diameter of the injection nozzle to make it difficult to clog, but if the diameter is too large, the liquid will be sprayed linearly when spraying, and the liquid will be applied over a wide area of the surface to be cleaned. There was a problem that the original convenience was lost.

[0004]

Means for Solving the Problems The inventors of the present invention have found that a liquid cleaning agent to be used in a spray-type container does not impair sprayability even if solid particles are contained, and troubles such as clogging of an injection nozzle can be solved. As a result of intensive investigations to obtain a cleaning composition having no specific composition, the composition contains spherical water-insoluble particles having a specific particle size, and a cleaning composition having a specific viscosity is sprayed with a specific nozzle diameter. It has been found that such a problem can be solved if used in a container, and the present invention has been completed.

That is, the present invention provides the following components (A), (B) and
(C), the content of the component (A) is 0.1 to 20% by weight,
(B) A detergent composition having a component content of 0.1 to 30% by weight and a viscosity at 20 ° C. of 1 to 2000 cps. Another object of the present invention is to provide a liquid cleaning composition in a spray-type container, which is used by spraying it onto a surface to be cleaned in the form of fine droplets. (A) Water-insoluble spherical particles having an average particle size of 0.01 to 15 μm (B) Surfactant (C) Water

[0006]

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

The component (A) of the present invention has an average particle size of 0.01 to 15 μm.
m of water-insoluble spherical particles. When the average particle size of the spherical particles is less than 0.01 μm, the performance as particles such as enhancement of detergency, imparting an opaque appearance cannot be exhibited, and
If it exceeds, the spray nozzle of the spray container is easily clogged, which is not preferable. A more preferable range of the average particle size is 0.1 to 10
μm, and more preferably 1 to 5 μm.

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 irradiation in any one of a dispersion medium of water, methanol, 1% C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₆ H aqueous solution. After performing the measurement, the particle size is measured with a light diffusion type particle size distribution analyzer (such as HORIBA LA-500). 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.

The mixing ratio of the component (A) in the detergent composition of the present invention is 0.1 to 20% by weight. 0.1% by weight
When the amount is less than the above, performances derived from solid particles such as abrasive power cannot be exhibited.

The component (A) must have a spherical shape.
In the case of an irregular shape, the injection nozzle of the spray container is easily clogged, which is not preferable. More specifically, in number percent
A shape in which the projected image of 90% or more particles draws a perfect circle or a circumcircle of the projected image, and all the contours of the projected image are included between the concentric circle having a radius of 90% of the circumscribed circle and the circumcircle It is particularly preferred to have

Although the material of the component (A) is not particularly limited, it has an effect on spray characteristics when used in a spray-type container, and the more hydrophobic the particle surface, the more difficult it is to cause clogging. Therefore, the main component of the spherical particles is
It is preferable that the surface energy measured on a plane alone is 60 mN / m or less.

The component (A) needs to be appropriately dispersed at the time of use. To disperse in a low-viscosity composition, the true specific gravity of the component (A) must be in the range of 0.5 to 2.5. preferable. Outside of this range, the separation in the detergent composition is accelerated, and it is not preferable because the separation occurs during use and the composition of the sprayed detergent changes significantly. Particularly preferred true specific gravity is in the range of 0.5 to 1.5.

Further, the dispersibility of the component (A) in the detergent composition is greatly affected by the particle size. If the particle size is too small, the particles tend to aggregate, which is not preferable. It is not preferable because the separation speeds up. For this reason, in order to obtain a good dispersion state in the composition, it is particularly preferable that the true specific gravity is 0.5 to 1.5 and the average particle size is in the range of 1 to 5 μm.

The component (A) of the present invention may satisfy one or more components selected from the group consisting of the following (A-1) to (A-5) in order to satisfy the above conditions. Are preferable, and particularly those selected from (A-2) are preferable.

(A-1): alkyl acrylates and methacrylates having 1 to 8 carbon atoms, mono- and di-alkyl (alkyl groups having 1 to 5 carbon atoms) itaconate and fumarate, maleic anhydride, vinylidene chloride, styrene, divinyl Benzene, 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 Acid, beta-acryloxypropionic acid, hydroxyalkyl (alkyl group having 1 to 6 carbon atoms)
A monomer containing at least one ethylenically unsaturated monomer selected from the group consisting of acrylates and methacrylates, or a polymer obtained by polymerizing these monomers.

(A-2): a silicone resin comprising a structural unit represented by the following general formula (I) or (I ')

[0018]

Embedded image

(Wherein R ₁ , R ₂ and R ₃ are the same or different and each have an alkyl group having 1 to 100 carbon atoms, an alkoxy group, a hydroxyalkyl group, an OH group, a carboxyl group, a carboxyalkyl group, an N- ( 2-aminoalkyl) aminoalkyl group, aminoalkyl group, amino group, epoxyalkyl group, epoxy group, methylpolyoxyethylenealkyl group, hydroxypolyoxyethylenealkyl group, methylpolyoxyethylene / polyoxypropylene group, hydroxypolyoxy An ethylene / polyoxypropylene group, an alkylpolyoxyethylene group, a polyoxyethylene group, a phenyl group or a fluorinated alkyl group).

(A-3): A resin of at least one of nylon, polyester, epoxy, aminoalkyd, urethane, polyacetal and polycarbonate.

(A-4): Polyorganosilsesquioxane obtained by hydrolyzing and condensing methyltrialkoxysilane or its partial hydrolysis / condensate in an aqueous solution of ammonia or amines (A-5): Silica or porous silica.

The method for producing the spherical particles as the component (A) of the present invention by synthesis or the like is not particularly limited.
When the constituent material of the spherical particles is a polymer, a polymer obtained by polymerizing a monomer in a state of being dispersed or emulsified in water is preferable because the desired spherical particles are easily obtained.

The surfactant of the component (B) of the present invention itself functions as a main component for washing, but also has a function of making the spherical particles of the component (A) easily wet with water and dispersing them uniformly in water. For this reason, if the compounding amount is insufficient, not only the detergency is insufficient, but also the ability of the component (A) to improve the wettability with water is insufficient, and the component (A) cannot be uniformly dispersed in water.
On the other hand, if the amount is too large, the composition becomes extremely thick and becomes unsuitable for use in a spray container. For this reason, the preferred blending ratio of the component (B) in the cleaning composition of the present invention is in the range of 0.1 to 30% by weight, more preferably 0.5 to 5% by weight.

The surfactant used in the present invention is not particularly limited, and one or more selected from the group consisting of the following (B-1) to (B-4) may be used as a component. Are preferred.

(B-1): The following general formula (II), (III) or
A compound represented by the formula (IV), a linear or branched fatty acid salt having 8 to 20 carbon atoms, an α-olefin sulfonate having 8 to 20 carbon atoms, an alkane sulfonate having 8 to 20 carbon atoms, and One or more anionic surfactants selected from the group consisting of chain alkyl (C6-18) benzenesulfonates (provided that the salts are alkali metal salts, alkaline earth metal salts, ammonium salts or It is an alkanolamine salt having 1 to 5 carbon atoms.)

[0026]

Embedded image

(Wherein, R ₄ is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, R ₅ is a linear or branched alkylene group having 2 to 4 carbon atoms, and g is 0 or Number of one, h
Is a number of 0 to 5, i is a number of 0 to 10 as an average value, M is an alkali metal, an alkaline earth metal, ammonium or an alkanolamine of 1 to 5 carbon atoms, and R ₆ is a straight chain of 5 to 15 carbon atoms. Or a branched alkyl or alkenyl group, R ₇ is the same as R ₆ or a hydrogen atom. Examples of the compound represented by formula (II), (III) or (IV) include alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether acetate, alkyl diphenyl ether disulfonate and the like. Can be

(B-2): One or more cationic surfactants selected from the group consisting of compounds represented by the following general formulas (V) and (VI).

[0029]

Embedded image

(Wherein R ₄ , g and h have the same meanings as described above, R ₈ represents a methyl group or a linear or branched alkyl or alkenyl group having 6 to 11 carbon atoms, and X represents a halogen atom. Represents an atom or an alkyl sulfate residue.) Examples of these cationic surfactants include alkyl trimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, and dialkyl dimethyl ammonium salts.

(B-3): The following general formulas (VII), (VIII) and (IX)
Or 1 selected from the group consisting of compounds represented by (X)
One or more nonionic surfactants.

[0032]

Embedded image

(Wherein, R ₄ , g, h and R ₅ have the same meanings as described above, j is an average number of 1 to 100, R ₉ is a hydroxyl group or a linear or branched group having 1 to 18 carbon atoms.) Chain alkoxy group, n
Is an average number of 1 to 10, p is an average number of 0 to 10, k is an average number of 0 to 5, G is a residue derived from a reducing sugar having 5 to 6 carbon atoms, m the number of 1-5 in average, R _10, R ₁₁
And R ₁₂ each represent an acyl group having 8 to 22 carbon atoms or a hydrogen atom, and q, r and s each represent a number of 0 to 100 on average. However, in the formula (X), at least one of R ₁₀ , R ₁₁ and R ₁₂ is an acyl group having 8 to 22 carbon atoms. Examples of these nonionic surfactants include polyoxyethylene alkyl ether, alkyl polyglycoside, fatty acid diethanolamide, fatty acid monoglyceride, and the like.

(B-4): One or more amphoteric surfactants selected from the group consisting of compounds represented by the following general formula (XI) or (XII).

[0035]

Embedded image

(Wherein R ₄ , g and h have the same meanings as above, R ₁₃ and R ₁₄ are alkyl or alkanol groups each having 1 to 3 carbon atoms, t is a number of 0 or 1, and Y is Hydrogen atom or hydroxyl group, u is a number from 0 to 5, Z is COO ^- or S
O ₃ ^- is shown. ) These amphoteric surfactants include alkyl betaines,
Examples include alkylhydroxysulfobetaine, amidopropylbetaine, tertiary amine oxide, and the like.

In the present invention, particularly preferred component (B) is, among the above (B-1) to (B-4), economical efficiency, detergency and (A)
In terms of dispersibility with respect to the components, one or more components selected from the group consisting of linear alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates, fatty acid salts, alkyl polyglycosides, and polyoxyethylene alkyl ethers are constituent components. It is assumed that.

The cleaning composition of the present invention can maintain good spray characteristics without causing clogging of the injection nozzle even when used in a spray type container. It is further improved by incorporating a polyorganosiloxane oil as the component (D) into the product. Although the detailed reason for this is not clear, it is thought that the polyorganosiloxane oil acts as a lubricant during use and prevents the spherical particles from sticking near the injection nozzle.

The compounding amount of the component (D) for the above purpose is (A)
The amount is preferably 1 to 1000 parts by weight based on 100 parts by weight of the spherical particles of the component. If the amount is less than 1 part by weight, the effect of adding the component (D) is insufficient, and if the amount is too large, the effect is saturated.
Addition exceeding 1000 parts by weight is wasteful and is economically undesirable. However, when the polyorganosiloxane oil of the component (D) is incorporated into the detergent composition, it can remain on the surface to be cleaned and impart various properties. For example, wiping at the time of work becomes lighter, gloss is applied to the surface to be cleaned after cleaning, and a darkening effect is applied to the surface to be cleaned. When the component (D) is blended for these purposes, the blending amount is not limited to the above.

Examples of the polyorganosiloxane oil as the component (D) include those having at least one group selected from the structural units represented by the general formula (I) or (I '). It is preferable that the organo group of the oil is one or more groups selected from an alkyl group having 1 to 80 carbon atoms or a phenyl group. In order to increase the mobility of the spherical particles, the viscosity of the polyorganosiloxane oil at 25 ° C. is more preferably 2 to 5000 cs.

Specific examples of the polyorganosiloxane oil used in the present invention include dialkylsiloxane, alkylphenyl silicone, alkyl-modified silicone,
Alkoxy-modified silicones, hydroxy-modified silicones, carboxy-modified silicones, epoxy-modified silicones, amino-modified silicones and the like include the following general formula (X
Compounds represented by III) are particularly preferred.

[0042]

Embedded image

(Wherein a1 and a2 are 0-100, b is 1-50
Indicates an integer of 00. The cleaning composition of the present invention can maintain good spray characteristics without causing clogging of the injection nozzle even when used in a spray type container. When the polymer dispersant is added as the component (E) in combination with the component (B) and the component (B), a remarkable effect is obtained.

The compounding amount of the polymer dispersant of the component (E) is preferably 1 to 100 parts by weight based on 100 parts by weight of the spherical particles of the component (A). A clear addition effect is not exhibited, and if it exceeds 100 parts by weight, conversely aggregation tends to occur, which is not preferable.

Preferred examples of the component (E) include those having 1 carbon atom.
To 8 alkyl acrylates and methacrylates, mono- and di-alkyl (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 (alkyl A monomer having at least one ethylenically unsaturated monomer selected from the group consisting of acrylates and methacrylates, vinylpyrrolidone and derivatives thereof Those was collected using the like. These polymer dispersants have a molecular weight of 1,
It is preferably in the range of 000 to 1,000,000, particularly in the range of 50,000 to 100,000 and water-soluble.

Preferred examples of the component (E) include high molecular polysaccharides. Examples of the high molecular polysaccharide include the following (E-1)
Preferably, one or more selected from the group consisting of (E-3) to (E-3) is used as a component.

(E-1): Guar gum, locust bean gum, quince seed gum, tara gum, carrageenan, alginic acid (or a salt thereof), fasseran, agar, arabinogalacta gum, gum arabic, tragacanth gum, karaya gum, pectin, starch, Xanthan gum, Zancote, Zanflo, curdlan, succinoglucan, schizophyllan, pullulan, gellan gum, welan gum, lanzan gum, galactomannan, hyaluronic acid (or salt thereof), chondroitin sulfate (or salt thereof), chitin,
Chitosan.

(E-2): Oxidized, methylated, carboxymethylated, hydroxyethylated, hydroxypropylated, sulfated, phosphorylated or cationized derivative of the polysaccharide shown in (E-1) : Water-soluble cellulose derivative The above-mentioned polymer polysaccharide has a molecular weight of 1,000 to 1,
Preferred are those which are in the range of 10 million, especially in the range of 5,000 to 1,000,000 and are water-soluble.

The viscosity of the cleaning composition of the present invention at 20 ° C. is 1 to 2000 cp for use in a spray container.
s range. If the viscosity is less than 1 cps, the particle size of the liquid sprayed in the form of droplets is too small, so that the liquid tends to be scattered, which is not preferable. If it exceeds 2,000 cps, the spray characteristics are remarkably impaired.

The spray type container for containing the cleaning composition of the present invention has a spray nozzle having a nozzle diameter of 0.1 to 2 mm, and the cleaning liquid is applied to the surface to be cleaned in a foam, mist, or fine droplet form. Any shape can be used as long as it can be ejected. If the injection nozzle diameter of the injection nozzle is less than 0.1 mm, it is difficult to spray the cleaning liquid regardless of the presence or absence of the spherical particles, which is not preferable. On the other hand, if it exceeds 2 mm, the sprayed droplets become rough or are sprayed linearly, and the sprayable area becomes extremely small, which is not preferable. A more preferable range of the nozzle diameter is a range of 0.3 to 1 mm.

Examples of the spray container include a trigger type spray container, a pump type spray container, and an aerosol. The trigger type spray container is particularly preferable from the viewpoint of general consumers' recognition, economy and environmental compatibility.

Although the use of the cleaning composition of the present invention is not particularly limited, it can be used for walls, floors, tatami mats, ceilings, inside and outside homes.
Washing of roofs, washing of bathroom fixtures such as bathroom walls, floors, doors, bathtubs, washbasins, etc., washing of kitchen walls, floors, around sinks, around microwave ovens, ventilation fans, cupboards, chests, table,
Washing of furniture such as desks, chairs, bookshelves, etc., washing of the surface of appliances such as refrigerators, TVs, personal computers, stereos, air conditioners, microwave ovens, washing machines, dryers, lighting equipment, etc. Cleaning of glass used for doors, windows of automobiles, etc., cleaning of screen doors, cleaning of toilet floors, walls, doors, toilets, toilet seats with a cleaning function, heating toilet seats, washing dishes, cooking utensils, automobiles, bicycles Suitable for cleaning painted surfaces, plated surfaces, plastic surfaces of motorcycles, etc., cleaning of automobile wheels, cleaning around exterior entrances, terraces, fences, fences, gates, and other hard surfaces in general. Furthermore, it is particularly suitable for cleaning painted surfaces, plated surfaces, plastic parts surfaces, window glasses and wheels of automobile bodies.

In practicing the present invention, various substances can be added to the composition of the present invention as long as the effects intended by the present invention are not impaired. Examples of such are fragrances, pigments, dyes, fungicides, fungicides, solubilizers, chelating agents, antioxidants, ultraviolet absorbers, pH adjusters, bleaching agents, thinners, thickeners. , Dispersants, solvents and the like.

[0054]

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.

Examples 1 to 14 and Comparative Examples 1 to 10 Using the water-insoluble spherical particles or the comparative water-insoluble particles of the present invention shown in Table 2 in the formulation shown in Table 1, the detergent composition of the present invention or the comparative example was used. Was prepared. The obtained cleaning composition was evaluated for clogging when used in a trigger type spray container by the following test method. Table 3 shows the results.
The viscosities of the cleaning compositions of Examples and Comparative Examples were all in the range of 1 to 50 cps at 20 ° C.

<Clogging Test> 500 ml of the detergent composition was placed in a commercially available trigger-type spray container (trigger type spray container used for a simple mypet (manufactured by Kao Corporation) with a nozzle diameter of 0.8 mm) at room temperature. It was stored in a constant temperature room at 65 ° C. and a humidity of 65% to obtain a test sample. This test sample is taken daily
Sprays were actually sprayed five times, and the presence or absence of clogging was checked. Such a test was continued for three months, and the ease of clogging was evaluated according to the following criteria.

Criteria ◎: No abnormality for 3 months ○: No abnormality for more than 2 months, but clogging occurs by the end of 3 months △: No abnormality for more than 1 month, but clogging by the end of 2 months ×: The clogging occurs in less than one month.

[0058]

[Table 1]

Note) * 1: Trade name KF-54, manufactured by Shin-Etsu Chemical Co., Ltd. * 2: Use hydrochloric acid or sodium hydroxide

[0060]

[Table 2]

Note) * 1: The sphericity is determined by taking an electron micrograph of a solid particle with a scanning electron microscope and finding that the particles do not overlap.
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. * 2: Trade name Tospearl 105, manufactured by Toshiba Silicone Co., Ltd. * 3: Trade name Tospearl 130, manufactured by Toshiba Silicone Co., Ltd. * 4: Trade name Tospearl 3120, manufactured by Toshiba Silicone Co., Ltd. * 5: Product name Tospearl 240, manufactured by Toshiba Silicone Co., Ltd.

[0062]

[Table 3]

Examples 15 to 20 and Comparative Examples 11 to 14 Cleaning compositions having the compositions shown in Table 4 were prepared, and clogging tests were carried out in the same manner as in Example 1. Table 4 shows the results.

[0064]

[Table 4]

Note) * 1: Trade name: Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.
Average particle size 2μm, true specific gravity 1.3, surface energy 28mN / m,
Sphericality 95 * 2: Trade name KF-96, manufactured by Shin-Etsu Chemical Co., Ltd. * 3: Using hydrochloric acid or monoethanolamine Examples 21 to 25 and Comparative Example 15 A cleaning composition having a composition shown in Table 5 Was prepared, and a clogging test was performed in the same manner as in Example 1. Table 5 shows the results.

[0066]

[Table 5]

Note) * 1: Trade name KMP-590, manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 2 μm, true specific gravity 1.3, surface energy 28 mN / m, sphericity
91 * 2: Trade name KF-96, manufactured by Shin-Etsu Chemical Co., Ltd. * 3: Trade name Kelzan AR, manufactured by Kelco * 4: Trade name Genugam RL-200, Copenhagen Pectin Factory * 5: Trade name Primal ASE -95NP, manufactured by Rohm & Haas Co. * 6: Using hydrochloric acid or monoethanolamine Examples 26 to 28 and Comparative Examples 16 to 17 A cleaning composition having the composition shown in Table 6 was prepared and sprayed as shown in Table 7 The same clogging test as in Example 1 and the following spray characteristic test were carried out in trigger type spray containers having different nozzle orifices. Table 7 shows the results.

<Spray Characteristics Test> A cleaning agent composition was prepared by changing the nozzle diameter at the tip of the nozzle of a trigger type spray container used in a commercially available trigger type spray container (Easy My Pet (Kao Co., Ltd.)). 500 ml of the sample was used as a test sample. Keep the black plastic plate horizontal,
The cleaning liquid was sprayed at an angle of about 90 degrees from a height of 30 cm above, and the ease of spraying and the spray pattern of the cleaning liquid sprayed on the plastic plate were evaluated according to the following criteria. In addition, switching of the spray pattern of the container was used in the "broad foam".

Ease of spraying ：: The trigger pull is light and easy to spray △: The trigger pull is heavy and difficult to spray ×: Cannot spray (no liquid) Spray pattern ○: Can be sprayed over a diameter of 10 cm or more ×: Can be sprayed only in a range of less than 10 cm in diameter

[0070]

[Table 6]

Note) * 1: Trade name: Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.
Average particle size 2μm, true specific gravity 1.3, surface energy 28mN / m,
Sphericality 95 * 2: Trade name KF-54, manufactured by Shin-Etsu Chemical Co., Ltd. * 3: Use hydrochloric acid or sodium hydroxide

[0072]

[Table 7]

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiyuki Nakazawa 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 17/04 C11D 17/08

Claims (20)

(57) [Claims] (1) It contains the following components (A), (B) and (C),
A cleaning composition having a component (A) content of 0.1 to 20% by weight, a component (B) content of 0.1 to 30% by weight, and a viscosity at 20 ° C. of 1 to 2000 cps. 0.1-2mm
A liquid cleaning composition in a spray-type container, which is sprayed from the spray-type container into a foam, a mist, or a fine droplet onto a surface to be cleaned. (A) Water-insoluble spherical particles having an average particle size of 0.01 to 15 μm (B) Surfactant (C) Water 2. A spherical image of the component (A), in which the projected image of particles having a number percentage of 90% or more makes a perfect circle or a circumcircle of the projected image, and has a radius of 90% of the radius of the circumscribed circle. The cleaning composition according to claim 1, wherein the cleaning composition has a shape including all the contours of the projected image between the concentric circle and the circumcircle. 3. The cleaning composition according to claim 1, wherein the main component of the spherical particles of component (A) has a surface energy of 60 mN / m or less as measured on its own plane. 4. The average particle diameter of the spherical particles of the component (A) is 0.1 to 0.1.
The cleaning composition according to any one of claims 1 to 3, which is 10 µm. 5. The spherical particles of component (A) have a true specific gravity of 0.5 to 2.
The cleaning composition according to any one of claims 1 to 4, wherein 6. The average particle diameter of the spherical particles of the component (A) is from 1 to 5.
and a true specific gravity of 0.5 to 1.5.
The cleaning composition according to any one of claims 5 to 10. 7. The spherical particles of the component (A) are as follows:
The cleaning composition according to any one of claims 1 to 6, which comprises one or more components selected from the group consisting of (A-5). (A-1): alkyl acrylates and methacrylates having 1 to 8 carbon atoms, mono- and di-alkyl (alkyl groups having 1 to 5 carbon atoms) itaconate and fumarate, maleic anhydride, vinylidene chloride, styrene, divinylbenzene, chloride Vinyl, vinyl acetate, vinyl acetal, ethylene, propylene, butene, butylene, methylpentene, butadiene, vinyltoluene, acrylonitrile,
Methacrylonitrile, acrylamide, acrylic acid,
Methacrylic acid, itaconic acid, fumaric acid, citraconic acid,
A monomer containing at least one ethylenically unsaturated monomer selected from the group consisting of crotonic acid, beta-acryloxypropionic acid, hydroxyalkyl (alkyl having 1 to 6 carbon atoms) acrylate and methacrylate, or polymerizing these monomers (A-2): a silicone resin comprising a structural unit represented by the following general formula (I) or (I ′): (Wherein R ₁ , R ₂ and R ₃ are the same or different and have 1 to 1 carbon atoms)
100 alkyl, alkoxy, hydroxyalkyl, OH, carboxyl, carboxyalkyl,
N- (2-aminoalkyl) aminoalkyl group, aminoalkyl group, amino group, epoxyalkyl group, epoxy group, methylpolyoxyethylenealkyl group, hydroxypolyoxyethylenealkyl group, methylpolyoxyethylene / polyoxypropylene group, It represents a hydroxypolyoxyethylene / polyoxypropylene group, an alkylpolyoxyethylene group, a polyoxyethylene group, a phenyl group or a fluorinated alkyl group. (A-3): any one or more resins of nylon, polyester, epoxy, amino alkyd, urethane, polyacetal or polycarbonate (A-4): methyltrialkoxysilane or its partial hydrolysis / condensate is ammonia or Polyorganosilsesquioxane obtained by hydrolysis and condensation in aqueous solution of amines (A-5): silica or porous silica 8. The method according to claim 1, wherein the spherical particles are obtained by polymerization in a state of being dispersed or emulsified in water.
The cleaning composition according to any one of claims 7 to 10. 9. The surfactant of the component (B) comprises the following component (B-1):
The cleaning composition according to any one of claims 1 to 8, comprising one or more components selected from the group consisting of (B-4) to (B-4). (B-1): a compound represented by the following general formula (II), (III) or (IV), a linear or branched fatty acid salt having 8 to 20 carbon atoms,
Α-olefin sulfonate having 8 to 20 carbon atoms, 8 carbon atoms
One or more anionic surfactants selected from the group consisting of alkane sulfonates of from 20 to 20 and linear alkyl (C 6 to C 18) benzene sulfonates (provided that the salts are alkali metal salts , Alkaline earth metal salts, ammonium salts or alkanolamine salts having 1 to 5 carbon atoms). Embedded image (In the formula, R ₄ is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, R ₅ is a linear or branched alkylene group having 2 to 4 carbon atoms, and g is a number of 0 or 1. , H is a number from 0 to 5, i is a number from 0 to 10 on average, M is an alkali metal,
Alkaline earth metals, ammonium or alkanolamines having 1 to 5 carbon atoms, R ₆ is a linear or branched alkyl or alkenyl group having 5 to 15 carbon atoms, R ₇ is the same as R ₆ or a hydrogen atom . (B-2): One or more cationic surfactants selected from the group consisting of compounds represented by the following general formula (V) or (VI). Embedded image (Wherein, R ₄ , g and h have the same meaning as described above, R ₈ represents a methyl group or a linear or branched alkyl or alkenyl group having 6 to 11 carbon atoms, and X represents a halogen atom or an alkyl (B-3): one or more selected from the group consisting of compounds represented by the following general formulas (VII), (VIII), (IX) or (X) Nonionic surfactant. Embedded image (Wherein R ₄ , g, h and R ₅ have the same meanings as described above;
Is an average number of 1 to 100, R ₉ is a hydroxyl group or a carbon number of 1 to 18
Is a linear or branched alkoxy group, and n is an average of 1
Number of ~ 10, p is the number of 0-10 on average, k is 0 of average
G is a residue derived from a reducing sugar having 5 to 6 carbon atoms, m is a number of 1 to 5 on average, and R ₁₀ , R ₁₁ and R ₁₂ are each an acyl group having 8 to 22 carbon atoms. Or, a hydrogen atom, q, r and s represent a number of 0 to 100 on average. However, in the formula (X), at least one of R ₁₀ , R ₁₁ and R ₁₂ has 8 carbon atoms.
To 22 acyl groups. (B-4): One or more amphoteric surfactants selected from the group consisting of compounds represented by the following general formulas (XI) or (XII). Embedded image (Wherein, R ₄ , g and h have the same meanings as described above, R ₁₃ and R ₁₄ are each an alkyl group or alkanol group having 1 to 3 carbon atoms, t is a number of 0 or 1, Y is a hydrogen atom or hydroxyl, u is the number of 0 to 5, Z is COO ^- or SO ₃ ^- shows a). 10. The method according to claim 1, further comprising 1 to 1000 parts by weight of a polyorganosiloxane oil as the component (D) based on 100 parts by weight of the spherical particles of the component (A). Detergent composition. 11. The washing according to claim 10, wherein the polyorganosiloxane oil as the component (D) has at least one group selected from the structural units represented by the general formula (I) or (I ′). Composition. 12. The polyorganosiloxane oil of component (D), wherein the organo group is at least one group selected from an alkyl group having 1 to 80 carbon atoms or a phenyl group.
Or the cleaning composition according to 11. 13. The polyorganosiloxane oil as component (D) has a viscosity at 25 ° C. of 2 to 5000 cs.
The cleaning composition according to any one of claims 12 to 12. 14. The cleaning composition according to claim 10, wherein the polyorganosiloxane oil as the component (D) is a compound represented by the following general formula (XIII). Embedded image (In the formula, a1 and a2 represent an integer of 0 to 100, and b represents an integer of 1 to 5000.) 15. A polymer dispersant as a component (E),
The cleaning composition according to any one of claims 1 to 14, which contains 1 to 100 parts by weight based on 100 parts by weight of the spherical particles of the component (A). (16) The polymer dispersant of the component (E) has 1 carbon atom.
To 8 alkyl acrylates and methacrylates, mono- and di-alkyl (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 (alkyl A monomer containing at least one ethylenically unsaturated monomer selected from the group consisting of acrylates and methacrylates, vinylpyrrolidone and derivatives thereof. 15. detergent composition according is obtained by. 17. The cleaning composition according to claim 15, wherein the polymer dispersant as the component (E) is a polymer polysaccharide. 18. The high-molecular polysaccharide comprises the following (E-1) to (E-3)
The cleaning composition according to claim 17, wherein one or more kinds selected from the group consisting of: (E-1): guar gum, locust bean gum, quince seed gum, tara gum, carrageenan, alginic acid (or a salt thereof), furcelan, agar, arabinogalacta gum, gum arabic, tragacanth gum, karaya gum, pectin, starch, xanthan gum, zancoat , ZanFlo, curdlan, succinoglucan, schizophyllan, pullulan, gellan gum, welan gum, orchid gum,
Galactomannan, hyaluronic acid (or its salt), chondroitin sulfate (or its salt), chitin, chitosan (E-2): oxidation, methylation, carboxymethylation, hydroxyethylation of the polysaccharide shown in (E-1) , Hydroxypropylated, sulfated, phosphorylated or cationized derivatives (E-3): water-soluble cellulose derivatives 19. The spray-type container according to claim 1, wherein the spray-type container is a trigger-type spray container having an injection nozzle diameter of 0.3 to 1 mm.
The cleaning composition according to any one of claims 18 to 18. 20. The cleaning composition according to claim 1, which is used for cleaning a painted surface of an automobile body, a surface of a plastic part, a plated surface, a window glass, or a wheel.