JP3354859B2 - Liquid detergent composition for hard surfaces - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel liquid cleaning composition for hard surfaces containing hydrophobic particles. More specifically, the present invention relates to a liquid cleaning composition for hard surfaces which can be easily redispersed even when hydrophobic particles settle, and has excellent detergency.

[0002]

2. Description of the Related Art For oily dirt firmly fixed to a hard surface, it is effective to use a polishing action of solid particles for cleaning. Examples of the solid particles include a lubricant, a pigment, and the like in addition to the abrasive, and these usually have a true specific gravity of greater than 1. Such solid particles may be used as they are in a powder form, but from the viewpoint of ease of use, it is preferable to use the solid particles dispersed in water as a liquid detergent.

However, there is a specific gravity difference between the solid particles and the water in which the solid particles are dispersed, and the solid particles settle in the water. Once settled, the solid particles solidify, making it difficult to evenly disperse again, even with shaking.

[0004]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies to obtain a liquid detergent composition that is easy to redisperse, by dispersing hydrophobic solid particles having a specific surface energy as secondary particles in a dispersion medium having a specific surface tension, The present inventors have found that a liquid detergent composition for hard surfaces that can be easily redispersed even when hydrophobic solid particles settle out is obtained, and the present invention has been completed.

[0005] That is, the present invention relates to (A) surface energy of 60 mN / m or less, preferably 10 to 50 mN / m, more preferably
In a dispersion medium (B) having a surface tension of 25 to 60 mN / m, preferably 25 to 50 mN / m, hydrophobic particles having a viscosity of 1 to 40 mN / m are dispersed in the form of secondary particles. It is intended to provide a liquid cleaning composition for hard surfaces of 1000 mPa · s, preferably 1 to 500 mPa · s, and more preferably 1 to 200 mPa · s.

In general, when hydrophobic particles are dispersed in water with a surfactant, a strong precipitate is formed upon settling,
It cannot be easily redispersed with gentle shaking. In the present invention, by dispersing the hydrophobic particles in the form of secondary particles, it is possible to easily re-disperse even when precipitated.

There have been various reports of converting hydrophobic particles from primary particles to secondary particles, and systems using this technique to improve redispersibility are used in the fields of inks and paints. . However, in the field of inks and paints, this technique is used where the viscosity of the dispersion is high, and when the viscosity is high, the dischargeability from the container deteriorates and the selectivity of the container narrows. In the liquid detergent composition for hard surfaces targeted by the present invention, it is preferable to provide the liquid detergent composition in a discharge container or the like in consideration of user's convenience, and from this viewpoint, in the present invention, a system in which the viscosity of the dispersion is low is used. And a technique for dispersing the secondary particles.

In the present invention, the component (A) is a hydrophobic particle having a surface energy of 60 mN / m or less, preferably 10 to 50 mN / m, more preferably 15 to 40 mN / m. If this requirement is satisfied, the hydrophobic particles may be of any shape, but if they are used as a trigger spray or squeeze container and the dispersion is discharged and used, clogging will occur at the discharge part Therefore, it is preferable to use spherical particles. The hydrophobic particles have a true specific gravity of 1.0 to 2.5, and the primary particles preferably have an average particle size of 0.01 to 15 μm, particularly 0.1 to 10 μm from the viewpoint of detergency.

The surface energy of the component (A) is determined by preparing a plane from the same material as the hydrophobic particles to be measured, and measuring the contact angles of water and iodomethane with respect to the plane.
Wu et al. (Souheng Wu, J. POLYMER.SCI .: PART C.,
34, 19- (1971)].

It is preferable that the hydrophobic particles of the component (A) specifically include one or more components selected from the group consisting of:

Alkyl (alkyl group having 1 to 1 carbon atoms)
8) Acrylate, alkyl (C 1 to C 1 of alkyl group)
8) methacrylate, mono- or di-alkyl (alkyl group having 1 to 5 carbon atoms) itaconate, mono- or di-alkyl (alkyl group having 1 to 5 carbon atoms) 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-acryloxypropionic acid, hydroxyalkyl (alkyl group having 1 carbon atom)
6) a monomer containing at least one ethylenically unsaturated monomer selected from the group consisting of acrylates and hydroxyalkyl (alkyl groups having 1 to 6 carbon atoms) methacrylate, or a polymer obtained by polymerizing these monomers. A silicone derivative having at least one group selected from the structural units represented by the following general formula (I) or (II).

[0012]

Embedded image

(Wherein R ₁ , R ₂ and R ₃ are the same or different and each represents an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyl 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, hydroxypolyoxyethylene / polyoxypropylene group, alkylpoly It represents an oxypropylene group, a polyoxyethylene group, a phenyl group or a fluorinated alkyl group. When these groups contain carbon atoms, they have 1 to 100 carbon atoms. ) Nylon, polyester, epoxy, amino alkyd, urethane, polyacetal or polycarbonate resin. A polyorganosilsesquioxane obtained by hydrolyzing and condensing methyltrialkoxysilane or a partially hydrolyzed / condensed product thereof in an aqueous solution of ammonia or amines. Silica or porous silica, aluminum oxide, magnesium oxide, titanium oxide, aluminosilicate, silicon carbide, calcium carbonate, calcium phosphate, chromium oxide, emery, quartz sand, dolomite, sand, natural crushed materials such as shells, mica powder, silica stone , Diatomaceous earth, kaoronite, halloysite, montmorillonite, illite, vermiculite.

Among them, polymethylsilsesquioxane is preferred, and the average particle size is particularly preferably 0.01 to 15 μm.
[For example, Trefil R-925, R-930, R-935 (manufactured by Dow Corning Toray Co., Ltd.)].

In the present invention, the component (A) is incorporated in the final composition in an amount of 0.01 to 50% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.

[0016] The liquid detergent composition of the present invention comprises, as secondary particles, some or all of the hydrophobic particles of the component (A).
Dispersion medium having a surface tension of 25 to 60 mN / m, preferably 25 to 50 mN / m
(B).

The hydrophobic particles (A) form secondary particles by adjusting the surface tension of the dispersion medium (B) and the surface energy of (A) itself. In the present invention, the average particle size of the secondary particles (b) is
It is 0.5 to 500 μm, preferably 0.5 to 200 μm, more preferably 1.0 to 200 μm. Average particle size of secondary particles (b)
Can be controlled by changing the surface tension of the dispersion medium (B). Furthermore, the average particle size of the primary particles of the hydrophobic particles (A) (a)
And the average particle size of the secondary particles (b) is: (b) / (a) = 1.1
It is preferably from 5000 to 5000, more preferably from 1.2 to 100, particularly preferably from 1.3 to 10.

In the present invention, the surface tension of the dispersion medium (B) is measured using a Kyowa CBVP surface tensiometer A-3 (manufactured by Kyowa Kagaku Co., Ltd.).

The dispersion medium (B) is of course suitable for cleaning hard surfaces, but typically comprises a surfactant (B-1) and water (B-2).

Here, the surfactant (B-1) includes a C1 to C4 trivalent alcohol, an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, Aromatic sulfonic acids or salts thereof (toluenesulfonic acid or alkali metal salts thereof, xylene sulfonic acid or alkali metal salts thereof, cumenesulfonic acid or alkali metal salts thereof) and the like. For these substances, the surface defined in the present invention by the difference in the structure of the lipophilic group (for example, the carbon chain length or branching of the alkyl group) or the difference in the structure of the hydrophilic group (for example, the sulfonic acid group, the carboxyl group, the hydroxyl group) The concentration at which tension can be applied also varies. In addition, for these substances, in general, when the alkyl group is short, the surface tension does not decrease even at a high concentration, and it is possible to form secondary particles. Is reduced, and the region where secondary particles can be formed shifts to a low concentration, so that the concentration at which the surface tension specified in the present invention can be imparted also varies depending on the substance. Specific examples include 0.1 to 60% by weight for ethanol, 0.001 to 0.5% by weight for sodium laurylbenzenesulfonate, 0.001 to 0.05% by weight for sodium lauryl sulfate, and sodium polyoxyethylene (n = 3) sodium lauryl sulfate ether. 0.001 to 0.05% by weight, and polyoxyethylene (n = 1 to 50) lauryl ether 0.001 to 0.1% by weight.
% By weight, 0.001 to 10% by weight for polyoxyethylene (n = 1 to 8) stearyl ether, 0.001 to 0.1% by weight for polyoxyethylene (n = 8 to 50) stearyl ether, polyoxyethylene (n = 1 to 5) ) For oleyl ether, 0.001 to 5% by weight, polyoxyethylene (n =
5 to 50) 0.001 to 0.1% by weight for oleyl ether, 0.001 to 2% by weight for octyl glucoside, 0.001 to 0.5% for decyl glucoside, 0.0 for dodecyl glucoside
01-0.3% by weight, lauryl dimethylamine oxide
0.001 wt%, chloride monoalkyl (C ₈ ~C ₁₈₎ 0.001~1 wt% trimethyl ammonium, 0.001 wt% chloride dialkyldimethylammonium, monoalkyl trimethyl ammonium -p- toluenesulfonate and dialkyldimethylammonium 0.001 to 10% by weight for ammonium p-toluenesulfonate, 0.001 to 1% by weight for methoxysulfate or ethoxysulfate of monoalkyltrimethylammonium and dialkyldimethylammonium, and 0.001 to 1% by weight for octylbenzyldimethylammonium chloride
0.001 to 10% by weight, 0.001 to 0.5% by weight for laurylbenzyldimethylammonium chloride, 0.001 to 0.1% by weight for lauroylamidopropyldimethylbetaine, lauryldimethylhydroxypropylsulfobetaine
0.001 to 5% by weight, and preferably 0.1 to 50% by weight for sodium m-xylene sulfonate. In the above, n
Is the average number of moles of ethylene oxide added. Also,
These weight percentages are concentrations in the final composition. However,
These concentration ranges are only a rough guide, and may be outside the above range as long as the surface tension of the dispersion medium (B) satisfies 25 to 60 mN / m.

Further, the liquid detergent composition of the present invention has a viscosity (25 ° C.) of 1 to 1000 mPa · s, preferably 1 to 500 mPa · s.
s, more preferably 1 to 200 mPa · s. Here, the viscosity is a value at 25 ° C. measured by a B-type viscometer. By setting the viscosity in this range, an appropriate viscosity is imparted to the composition, which is desirable in terms of handleability.Specifically, when the composition is filled into various containers to form a product, the dischargeability from the container is improved. , A container such as a trigger sprayer or a squeeze former can be selected.

The liquid detergent composition of the present invention preferably contains a viscosity modifier (C) in order to obtain a desired viscosity of the composition. As the component (C), one or more selected from polysaccharides or derivatives thereof, polyacrylic acid or alkali metal salts thereof, and polyvinyl alcohol or derivatives thereof may be mentioned. Specifically, xanthan gum,
Welan gum, ramzan gum, gellan gum, guar gum, tara gum, locust bean gum, carrageenan,
Pectin, alginic acid or an alkali metal salt thereof, carboxymethylcellulose, hydroxyethylcellulose,
One or two selected from hydroxypropylcellulose, sodium polyacrylate and polyvinyl alcohol
Species or more. The component (C) is preferably blended in the range of 0.001 to 5% by weight.

In the liquid detergent composition of the present invention, a water-insoluble or water-soluble solvent used in a general detergent is used for enhancing the detergency of oily stains.
When used as (D), a cleaning effect can be imparted without impairing redispersibility. Specifically, paraffin which is a water-insoluble solvent, polyoxyethylene phenol ether which is a water-soluble solvent, and butyl diglycol are used in amounts of 0.1 to 20.
It is preferable to mix by weight%.

The liquid detergent composition of the present invention can impart a polishing effect without impairing redispersibility by incorporating a polishing component (E). What is blended as the polishing component (E) may be any of those generally used, but it is particularly preferable to use polyorganosiloxane from the viewpoint of the polishing effect. It is preferable that the polyorganosiloxane is incorporated in an amount of 0.1 to 10% by weight.

The liquid detergent composition of the present invention is used for cleaning hard surfaces. The target hard surface is not limited.Washing of walls, floors, tatami mats, ceilings, roofs, etc. inside and outside the house, washing of bathroom equipment such as walls, floors, doors, bathtubs, basins, etc. Cleaning of kitchen walls, floors, around sinks, around microwave ovens, ventilation fans, furniture such as cupboards, chests, tables, desks, chairs, bookshelves, refrigerators, TVs, personal computers, stereos, air conditioners, microwaves, Washing of the surface of appliances such as washing machines, dryers, certification devices, etc., washing of windows used in dwellings, doors, furniture doors, windows of automobiles, etc., washing of screen doors, toilet floors, walls, Cleaning of doors, toilets, toilet seats with cleaning functions, heating toilet seats, etc., cleaning of dishes, cooking utensils, cleaning of painted surfaces, plating surfaces, plastic surfaces of automobiles, bicycles, motorcycles, etc., cleaning of automobile wheels, exterior entrances Week , Terrace,
Suitable for cleaning fences, fences, gates and other hard surfaces. Furthermore, it is particularly suitable for cleaning painted surfaces, plated surfaces, plastic parts surfaces, window glasses and wheels of automobile bodies.

[0026]

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

Examples 1 to 22 and Comparative Examples 1 to 2 The liquid detergent compositions shown in Tables 1 to 3 were prepared, and the following evaluation tests were carried out. The results are shown in Tables 1 to 3.

<Evaluation of Physical Properties> Viscosity Measured with a B-type viscometer. -Average particle diameter The average particle diameter of the primary particles and the average particle diameter of the secondary particles of the component (A) were measured using PARTCLE SIZE ANALYZER LA-700 manufactured by Horiba, Ltd. The primary particles were measured by dispersing each particle in ethanol. The weight ratio of particles / ethanol was determined by adding particles until the concentration indicated by the particle size distribution analyzer was displayed as "optimal". Regarding the secondary particles, each composition was diluted with a dispersion medium, and the measurement was performed when the concentration indicated value was displayed as “optimum”. Here, a particle having the same particle diameter of the primary particle and the secondary particle means that the secondary particle is not formed.

<Evaluation of Performance> Redispersibility 100 ml of the detergent composition was allowed to stand at room temperature for one week, and then shaken up and down five times to redisperse. · The rapeseed oil was uniformly applied to the detergency iron plate 100 cm ^2, baked at 180 ° C. 30 minutes, using a model contamination plate having formed thereon the most dry film, 1 ml of the detergent composition horizontally fixed the model contamination plate The degree of washing after dripping and rubbing with a dry towel 10 times was visually observed, and the ratio (%) of the area where the solidified rapeseed oil film peeled off in the rubbed area was calculated. Polishing effect 1 ml of the detergent composition was wiped on a 500 cm ² floor of a flooring with a dry towel and then dried. After that, a glossiness of 60 degrees was obtained with a gloss meter (IG320 type, manufactured by Horiba, Ltd.).

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

The components shown in Tables 1 to 3 were as shown in Table 4 below.

[0034]

[Table 4]

N in Tables 1 to 4 is the average number of moles of ethylene oxide added.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Michio Yokosuka 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Laboratory (56) References JP-A-8-209117 (JP, A) JP-A-57-192922 (JP, A) JP-A-53-67706 (JP, A) JP-A-8-257898 (JP, A) Wetting and surface energy of surface-treated fine powder, "Powder and Powder Metallurgy", 1981, Vol. 28, No. 7, pp. 245-250 (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 3/37 C11D 3/12 C11D 17/08 Patent file (PATOLIS) JICST file (JOIS)

Claims (10)

(57) [Claims] (A) from the group consisting of:
Hydrophobic particles having a surface energy of 60 mN / m or less , comprising one or more selected components as constituents, have a surface tension of 25 to
A liquid detergent composition for hard surfaces having a viscosity (25 ° C.) of 1 to 1000 mPa · s dispersed in the form of secondary particles in a dispersion medium (B) of 60 mN / m. Alkyl (alkyl group having 1 to 1 carbon atoms)
8) Acrylate, alkyl (C 1 to C 1 of alkyl group)
8) methacrylate, mono- or di-alkyl (al
C1-C5 kill group, itaconate, mono or di
-Alkyl (alkyl group having 1 to 5 carbon atoms) fumarate,
Maleic anhydride, vinylidene chloride, styrene,
Divinylbenzene, vinyl chloride, vinyl acetate, vinyl alcohol
Cetal, ethylene, propylene, butene, isobutyle
, Methylpentene, butadiene, vinyltoluene,
Acrylonitrile, methacrylonitrile, acrylamide
, Acrylic acid, methacrylic acid, itaconic acid, fumaric acid
Acid, citraconic acid, crotonic acid, β-acryloxypro
Pionic acid, hydroxyalkyl (alkyl group having 1 carbon atom
-6) acrylate and hydroxyalkyl (alkyl
Selected from the group consisting of methacrylates having 1 to 6 carbon atoms
Containing at least one ethylenically unsaturated monomer
Monomer, or obtained by polymerizing these monomers.
Polymer. Nylon, polyester, epoxy,
Amino alkyd, urethane, polyacetal or
Any one or more resins of carbonate. Methyl
Trialkoxysilane or its partial hydrolysis / condensation
Is hydrolyzed in aqueous solution of ammonia or amines.
Polyorganosilsesquioxane obtained by condensation. 2. The component (A) is a hydrophobic spherical particle having a true specific gravity of 1.0 to 2.5 and an average particle diameter (a) of 0.1 to 10 μm, and an average particle diameter (b) of the secondary particles in the dispersion is The liquid cleaning composition for hard surfaces according to claim 1, wherein the composition has a thickness of 0.5 to 500 µm and (b) / (a) = 1.1 to 5000. 3. The liquid cleaning composition for hard surfaces according to claim 1, wherein the component (A) is polymethylsilsesquioxane. 4. A dispersion medium (B) comprising a C1-4 alcohol having 1 to 3 carbon atoms, an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant and an aromatic sulfonic acid. One or more selected from the salts (B-
The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, comprising 1) and water (B-2). 5. The liquid cleaning composition for hard surfaces according to claim 1, wherein the composition contains 0.01 to 50% by weight of the component (A). 6. The method according to claim 1, wherein (C) is at least one member selected from the group consisting of a polysaccharide or a derivative thereof, polyacrylic acid or an alkali metal salt thereof, and polyvinyl alcohol or a derivative thereof.
6. Any one of claims 1 to 5, comprising at least one kind of viscosity modifier.
Item 10. A liquid cleaning composition for hard surfaces according to item 8. 7. The component (C) comprises xanthan gum, welan gum, ramzan gum, gellan gum, guar gum, cod gum, locust bean gum, carrageenan, pectin, alginic acid or an alkali metal salt thereof, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyacrylic. The liquid detergent composition for hard surfaces according to claim 6, wherein the composition is one or more selected from sodium acid and polyvinyl alcohol. 8. The liquid cleaning composition for hard surfaces according to claim 6, wherein the composition contains 0.001 to 5% by weight of the component (C). 9. Further, paraffin, as a washing component (D),
0.1-20% by weight of one or more selected from polyoxyethylene phenyl ether and butyl diglycol
The liquid cleaning composition for a hard surface according to any one of claims 1 to 8, which comprises the composition. 10. The composition according to claim 1, further comprising 0.1 to 10% by weight of a polyorganosiloxane as a polishing component (E).
The liquid detergent composition for hard surfaces according to any one of the above.