JP2002332498A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition blended with a large amount of an alkali and excellent in cleaning power. SOLUTION: This liquid detergent composition is provided by containing (q) an alkali, (b) liquid having 30-100 specific dielectric constant (at 25 deg.C) in specific ratios, having a part of the alkali existing in a solid state, and showing pH 9-11 (at 25 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is a liquid detergent composition useful in a wide range of fields, such as laundry detergents for textiles, kitchen detergents, residential detergents, detergents for cleaning various hard surfaces, and liquid cleansers. About things.

[0002]

2. Description of the Related Art Generally, liquid detergents have excellent features such as being excellent in solubility in water and being directly applicable to soiled portions.
However, the conventional liquid detergent containing a large amount of water has a problem in that a large amount of a builder for improving the detergency, especially a large amount of a strong alkaline agent, is incorporated. In other words, in such a system, the pH of the cleaning agent rises remarkably, and when directly applied to plant stains such as tea, grass juice, grape juice and the like adhered to the object to be cleaned, the pH is caused by the high pH of the cleaning solution. Then, discoloration occurs, and conversely, washing becomes difficult. On the other hand, a non-aqueous liquid detergent that does not substantially contain water has a problem that the dissociation of the alkaline agent is small and the pH is too low.

[0003] An object of the present invention is to provide a detergent composition which is excellent in detergency and contains a large amount of an alkaline agent and has a pH adjusted to an appropriate range.

[0004]

The present invention provides (a) an alkali agent (hereinafter, referred to as a component (a)) of 1 to 70% by mass,
(B) a liquid having a relative dielectric constant (25 ° C.) of 30 to 100 [hereinafter referred to as a component (b)] 4 to 30% by mass,
Part of (a) exists in a solid state and has a pH (25
C) is from 9 to 11.

According to the present invention, there is provided a liquid detergent composition comprising a liquid dispersion medium and a solid dispersoid dispersed in the liquid dispersion medium, wherein the alkaline agent (a) is contained in a ratio of 1 to 3 in the composition. 7
0% by mass, a part of the alkali agent (a) is present as a solid dispersoid, and at least a part of the liquid dispersion medium has a relative dielectric constant (25 ° C.) of 4 to 30% by mass in the composition. 30 ~
100 liquid (b) and the pH (25 ° C.) is 9 to
11, a liquid detergent composition is provided.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS <Component (a)> The alkaline agent as the component (a) of the present invention is a solid at 20 ° C. and has a pH value of 0.1% by mass when dissolved in ion-exchanged water.
(20 ° C.) indicates 10 or more. Two or more types of the component (a) may be mixed as necessary. The component (a) is 1 to 70% by mass in total in the composition in terms of detergency,
Preferably, the content is 3 to 50% by mass, more preferably 5 to 30% by mass. The dispersion average particle size of the component (a), which is present in a solid state in the composition, is preferably 1 μm or less, more preferably 0.5 μm or less, from the viewpoint of stability (prevention of sedimentation over time). is there. The dispersion average particle size can be measured, for example, using a laser diffraction particle size distribution analyzer (LA-92).
0; manufactured by Horiba, Ltd.). As the solvent to be diluted at the time of measurement, a solvent that does not dissolve these alkaline agents is selected. In addition, this particle diameter indicates a median diameter calculated on a volume basis, and hereinafter, all the particle diameters are represented by this.

The component (a) includes carbonate, silicate,
Metasilicate, alkali metal hydroxide, phosphate and the like, from the viewpoint of adjusting the composition to an appropriate pH,
Carbonates are particularly preferred. Examples of the carbonate include sodium carbonate and potassium carbonate, and a salt of an alkali metal is particularly preferable. SKS-6 as silicate
(Made by Hoechst), a crystalline silicate described in JP-A-5-184946, an amorphous silicate described in JP-A-11-106786, and the like. As metasilicates,
And sodium metasilicate. As hydroxides of alkali metals, sodium hydroxide, potassium hydroxide,
Lithium hydroxide and the like. Examples of the phosphate include tripolyphosphate such as sodium tripolyphosphate, pyrophosphate and the like.

These components may be blended as they are, or the surfaces of these components may be blended after being coated with a polymer, an inorganic substance or the like in advance.

<Component (b)> The component (b) of the present invention comprises 2
It is liquid at 0 ° C. and has a relative dielectric constant (with respect to air) of 30 to 10 at 25 ° C. measured by a general dielectric constant measuring instrument.
It means what is 0. Specifically, ethylene glycol, diethylene glycol, 1-3 propylene glycol, 1-4 butanediol, 1,2,6 hexanetriol, hydroxybutanoic acid, formic acid, monoethanolamine, glycerin, methanol, water, hydrogen peroxide, etc. Is mentioned.

The composition of the present invention contains the component (b) in an amount of 4 to 30% by mass, preferably 5 to 30% by mass, from the viewpoint of adjusting the pH of the composition.
The content is 25% by mass, more preferably 6 to 23% by mass.
In particular, water has a large dielectric constant, so that the pH of the composition tends to increase. Therefore, the compounding amount is suitably 3 to 15% by mass, more preferably 3 to 12% by mass, and particularly preferably 3 to 10% by mass in the composition. In this case, water contained as crystallization water in the inorganic compound such as zeolite is excluded from the component (b) and is not included in the mass of the component (b). The component (b) may be used in combination of two or more if necessary.
The amount of the component (b) is the sum of them.

In the measurement of the relative dielectric constant, samples other than water are prepared in advance so that the water content is 0.2% by mass or less. As a dielectric constant measuring device, for example, LCR meter AG-4311, manufactured by Ando Electric Co., Ltd., test lead AG-4
917, a system including the liquid electrode LE-22, or the like is used.

In general, the dissociation degree of a salt such as the component (a) is related to the dielectric constant of a medium, and the salt is easily dissociated in a liquid having a high dielectric constant. This is because when a salt dissociates into ions, an attractive force (Coulomb force) acts between the ions (heterogeneous), but the magnitude is proportional to the reciprocal of the dielectric constant.
This is because the attractive force becomes smaller in a medium having a higher dielectric constant, and the dissociated state becomes more stable. In the present invention, the dissociation degree of the component (a) is controlled by optimizing the amount of the liquid having a high dielectric constant, that is, the component (b), so that the pH of the composition is safe and the optimum value for coating and washing is obtained. Range (9.0-
11.0). In the liquid detergent composition of the present invention, the component (a) is completely dissolved at the time of dilution, and thereby a high detergency can be realized.

<Other Components> Although not essential components, the following components can be added to the present invention.

In the present invention, a surfactant which is conventionally known to be incorporated into a liquid detergent composition can be used. In order to enhance detergency, it is preferable to use an anionic surfactant or a nonionic surfactant as a main surfactant. When used in combination with a cationic surfactant to further enhance flexibility, a nonionic surfactant is preferably used as the main surfactant.

As the anionic surfactants, those having 10 carbon atoms
Alkali metal salts such as linear alkyl benzene sulfonic acid having an alkyl chain of -18, alkyl sulfate, polyoxyalkylene alkyl ether sulfate, alpha sulfo fatty acid alkyl (for example, methyl) ester, and fatty acid having 8 to 20 carbon atoms are preferable.

As a counter ion of the anionic surfactant, in addition to alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and / or alkanolamines such as mono, di and triethanolamine are used. In particular, the use of alkanolamine is preferable since the liquid stability is improved. In that case, the content of the anionic surfactant in the composition is preferably 5 to 50% by mass, more preferably 10 to 50% by mass.

As the nonionic surfactant, the following (1)
(1) having an alkyl group derived from a linear primary alcohol or a linear secondary alcohol having an average carbon number of 8 to 20 or an alkyl group or an alkenyl group derived from a branched alcohol; A polyoxyethylene alkyl or alkenyl ether to which ethylene oxide (hereinafter referred to as EO) is added in an average of 1 to 20 mol. (2) Polyoxy having an alkyl group or an alkenyl group having an average carbon number of 8 to 20, and having an average of 1 to 15 mol of EO and an average of 1 to 5 mol of propylene oxide (hereinafter referred to as PO). Alkylene alkyl or alkenyl ether. In this case, EO and PO may be either random addition or block addition. (3) An alkyl polysaccharide surfactant represented by the following general formula (3-1). R- (OR ′) _i G _j (3-1) wherein R is a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms or an alkylphenyl group;
R ′ is an alkylene group having 2 to 4 carbon atoms; G is a residue derived from a reducing sugar having 5 or 6 carbon atoms; i is a number having an average value of 0 to 6;
Indicates the number of average values 1 to 10. (4) Fatty acid alkanolamides and polyhydroxy fatty acid amides.

In particular, the polyoxyalkylene alkyl ether (1) or (2) is preferable from the viewpoint of oily soil detergency. The content of the nonionic surfactant in the composition is preferably 5 to 50% by mass, more preferably 10 to 50% by mass.
% By mass.

Further, in order to further improve the flexibility to clothing and the like, a cationic surfactant such as a mono-long-chain alkyl quaternary ammonium salt is preferably added to the composition in an amount of 0.5 to 10%.
%, More preferably 1 to 5% by mass. In terms of the effect of improving flexibility, the long-chain alkyl group has 12 to 22 carbon atoms,
Particularly, a long-chain alkyltrimethylammonium salt having 14 to 20 alkyl groups is preferable. The counter ion of the cationic surfactant includes a halogen ion, CH ₃ SO ₄ ⁻ , C ₂
H ₅ SO ₄ ⁻ , CH ₃ COO ⁻ and HCOO ⁻ are preferred. In order to further increase the flexibility, the cationic surfactant is added to the anionic surfactant, ie, cationic surfactant / anionic surfactant = 3/1 to 1/2, and further 2/1 to 1/2. It is particularly preferred to mix them in a molar ratio of 1.2 / 1 to 1 / 1.2.

In addition, an amphoteric surfactant may be blended as a surfactant in view of the stability of the liquid and the ability to clean mud. As the amphoteric surfactant, alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine, alkylimidazoline type betaine and the like can be blended. The amphoteric surfactant is preferably contained in the composition in an amount of 1 to 20% by mass.

In the present invention, it is preferable to incorporate an aluminosilicate represented by the following formula from the viewpoint of detergency. [M (1) _p M (2) _q M (3) _r O] · u [M (4) _s M (5) _t O] · v (Al ₂ O ₃ ) · w
(SiO ₂ ) [wherein, M (1), M (2), and M (3) each represent Na, K or H, and M (4) and M (5) represent Ca and Mg, respectively. p, q,
r is 0 to 2 (where p + q + r = 2), s and t are each 0 to 1 (where s + t = 1), u is 0 to 1, preferably 0.1 to 0.5, and v is 0 to 1. Preferably 0
0.1 and w are 0 to 0.6, preferably 0.1 to 0.5. ].

Examples of such aluminosilicates include, for example, various zeolites generally used as detergents. These are A-type, X-type, Y-type
Although it is classified into a type and a P type, an A type zeolite which is generally excellent in cation exchange capacity is preferable. X-ray diffraction pattern of A-type zeolite is JCPDS (Joint Comm).
item on Powder Diffraction
Standards), which has a diffraction peak at the position shown in the type 4A zeolite (No. 38-241). Examples of such zeolites include Toyobuilder commercially available from Toyo Soda Co., Ltd. It is also preferable to use fine-particle zeolite produced by the method described in Japanese Patent Application No. 11-318604, since it is easily pulverized in the production process of the present detergent composition, whereby dispersion stability is enhanced. These aluminosilicates are preferably in the composition
-50 mass%, more preferably 5-40 mass%.

Further, in the present invention, in order to stably disperse the components present as solids in the composition, it is preferable to add a polymer type dispersant. Examples of such a polymeric dispersant include a monomer group constituting a polymer that is soluble or homogeneously dispersible in the liquid phase of the composition, and a monomer group having a functional group having an affinity for a solid component in the composition. And those obtained by polymerization or polycondensation of at least one monomer selected from the following by a known method.

Examples of the monomer group constituting the polymer which is soluble or homogeneously dispersed in the liquid phase include the following (i) to (i).
(Q). (I) Vinyl ethers having an unsubstituted or substituted saturated or unsaturated alkyl group having 1 to 22 carbon atoms or an aralkyl group. Preferably, methyl vinyl ether, ethyl vinyl ether, 4-hydroxybutyl vinyl ether, phenyl vinyl ether and the like are used. (J) Unsubstituted or substituted having a saturated or unsaturated alkyl or aralkyl group having 1 to 12 carbon atoms on nitrogen
(Meth) acrylamides. Preferably (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth)
Acryloylmorpholine, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, N-methylol (meth) Acrylamide, N-butoxymethyl (meth) acrylamide and the like. (K) N-vinyl aliphatic amides. Preferably, N-vinylpyrrolidone, N-vinylacetamide, N-vinylformamide and the like. (L) (meth) acrylic esters having 1 to 22 carbon atoms and having an unsubstituted or substituted, saturated or unsaturated alkyl group or aralkyl group. Preferably methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2- (meth) acrylate Methoxyethyl and the like. (M) alkylene oxides. Preferably, ethylene oxide, propylene oxide and the like are used. (N) Cyclic imino ethers. Preferably 2-methyl-
2-oxazoline, 2-phenyl-2-oxazoline and the like. (O) Styrenes. Preferably, styrene, 4-ethylstyrene, α-methylstyrene and the like are used. (P) Vinyl esters. Preferably vinyl acetate, vinyl caproate and the like. (Q) Allyl ethers having an unsubstituted or substituted saturated or unsaturated alkyl group or aralkyl group having 1 to 22 carbon atoms. Preferably methyl allyl ether, ethyl allyl ether, 4-hydroxybutyl allyl ether,
Phenylallyl ether and the like.

In addition to the polymer obtained from the above-mentioned monomer group, examples of the polymer soluble or homogeneously dispersed in the liquid phase include the following structures (r) to (t). Also preferred are polymers consisting of one or more monomers having a functional group with a high affinity for the component. (R) Polyesters comprising a dihydric alcohol and a dihydric carboxylic acid. Preferably, polyethylene glycol and terephthalic acid, or a polycondensate of 1,4-butanediol and succinic acid, and the like. (S) Polyamides. Preferably, a ring-opened polymer of N-methylvalerolactam. (T) polyurethanes. Preferably polyethylene glycol, hexamethylene diisocyanate and N-methyl-
Diethanolamine or polyadducts of 1,4-butanediol.

Preferred functional groups having a high affinity for solid components include carboxy groups, sulfonic groups, hydroxyl groups and primary to quaternary ammonium groups. As a monomer having such a functional group, for example, (meth) acrylic acid and its salts, styrene carboxylic acid and its salts, maleic acid and its salts, itaconic acid and its salts, styrene sulfonic acid and its salts, (meth) allyl sulfone Acid and its salts, 2-acrylamido-2-methylpropanesulfonic acid and its salts, vinylsulfonic acid and its salts, vinyl alcohol, (meth) acrylic acid 2
-Hydroxyethyl, 2-hydroxyethyl (meth) acrylamide, 4-hydroxymethylstyrene, mono-2-((meth) -acryloyloxy) ethyl phosphate, chloride 2
-((Meth) acryloyloxy) ethyltrimethylammonium, vinylbenzyltrimethylammonium chloride,
2-((meth) acryloyloxy) ethyldimethylethylammonium ethylsulfate; 3-((meth) acrylamido) propyltrimethylammonium chloride; diallyldimethylammonium chloride; vinylpyridine;

Among them, a preferred polymer type dispersant is a block or graft polymer of a polymer soluble or homogeneously dispersed in a liquid phase and a polymer having a functional group having a high affinity for a solid component.

The presence of two types of segments allows
Both effects appear without being offset. It is particularly preferable to use a graft polymer in order to express both effects more highly. The mass ratio of the two types of segments in the block or graft polymer [(polymer segment soluble or homogeneously dispersed in liquid phase) / (polymer segment having functional group having high affinity for solid component)] is 5 / 95-95 / 5 is preferred. The method for synthesizing such a block or graft polymer is not particularly limited, and a known method can be selected. Among them, a method of polymerizing a vinyl monomer or the like using a macroazo initiator having an azo group in a polymer chain (macroazo initiator method) A method of using a compound having a polymerizable group at one end of a polymer chain
(Macromonomer method), and a method in which a monomer is radically polymerized again in the presence of a polymer, and a newly generated polymer chain is linked to a polymer chain that has been coexisted by a chain transfer reaction (chain transfer method). preferable. Examples of the polymer dispersant obtained by these methods include, for example, a block polymer obtained by radical polymerization of acrylic acid (or a salt thereof) using a polyethylene glycol macroazo initiator, polyethylene glycol mono (meth) acrylic acid Copolymer of ester and (meth) acrylic acid or its salt, copolymer of polyethylene glycol mono (meth) acrylate and styrene sulfonic acid or its salt, polyethylene glycol mono (meth) acrylate and chloride 2 -Copolymer with ((meth) acryloyloxy) ethyltrimethylammonium, copolymer of polyethylene glycol mono (meth) acrylate and 2-hydroxyethyl (meth) acrylate, polyethylene glycol or polypropylene glycol or polyethylene glycol Propylene grease Acrylic acid and maleic acid in Lumpur
(Or a salt thereof), and a graft polymer obtained by radical polymerization of diallyldimethylammonium chloride in an aqueous solution of a poly (N, N-dimethylacrylamide / styrene) copolymer; , N-dimethyl (meth) acrylamide) aqueous solution, and a graft polymer obtained by radical polymerization of styrenesulfonic acid (or a salt thereof). The weight-average molecular weight of these polymeric dispersants is 1,000,000 or less, and more preferably 1,000 to 50, for the purpose of preventing an excessive increase in viscosity.
It is preferably 10,000, especially 10,000 to 300,000. These polymer type dispersants are preferably contained in the composition in an amount of 0.01 to 10%.
% By mass.

Further, the following components can be added to the liquid detergent composition of the present invention. Liquid alkaline agent not corresponding to component (b) such as alkanolamine 0.01 to 10
Mass%; sulfuric acid, hydrochloric acid, phosphoric acid, a fatty acid having 1 to 12 carbon atoms,
Acid agent for pH adjustment such as alkyl sulfuric acid having 1 to 3 carbon atoms 0.0
1 to 10% by mass; alcohols having 2 or more carbon atoms such as ethanol, diols and polyols not falling under the component (b) such as 1,3 butanediol and 1,5 pentanediol, paratoluenesulfonic acid, benzoate (It also has an effect as a preservative), a viscosity reducing agent such as urea and 0.01 to 30% by mass; a phase adjuster such as polyoxyalkylene benzyl ether and polyoxyalkylene phenyl ether; 0.01 to 30% by mass; aminopolyacetic acid such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, iminoniacetic acid, diethylenetriaminepentaacetic acid, glycoletherdiaminetetraacetic acid, hydroxyethyliminoniacetic acid and triethylenetetramine hexaacetic acid; Salt, malonic acid, succinic acid, diglycolic acid, malic acid, tartaric acid and citric acid Metal ion scavenger 0.1 to 20 mass% of salt and the like; carboxymethylcellulose, naphthalene sulfonate formalin condensate, JP 59-
Nos. 1 to 21 of JP-A-62614 (1 page, 3 columns, 5 lines to 3 lines)
(Page 4, column 14, line 14)
1 to 10% by mass; color transfer inhibitor 0.01 to 10% by mass;
Bleaching agent such as sodium percarbonate or sodium perborate
01 to 10% by mass; tetraacetylethylenediamine,
The general formulas (I-2) and (I-
3), (I-4), (I-5), (I-6), (I-
Bleach activator 0.01 such as bleach activator represented by 7)
-10% by mass: 0.001-2% by mass of enzymes such as amylase, protease, lipase and cellulase; 0.001-2% by mass of enzyme stabilizer such as calcium chloride, calcium sulfate, formic acid, boric acid (boron compound) Fluorescent dyes 0.0 such as Tinopearl CBS-X (manufactured by Ciba Specialty Chemicals) and Whitetex SA (manufactured by Sumitomo Chemical).
01 to 1% by mass; silicone, JP-B-56-29691
And a surface modifier 0.01 to 2% by mass; oxidation prevention of butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogen sulfite and the like. 0.01 to 2% by mass; inorganic salts such as sodium chloride, sodium hydrogen carbonate and magnesium sulfate 0.01 to 5% by mass; inorganic pigments such as titanium oxide and silica; alkanes and alkenes such as paraffin oil; Perfume; legal dyes; antimicrobial preservatives and the like.

The pH of the liquid detergent composition of the present invention (25
° C) is 9 to 11 from the viewpoint of coating and cleaning properties. Also,
From the viewpoint of the cleaning performance during normal use, the pH (25) when the composition was diluted 1500 times with ion exchanged water on a mass basis.
C) is preferably 9 to 11. Here, the pH is JIS
Measured according to Z8802. The measuring device is, for example, a glass electrode type pH meter (D-1 manufactured by Horiba, Ltd.)
4) is used.

In the liquid detergent composition of the present invention, the term "liquid" means a substance having fluidity at 20 ° C. Here, whether or not it has liquidity is determined as follows. Inner diameter 30
A cylindrical glass container having a height of 5 cm and a height of 5 cm and having an open top is prepared, the composition is filled up to a height of 3 cm from the bottom, the top is closed, and the container is allowed to stand at 20 ° C. in a vertical state for one day. Thereafter, when the upper part is opened and the contents flow within one minute when the container is tilted by 90 degrees and reaches the opening of the glass container, it is determined that the glass container has fluidity.

The viscosity of the liquid detergent composition of the present invention (20
° C) is 10 to 2500 mPa · from the viewpoint of usability.
s, more preferably 50 to 2000 mPa · s, especially 100 to 15
00 mPa · s is preferred. These viscosities were measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., VISCOMMETER M).
ODEL DVM-B) and the rotor used is 3
Alternatively, it is measured under the conditions of 4, the number of rotations is 60 r / min, and the measurement time is 60 s.

The liquid detergent composition of the present invention preferably has a phosphorus content of 1% by mass or less, more preferably 0.5% by mass.

As a method for producing the composition of the present invention, stirring using a disperser, a homomixer, a paint shaker, etc., a wet mill using a medium such as a sand mill, a sand grinder, a dyno mill, a wet vibration mill, an attritor, a nanomizer, a microfluidizer A high-pressure impact mill such as a dizer or the like, a roll mill such as a three-roll mill, a kneader, an extruder, an ultrasonic disperser, or the like is used. From the viewpoint of the milling power and productivity, a wet milling method using a medium is particularly preferable. Known media such as titania, zirconia, and silica can be used as the media.
The media diameter is particularly preferably 0.1 to 3 mm. If the solid component as the raw material is larger than the particle size suitable for the wet pulverization, or if it is desired to reduce the processing time by the wet pulverization as much as possible, the material is previously pulverized to an appropriate particle size by a dry pulverization method, for example, to about 80 to 300 μm. Is good.

[0035]

EXAMPLES Example 1 Nonionic surfactant (Softanol 70; manufactured by Nippon Shokubai), ethylene glycol (manufactured by Wako Pure Chemical), 2-phenoxyethanol (manufactured by Wako Pure Chemical), fatty acid, polymer type dispersant (Aqualoc) FC600S; Nippon Shokubai) and ion-exchanged water were mixed and uniformly dissolved. A batch type sand mill (manufactured by IMEX Co., Ltd.) in which soda ash (dense ash; central glass) and zeolite (Toyobuilder; manufactured by Toyo Soda Co., Ltd.) were suspended and filled with 400 g of zirconia beads having a diameter of 0.8 mm was filled. ), And wet grinding was performed for 30 minutes at a disk rotation speed of 1500 r / min. Thereafter, the media was removed through a 40-mesh sieve to obtain a liquid detergent composition shown in Table 1. In this composition,
Some of the dens ash and zeolite were present in the solid state. A part of this liquid was sampled, and the particle size distribution of the solid particles was measured with a particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) using a dispersion medium ethanol. The median diameter (by volume) was 0.8 μm. there were. The following evaluation was performed about the obtained liquid detergent composition. Table 1 shows the results.

Examples 2 to 6, Comparative Examples 1 to 6 Using the components shown in Table 1, liquid detergent compositions were prepared in the same manner as in Example 1, and the following evaluations were made. Table 1 shows the results. In the compositions of Examples 2 to 6, some of the solid components were present in the solid state as particles having a dispersion average particle diameter of 1 μm or less (the measurement method was the same as in Example 1).

<Evaluation> (1) Measurement of relative dielectric constant of raw material components Each raw material component (excluding water) was purified so that the water content was 0.2% or less, and then LCR meter AG-431 manufactured by Ando Electric.
1. Test lead AG-4917, liquid electrode LE-2
2 was measured in a system consisting of:

(2) Measurement of pH of Composition The pH of the composition and its 1500-fold dilution with ion-exchanged water (approximately 0.7 g of the composition was added to 1 L of water) were measured using a glass electrode type pH meter (Horiba Seisakusho) D-14). In addition, each pH was set to the value shown 10 minutes after inserting the pH electrode into the composition or diluent.

(3) Cleaning test (3-1) Cleaning test 1 (cleaning rate of sebum / carbon stained cloth) 15% by mass of carbon black, 60% by mass of cottonseed oil, 5% by mass of cholesterol, 5% by mass of oleic acid, palmitin Mixture 100 of 5% by weight of acid and 10% by weight of liquid paraffin
g was dissolved and dispersed in 8 L of perchrene, and 10 cm × 10
A cotton white cloth (2003 cloth) was immersed in dirt by adhering dirt.
A carbon soiled cloth (artificial soiled cloth) was prepared.

A set of five sebum / carbon stained cloths was put into 1 L of an aqueous detergent solution for evaluation, and a tergotometer was used for a cleaning time of 10 minutes and a detergent composition of 0.7 g /
1 L of detergent aqueous solution for evaluation, water hardness 71.2 mg CaCO
₃ / L, water temperature 20 ° C, tergotometer rotation speed 10
The washing test was performed under the conditions of 0 r / min and running water rinsing with 20 ° C. tap water for 5 minutes.

The detergency was determined by measuring the reflectance at 550 nm of the original cloth before contamination and the contaminated cloth before and after cleaning using a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was determined by the following equation. Table 1 shows the results. Cleaning rate (%) = ｛(reflectance after cleaning-reflectance before cleaning) /
(Reflectance of original cloth-Reflectance before washing) Δ × 100.

(3-2) Washing test 2 (cleaning rate of grape stain-contaminated cloth) Kyoho was ground with a food mixer and filtered with a cloth to remove solids to obtain a grape extract. 10cm ×
Grape stains were adhered by immersing a cotton white cloth (gold cloth 2003) cut to 10 cm, and then naturally dried in the shade to prepare grape stain-contaminated cloth.

A pair of the above-mentioned grape stain-contaminated cloths was uniformly coated with a detergent for evaluation (0.35 g / sheet), and then a cleaning time of 10 minutes and a cleaning composition of 0.70 g (0.3
5g x 2), water volume 1L, water hardness 71.2mg CaCO
₃ / L, water temperature 20 ° C, tergotometer rotation speed 10
Rinsing was performed under running conditions of 0 r / min and 20 ° C. tap water for 5 minutes.

Each of the washed samples (2 sheets) was visually compared with the washed samples (2 sheets) of Example 1 by three expert panelists and evaluated according to the following criteria. Was calculated. +1: Judged to be higher than the detergency of Example 1 0: Judged to be equivalent to the detergency of Example 1 -1: Judged to be lower than the detergency of Example 1 The following was discarded to make the final judgment results shown below. Table 1 shows the results. ◎: +2 points or more ：: +1 to -1 point △: -2 points ×: -3 points

[0045]

[Table 1]

(Note) ・ Soda ash; Dense ash (manufactured by Central Glass) ・ Zeolite; Toyobuilder (manufactured by Toyo Soda Co., Ltd.) ・ Fatty acid: saturated fatty acid having 12 carbon atoms ・ Polymer type dispersant; Aqualoc FC600S ( -Non-ionic surfactant (1); Sophthalanol 70 (Nippon Shokubai) -Non-ionic surfactant (2); Emulgen LC-110
(Manufactured by Kao) • Polyethylene glycol; weight average molecular weight 400.

[0047]

According to the present invention, there is provided a liquid detergent composition containing a large amount of an alkaline agent and adjusting the pH to an appropriate range. When this cleaning agent is used, discoloration of stains when directly applying to the object to be cleaned and performing cleaning is suppressed, and at the time of normal cleaning, the alkaline agent is completely dissolved and high cleaning power is exhibited.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazutoshi Ide 1334 Minato, Wakayama-shi, Wakayama F-term in the Kao Research Laboratory (Reference) 4H003 AB03 AC08 AC09 BA12 DA01 DA04 DA05 DA17 EA15 EA16 EA28 EB04 EB06 EB30 EB36 ED02 FA28 FA30

Claims (7)

[Claims] (A) 1 to 70% by mass of an alkali agent,
(B) Liquids 4 to 3 having a relative dielectric constant (25 ° C.) of 30 to 100
A liquid detergent composition containing 0% by mass, a part of (a) being present in a solid state in the composition, and having a pH (25 ° C) of 9 to 11. 2. The liquid detergent composition according to claim 1, wherein the content of water is 3 to 15% by mass. 3. The liquid detergent composition according to claim 1, wherein (a) present in a solid state is a particle having a dispersed average particle diameter of 1 μm or less. 4. A viscosity (20 ° C.) of 10 to 2500 mPa
The liquid detergent composition according to any one of claims 1 to 3, which is s. 5. The liquid detergent composition according to claim 1, wherein the content of phosphorus is 1% by mass or less. 6. A monomer group constituting a polymer having solubility or uniform dispersibility in a liquid phase of the composition, and a monomer group having a functional group having an affinity for a solid component in the composition. The liquid detergent composition according to any one of claims 1 to 5, further comprising a polymer type dispersant obtained by polymerizing one or more monomers. 7. A liquid detergent composition comprising a liquid dispersion medium and a solid dispersoid dispersed in the liquid dispersion medium, comprising 1 to 70% by mass of an alkali agent (a) in the composition. A part of the alkaline agent (a) is present as a solid dispersoid, and at least a part of the liquid dispersion medium has a ratio of 4% in the composition.
A liquid (b) having a relative dielectric constant (25 ° C.) of ３０30% by mass (25 ° C.) and a pH (25 ° C.) of 9-11;
Liquid detergent composition.