JP2002332500A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition excellent in cleaning power and having a good dispersion stability. SOLUTION: This liquid detergent composition is provided by containing a liquid phase [(a) phase], a polymer type dispersing agent [(b) component] and a crystalline silicate compound and/or an aluminosilicate compound [(c) component], and showing <=5% volume separation rate after preserving it at 25 deg.C for 1 month [provided that in the case that the water content in the composition is <=5 wt.% and also using only the aluminosilicate compound as the (c) component, or in the case that a water content in the composition exceeds 5 wt.%, the (b) component has >=120 CaCO3 mg/g cation exchange capacity], and the method for producing the same is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to 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.

[0002]

2. Description of the Related Art Liquid detergents generally have better solubility in water than powder detergents.
In addition to the advantage of being able to be applied directly to dirty parts, there is no drying step, and it is possible to mix heat-labile substances that cannot be added to powder detergents, and requires complicated equipment such as drying equipment. It has advantages such as not.

[0003] It is desired that a liquid detergent contains an alkaline agent, a calcium scavenger, a bleach, an enzyme, an abrasive, etc., which have an auxiliary effect of washing. However, especially in the case of a liquid detergent containing a solid component, the solid component precipitates and separates during storage and is not easily redispersed,
The problem that the product viscosity is too high and it is not easy to inject into the washing tub tends to occur. In order to suppress the sedimentation of solid components, methods such as increasing the viscosity of the liquid phase or reducing the particle size of the solid have been adopted, but there is a limit to thickening due to problems during injection. However, stable dispersion was not realized only by reducing the solid particle size.

[0004] For the purpose of stabilizing the dispersion of solid components,
JP-A-39319 discloses a copolymer of maleic anhydride and ethylene or vinyl methyl ether hydrolyzed at least 30%, and JP-A-3-86800 discloses an amphiphilic carboxy-containing polymer; JP-A-5-140599.
Japanese Patent Application Laid-Open No. 7-508781 discloses a copolymer having a monomer having a group capable of extending from the surface of a solid phase and a monomer having a group capable of associating with a solid phase. A liquid detergent composition using a polymer type dispersant such as a polymer having a soluble monomer is disclosed. However, the solid components used in these compositions are stabilized by the network structure formed by the polymer, but are not satisfactory in terms of dispersion stability and detergency.

[0005] An object of the present invention is to provide a liquid detergent composition which has excellent detergency and good dispersion stability.

[0006]

Means for Solving the Problems The present inventors have improved the detergency by using a polymer type dispersant having a high cation exchange capacity, that is, a high calcium-capturing ability, and have improved both the liquid phase and the solid component. It has been found that excellent stability can be achieved by using a polymer type dispersant having a high affinity for the components.

[0007] In particular, when the water content in the detergent composition is 5% by weight or less, the crystalline silicate compound becomes an excellent alkali agent and calcium scavenger, and thus has high detergency, and further has a liquid phase and a solid component. It has been found that excellent stability can be achieved by using a polymer type dispersant having high affinity for both components.

The present invention comprises a liquid phase [(a) phase], a polymer type dispersant [component (b)], and a crystalline silicate compound and / or an aluminosilicate compound [component (c)]. And a liquid detergent composition having a volume separation rate of 5% or less after storage at 25 ° C. for one month [provided that the water content in the composition is 5% by weight.
Below, when only the aluminosilicate compound in the component (c) is used, or when the water content in the composition exceeds 5% by weight, the component (b) has a cation exchange capacity of 120 CaCO ₃ mg / g or more. Have. And a method for producing the same.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION [(a) Phase: Liquid Phase] The content of the liquid phase (a) is 30 to 95 in the liquid detergent composition.
% By weight, more preferably from 40 to 90% by weight.
The content of the (a) phase is determined by a centrifuge (h
The solid content in the liquid detergent composition was precipitated using imac CR22F) (separation conditions: 10,000 rotations / 1 minute, 30 minutes / 25 ° C.), and a 0.1 μm membrane filter (A
The sedimentation component can be obtained as a filtrate amount (25 ° C.) obtained by filtering a sediment component using DVANTEC (material: PTFE).

[0010] The (a) phase comprises a surfactant as an essential component,
Further, if necessary, water and a water-soluble organic solvent are contained. This (a) phase may contain water, but for compactness of the detergent composition, the content of water in the (a) phase is preferably 60% by weight or less, and (a) More preferably, the phase is a non-aqueous liquid phase substantially free of moisture. The non-aqueous system is a system in which water is not intentionally added, and the content of water is preferably 5% by weight or less, more preferably 2% by weight or less in the liquid detergent composition.

(A) The surfactant content in the phase is 10 to 1
It is preferably 00% by weight, more preferably 50 to 100% by weight, and particularly preferably 60 to 100% by weight. As the surfactant, a nonionic surfactant is preferable. Anionic surfactant, cationic surfactant, and zwitterionic surfactant are also used together with the nonionic surfactant as long as they do not inhibit the stability of the product ( a) It can be used by dissolving in the phase.
It is also preferred that (a) phase is a non-ionic surfactant.

A-1: Nonionic surfactant A nonionic surfactant has been conventionally used in a detergent composition, and is suitable in that it has excellent detergency and stability. . The content of the nonionic surfactant is preferably 70 to 100% by weight in the surfactant, and more preferably 90 to 100% by weight.
100% by weight, especially 100% by weight, is preferred.

As the nonionic surfactant, for example, a known nonionic surfactant described in Japanese Patent Office Publication “Chapter 3-1 of the Collection of Well-known and Conventional Techniques (Powder Detergent for Clothing)” can be used. .

In the liquid detergent composition of the present invention, it is particularly preferable to use a nonionic surfactant of the polyethylene oxide and / or polypropylene oxide type, especially a linear or branched chain having 8 to 18 carbon atoms. Polyoxyethylene alkyl ethers having an average of 5 to 20 moles of ethylene oxide added to a primary or secondary alcohol of the formula: and polyoxyethylene polyoxypropylene having an average of 5 to 15 moles of ethylene oxide and an average of 1 to 5 moles of propylene oxide added It is preferable to use one or more selected from alkyl ethers (however, ethylene oxide and propylene oxide may be added randomly or in blocks).

Other nonionic surfactants include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, sucrose fatty acid esters,
Fatty acid glycerin monoesters, higher fatty acid alkanolamides, polyoxyethylene higher fatty acid alkanolamides, amine oxides, alkyl glycosides, alkyl glyceryl ethers, N-alkyl gluconamides and the like can also be used.

A-2: Anionic surfactant The liquid detergent composition of the present invention includes, for example, Japanese Patent Office Publication "Chapter 3-1 of the Collection of Well-known and Conventional Techniques (Powder Detergent for Clothing)".
The known anionic surfactants described can be used. In particular, a sulfonate type, a sulfate type, a phosphate type and / or a carboxylate type anionic surfactant are suitably blended.

Specifically, it has a linear or branched alkyl or alkenyl group having an average of 8 to 22 carbon atoms,
One or more anionic surfactants selected from alkylbenzene sulfonates, alkyl sulfates, polyoxyethylene alkyl ether sulfates (average ethylene oxide addition moles: 0.5 to 6 moles), monoalkyl phosphates and fatty acid salts Agents are preferred.

Examples of counter ions of these anionic surfactants include cations obtained by protonating amines such as sodium, potassium, magnesium, calcium, and ethanolamines, quaternary ammonium salts, and mixtures thereof. . When blending an anionic surfactant, a method of blending in an acid form and separately adding an alkali (eg, ethanolamine) may be used.

A-3: Cationic surfactant The liquid detergent composition of the present invention includes, for example, Japanese Patent Office Publication "Chapter 3-1 of the Collection of Well-known and Conventional Techniques (Powder Detergent for Clothing)".
The known cationic surfactants described can be used, and for example, a quaternary ammonium salt such as a benzalkonium type is suitably blended.

A-4: Amphoteric Surfactant The liquid detergent composition of the present invention includes, for example, the Japanese Patent Office Publication “Chapter 3-1 of the Collection of Well-known and Conventional Techniques (Powder Detergent for Clothing)”.
The known zwittersurfactants described above can be used, and for example, alkyl betaine type zwittersurfactants and the like are suitably blended.

A-5: Water-soluble organic solvent The water-soluble organic solvent is a liquid detergent of the present invention for the purpose of adjusting the viscosity of a product, preventing gelation of a nonionic surfactant, and adjusting the solubility in washing water. Formulated in the composition.

Specifically, polyhydric alcohols such as butanediol, pentanediol, hexanediol, glycerin, trimethylolpropane and pentaerythritol, mono-, di- or tri-alkyl ethers of polyhydric alcohols, ethylene glycol , Glycols such as propylene glycol, polyethylene glycol and polypropylene glycol, monoalkyl ethers and monoaryl ethers of glycols, especially monophenyl ether, polyether, alkylamine, aliphatic amine, amide or alkyl of aliphatic or aromatic carboxylic acid Esters, lower alkyl esters, ketones, aldehydes, glycerides and the like can be mentioned. One or two of these organic solvents are used.
It is blended as a mixture of more than one kind, and its content is preferably 0 to 90% by weight, more preferably 0 to 50% by weight, particularly 0 to 50% by weight in the phase (a) from the viewpoint of detergency and compactness of the detergent composition. 40% by weight is preferred.

[Component (b): Polymeric dispersant] The content of the component (b), which is a polymer type dispersant, is selected from the group consisting of a liquid to obtain good dispersibility and to prevent an excessive increase in viscosity. 0.1 to 10% by weight in the detergent composition is preferred, and 0.1 to 5% by weight.
%, More preferably 0.1 to 3% by weight.

The polymer type dispersant is a polymer having good solubility or uniform dispersibility in the phase (a) and stable dispersibility of the solid component including the component (c).

The component (b) has solubility or uniform dispersibility in the phase (a). In this method, 2 g of a dry matter of a polymer is put into a 300 mL beaker, and 36.8 g of the phase component (a) used in the composition containing the component (b) is poured into the beaker. (3 cm), heated to 50 ° C. at 150 r / min, stirred for 5 hours, cooled, and allowed to stand for 30 minutes (25 ° C.), and confirmed that no precipitate was visually observed at the bottom of the beaker. it can.

The component (b) has a stable dispersibility of the solid component including the component (c). What is stable dispersibility?
It shows that the volume separation ratio after storage of the liquid detergent composition of the present invention at 25 ° C. for one month after production is 5% or less. The volume separation ratio is a ratio of a volume of a transparent liquid phase generated at an upper portion due to sedimentation and separation of a solid component in a total volume of the composition. Specifically, it is measured by a method described later.

The liquid detergent composition of the present invention comprises a liquid phase [(a) phase], a polymer type dispersant [component (b)], and a crystalline silicate compound and / or an aluminosilicate compound [( c) after storage at 25 ° C. for one month, the volume separation rate is 5% or less, the water content in the composition is 5% by weight or less, and the aluminosilicate compound in the component (c) When only water is used, or when the water content in the composition exceeds 5% by weight, the component (b) contains 120 CaCO ₃ m
It has a cation exchange capacity of at least g / g, preferably at least 150 CaCO ₃ mg / g, more preferably at least 180 CaCO ₃ mg / g. A larger cation exchange capacity is preferable because of a higher detergency.

Particularly preferred liquid detergent compositions are those having a liquid phase [(a) phase] of at least 120 CaCO ₃ mg / g, preferably at least 150 CaCO ₃ mg / g, more preferably at least 180 CaCO ₃ mg / g. It contains a polymer type dispersant [component (b)] having a cation exchange capacity, and a crystalline silicate compound and / or an aluminosilicate compound [component (c)], and has a volume after storage at 25 ° C. for one month. The separation rate is 5% or less. The cation exchange capacity of the component (b) may be 320 CaCO ₃ mg / g or less.

The cation exchange capacity referred to here is a value obtained by measuring by the following method. (B) component about 0.1
g was precisely weighed, and 0.1 M NH ₄ Cl—NH ₄ having a pH of 10.
Dissolve in 100 mL of OH buffer. This was kept at 25 ° C., and while measuring the potential, titration was performed using a calcium ion solution of pH = 10 and 20,000 ppm in terms of CaCO ₃ , and calcium remaining in the solution was determined from the relationship between the amount of drop and the potential difference. The ion concentration is estimated, and the amount of trapped calcium ions is calculated therefrom. The calcium ion trapping amount obtained by this method is expressed as a cation exchange capacity.

The component (b) includes two types of polymer chains having a polymer chain having solubility or uniform dispersibility in the phase (a) and a polymer chain having stable dispersion of the solid component including the component (c). It is preferably a polymer comprising the above polymer chains, and more preferably a block or graft polymer.

Further, (a) a polymer chain having solubility or uniform dispersibility in the phase, (c) a polymer chain having a functional group having a high affinity for the component, and a carboxyl group which is effective for capturing calcium. A polymer chain having a polymer chain composed of a vinyl monomer (preferably having a cation exchange capacity of 120 CaCO ₃ mg / g or more as measured by the above method) is particularly preferred. In each polymer chain, monomers can overlap.

(A) The following monomers (1) to (1) are used to form a polymer chain having solubility or uniform dispersibility in the phase.
One or more kinds selected from the monomers of 3) can be used. Although not particularly limited, since the monomers (1) and (2) have relatively high affinity for water, (a) of the liquid detergent composition mainly having a water content of more than 5% by weight of the whole composition. A polymer chain that exhibits good solubility in the phase. The monomers (3) to (13) have a relatively high affinity for surfactants and water-soluble organic solvents. 5% by weight or less of the liquid detergent composition to form a polymer chain having good solubility in the phase (a). (1) Vinyl monomers having a sulfonic acid group. For example, styrenesulfonic acid (or a salt thereof), 2-acrylamido-2-methylpropanesulfonic acid (or a salt thereof),
(Meth) allylsulfonic acid (or a salt thereof) is preferred. (2) Vinyl monomers having a cationic group. For example, 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, 2-[(meth) acryloyloxy] ethyldimethylethylammonium chloride, ethyl sulfate,
[(Meth) acrylamide] propyltrimethylammonium, diallyldimethylammonium chloride and the like are preferred. (3) Vinyl ethers having an unsubstituted or substituted C1-C22 saturated or unsaturated alkyl group, aryl group or aralkyl group. For example, methyl vinyl ether, ethyl vinyl ether, 4-hydroxybutyl vinyl ether, phenyl vinyl ether and the like are preferable. (4) Unsubstituted or substituted (meth) acrylamides having a saturated or unsaturated alkyl or aralkyl group having 1 to 12 carbon atoms on nitrogen. For example, (meth) acrylamide, N-methyl (meth) acrylamide, N,
N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- [2
-(N, N-dimethylamino) ethyl] (meth) acrylamide, N- [3- (N, N-dimethylamino) propyl] (meth) acrylamide, N- [2-hydroxyethyl] (meth) acrylamide, N -Methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide and the like are preferred. (5) N-vinyl aliphatic amides. For example, N-vinylpyrrolidone, N-vinylacetamide, N-vinylformamide and the like are preferable. (6) C1-C22 unsubstituted or substituted (meth) acrylic esters having a saturated or unsaturated alkyl group or an aralkyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylate
(N, N-dimethylamino) ethyl, 2-methoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and the like are preferred. (7) Alkylene oxides. For example, ethylene oxide and propylene oxide are preferred. (8) Cyclic imino ethers. For example, 2-methyl-2-
Oxazoline, 2-phenyl-2-oxazoline and the like are preferred. (9) Styrenes. For example, styrene, 4-ethylstyrene, α-methylstyrene and the like are preferable. (10) Vinyl esters. For example, vinyl acetate, vinyl caproate and the like are preferable. (11) Polyesters comprising a dihydric alcohol and a dicarboxylic acid. For example, a polycondensate of polyethylene glycol and terephthalic acid, or 1,4-butanediol and succinic acid is preferable. (12) Polyamides. For example, a ring-opened polymer of N-methylvalerolactam is preferred. (13) Polyurethanes. For example, polyethylene glycol, hexamethylene diisocyanate, and a polyadduct of N-methyl-diethanolamine or 1,4-butanediol are preferable.

Although other copolymerizable monomers can be copolymerized, the structural units derived from the above monomers have a solubility in the phase (a) of 60 mol / mol in the polymer chain. % Or more, preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%.

As a functional group having a high affinity for the component (c),
Examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, a primary to tertiary amino group, and a quaternary ammonium group. (C) As monomers for forming a polymer chain having a functional group having a high affinity for the component, (meth) acrylic acid and its salts, styrene carboxylic acid and its salts, maleic acid and its salts, itaconic acid and its salts, styrene sulfone Acid and its salts, (meth) allylsulfonic acid and its salts, 2-acrylamido-2-methylpropanesulfonic acid and its salts, vinylsulfonic acid and its salts, vinyl alcohol, 2-hydroxyethyl (meth) acrylate, N -[2-hydroxyethyl] (meth) acrylamide, 4-hydroxymethylstyrene, mono-2-[(meth) acryloyloxy] ethyl phosphate, 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride, vinylbenzyl chloride Trimethylammonium, ethyl sulfate 2- [ Meth) acryloyloxy] ethyl dimethylethyl ammonium chloride, 3-
[(Meth) acrylamide] One or more selected from propyltrimethylammonium, diallyldimethylammonium chloride, vinylpyridine and the like can be used.
Other copolymerizable monomers can also be copolymerized, but in order to increase the affinity for the component (c), the constituent units derived from the above-mentioned monomers are at least 60 mol% in the polymer chain, and It is preferably at least 90 mol%, more preferably at least 90 mol%, particularly preferably 100 mol%.

Monomers which form a polymer chain composed of a vinyl monomer having a carboxyl group and are effective for capturing calcium include (meth) acrylic acid and salts thereof, styrenecarboxylic acid and salts thereof, maleic acid and salts thereof, and itaconic acid. And salts thereof, and one or more selected from these can be used. Other copolymerizable monomers can also be copolymerized, but in order to increase the ability to capture calcium, the constituent units derived from the above monomers are at least 60 mol% in the polymer chain, and at least 80 mol%. Is preferable, and 90 mol% or more is more preferable.
100 mol% is particularly preferred.

The polymer chain composed of a vinyl monomer having a carboxyl group has a high affinity for the component (c), and the component (b) having the polymer chain has a high affinity for the component (c).
There is no need for high affinity polymer chains for the components.

More preferred as component (b) are
(A) a polymer having a polymer chain having solubility or uniform dispersibility in a phase (hereinafter referred to as polymer chain 1) and a polymer chain having a functional group having high affinity for the component (c) (hereinafter referred to as polymer chain 2); A block or graft polymer consisting of chains 1 and 2. Particularly preferred as the component (b) is a polymer chain having a functional group having a high affinity for the component (c) and derived from a vinyl monomer having a carboxyl group.

By the presence of these two types of polymer chains, the performance of both types is effectively exhibited. In order to more effectively exhibit the performance of both, a graft polymer is particularly preferable. The weight ratio of the two polymer chains [(polymer chain 1) / (polymer chain 2)] 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), 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 previously coexisted by a chain transfer reaction (chain transfer method). A method of reacting and linking another type of polymer end to the functional group is preferable.

Preferred examples of the component (b) obtained by these methods include the following 1 to 12. 1. 1. A block polymer obtained by radical polymerization of (meth) acrylic acid (or a salt thereof) using a polyethylene glycol macroazo initiator. 2. Copolymer of polyethylene glycol mono (meth) acrylate and (meth) acrylic acid (or a salt thereof) 3. Copolymer of polyethylene glycol mono (meth) acrylate and styrene sulfonic acid (or a salt thereof) 4. Copolymer of polyethylene glycol mono (meth) acrylate and 2-((meth) acryloyloxy) ethyltrimethylammonium chloride 5. Copolymer of polyethylene glycol mono (meth) acrylate and 2-hydroxyethyl (meth) acrylate 6. Graft polymer obtained by radical polymerization of acrylic acid and maleic acid (or a salt thereof) in polyethylene glycol, polypropylene glycol or polyethylene glycol propylene glycol. 7. Graft polymer obtained by radical polymerization of diallyldimethylammonium chloride in an aqueous solution of poly (N, N-dimethylacrylamide / styrene) copolymer Poly (N, N-dimethyl (meth) acrylamide)
8. Graft polymer obtained by radical polymerization of 2-acrylamido-2-methyl-propanesulfonic acid (or a salt thereof) in an aqueous solution. 9. A graft polymer obtained by connecting poly (meth) acrylic acid and polyethylene glycol having a hydroxyl group at a terminal by a dehydration reaction. 10. A graft polymer obtained by radical polymerization of acrylic acid and maleic acid (or a salt thereof) in an aqueous solution of polystyrene sulfonate. 11. Graft polymer obtained by radical polymerization of diallyldimethylammonium chloride in poly (acrylic acid / maleic acid) aqueous solution Graft polymer obtained by radical polymerization of polyethylene glycol allyl ether and maleic acid In the above 1 to 12, the compound having a polyethylene glycol skeleton may have an alkoxy group such as a methoxy group.

Among these, particularly preferred polymers are
1, 2, 6, 9 and 12 polymers.

In the liquid detergent composition of the present invention, when the water content is 5% by weight or less based on the whole composition, the order of 2, 6, 12, 9, 1, etc. is particularly preferable. These polymers have a relatively high solubility or homodispersity in liquid phases with a water content of less than 5% by weight.

In the liquid detergent composition of the present invention, when the water content is more than 5% by weight of the whole composition, the order is particularly preferably from 10, 6, 2, 12, 9, and so on. These polymers have a relatively high solubility or homodispersity in liquid phases with a water content of more than 5% by weight. 2, 6, 12, 9
Can increase the affinity for both liquid phases.

The salts of component (b) include basic amino acid salts, alkali metal salts such as sodium and potassium, ammonium salts, alkyl or alkenyl ammonium salts having 1 to 12 carbon atoms, and alkanols having 1 to 12 carbon atoms. Examples thereof include an ammonium salt, and the like, preferably an alkali metal salt, and more preferably a sodium salt.

The weight average molecular weight of the component (b) is preferably 1,000,000 or less, more preferably 1,000 to 500,000, and particularly preferably 5000 to 300,000, for the purpose of preventing an excessive increase in viscosity.

[Component (c): crystalline silicate compound and / or aluminosilicate compound] The component (c) is at least one selected from crystalline silicate compounds and aluminosilicate compounds. The total content is preferably 3 to 69.9% by weight in the liquid detergent composition, and 10 to 60% by weight.
% By weight is more preferred.

As the crystalline silicate compound, there can be mentioned a compound represented by the general formula (I).

[0047] ^{_{(M 1 p M 2 q M}} 3 r O) (M 4 s M 5 t O) x (SiO 2) y (I) [ wherein, M ^1, M ² and M ³ respectively Na, K Or H, and M ⁴ and M ⁵ each represent Ca or Mg. p, q
And r are each a number from 0 to 2 (where p + q + r = 2);
s and t are numbers from 0 to 1 (s + t = 1), x
Represents a number of 0 to 1, and y represents a number of 0.9 to 3.5. The crystalline silicate compound is specifically a layered sodium silicate, for example, SKS-6 (manufactured by Hoechst) or Patent No. 25
No. 25318, Japanese Patent No. 2759243, Japanese Patent No. 2618799, Japanese Patent No. 2525342, and Japanese Patent Application Laid-Open No. 5-184946.

The aluminosilicate compound includes a compound represented by the general formula (II).

(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 ) (II) wherein M ¹ , M ² , M ³ , M ⁴ , M ⁵ , p, q, r, s and t have the same meaning as described above. u is a number from 0 to 1, preferably 0.1 to 0.5, and v is 0 to 1, preferably 0 to 0.
The number 1 and w represent a number of 0 to 0.6, preferably 0.1 to 0.5. Examples of such aluminosilicate compounds include, for example, types A, X, and P of various zeolites generally blended in a detergent, and type A is particularly preferable. Zeolite is a very excellent detergent builder due to its high cation exchange ability, and is preferred because it greatly increases the detergency of the detergent composition. Such zeolites include, for example, Toyobuilder commercially available from Toyo Soda Co., Ltd. In addition, in the manufacturing process of the cleaning composition of the present invention described below, finely divided zeolite is used because it is easily pulverized, thereby improving the dispersion stability. Thus, the zeolite manufactured by the method described in Japanese Patent Application No. 11-318604 is used. It is also preferred. Generally, commercial zeolites contain about 20% moisture. When producing a liquid detergent composition that is substantially free of moisture,
It is preferable to use such a commercially available zeolite after firing at 450 to 600 ° C. to remove moisture.

The average particle size of the component (c) is preferably 500 μm or less, preferably 0.1 to 20 μm, more preferably 0.1 to 2 μm, and particularly preferably 0.1 to 1.0 μm. Here, the average particle size refers to a laser diffraction /
It is an average particle diameter of a volume-based particle diameter measured by a scattering type particle size distribution analyzer LA-910, and means this unless otherwise noted.

[(D) Other components] The liquid detergent composition of the present invention further comprises, as other components, a surfactant, an inorganic builder, an organic builder, a bleach,
Common detergent additives can be included.

When these are solid, similarly to the component (c), they can be finely divided by the method described later and dispersed and blended in the present detergent composition. At this time, the average particle size of each solid component is preferably 500 μm or less, preferably 0.1 to 20 μm, more preferably 0.1 to 2 μm, and particularly preferably 0.1 to 1.0 μm.

D-1: Surfactant Insoluble in (a) Phase The liquid detergent composition of the present invention contains a surfactant in the (a) phase. A surfactant which is insoluble in the phase may be dispersed and blended as a solid component.

D-2: Inorganic builder In addition to the component (c), known silicates and metasilicates,
Detergent builders such as carbonates can be arbitrarily compounded. These are preferably alkali metal salts.

For example, phosphates such as tripolyphosphate and pyrophosphate, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) Alternatively, salts thereof can also be used.

D-3: Organic builder The liquid detergent composition of the present invention can also contain a known organic builder that is soluble or / and insoluble in the phase (a). Specifically, polycarboxylic acids such as citric acid, succinic acid, and malonic acid; amino acids such as aspartic acid and glutamic acid; aminopolyacetic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid; polyacrylic acid; and acrylic acid / maleic acid High molecular polycarboxylic acids such as polymers,
These are preferably in the form of a salt such as an alkali metal salt, an ammonium salt, or a substituted ammonium salt.

D-4: Bleaching agent The liquid detergent composition of the present invention preferably contains a bleaching agent. As the bleaching agent, an inorganic peroxygen bleach or a combination of an inorganic peroxygen bleach and a bleach activator can be used.

Examples of the inorganic peroxygen bleach include alkali metal perborates, percarbonates, persilicates, and perphosphates, and particularly preferred are sodium perborate and sodium percarbonate. In order to enhance the dispersion stability of the product, the product is coated with a carboxylic acid-based polymer and / or a polycarboxylic acid as described in JP-A-11-279593, page 2, column 2, lines 13 to 44. Percarbonate can be used.

When a combination of an inorganic peroxygen bleach and a bleach activator is used, the bleach activator is usually an organic compound having at least one reactive acyl group forming a peracid,
The bleaching action is more effective than using the inorganic peroxygen bleach alone. The structure of the bleaching activator is not particularly limited, but those represented by the general formula (III) are preferred.

[0060]

Embedded image

[Wherein, R ¹ represents a linear or branched alkyl group having 1 to 15 carbon atoms, and X represents COOM or SO ₃ M
(Where M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom). In the bleaching activator represented by the general formula (III), in the general formula (III), R ¹ is a linear or branched alkyl group having 7 to 11 carbon atoms, and X is COOH or SO ₃ Na. Is preferred. Examples of such a bleach activator include sodium lauroyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium octanoyloxybenzenesulfonate, lauroyloxybenzoic acid, decanoyloxybenzoic acid, and octanoyloxybenzoic acid. Can be mentioned.

Polymers such as polyethylene glycol and carboxymethyl cellulose used in general detergents, color transfer inhibitors such as polyvinylpyrrolidone, enzymes such as protease, cellulase and lipase, and enzyme stabilization such as calcium chloride, formic acid and boric acid. An antifoaming agent such as an agent, an antifoaming agent such as silicone, an antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite, and sodium hydrogen sulfite, a fragrance component, a dye, a fluorescent dye, and a pigment may be included as necessary.

[Production Method] The liquid detergent composition of the present invention comprises a step of wet-milling the components (b) and (c) in the phase (a) to obtain a finely divided solid component slurry, preferably It is produced by the production method 1 comprising the first, second and third steps, or the component (c) in the (a) phase is wet-milled to obtain a finely divided solid component slurry, and then the component (b) is added. Preferably, it is produced by a production method 2 comprising first, second, third and fourth steps.

Production Method 1 As a first step, a surfactant as a phase (a), and a water-soluble organic solvent and ion-exchanged water as required, are mixed, and the component (b) is dissolved or uniformly dispersed therein (hereinafter, referred to as a “dispersion”). Dispersion medium (1)). At this time, an appropriate temperature, for example, 50 to 6
It can be heated to 0 ° C. It is preferable to add a bleach activator, a peroxygen bleach component, an enzyme, a brightener, a fragrance and the like in the third step described later.

In the second step, the mixture of the component (c) and the other solid component requiring pulverization is wet-pulverized in the dispersion medium (1). When the component (c) is finely divided, the calcium exchange rate increases with an increase in the surface area, so that the component becomes a more excellent detergent builder. However, this is known to cause a gradual chemical change due to water vapor and carbon dioxide in the air, resulting in a decrease in calcium exchange capacity. This phenomenon is promoted by an increase in surface area, so powder detergents and the like are used. It was difficult to incorporate a finely divided crystalline silicate compound or aluminosilicate compound into the mixture. Patent No. 2958
No. 506 discloses a method for producing a fine-particle solid builder by wet-pulverizing a solid builder such as a crystalline silicate compound or an aluminosilicate compound in a dispersion medium containing a surfactant. An excellent microcrystalline silicate compound or aluminosilicate compound having a high calcium exchange ability can be obtained. The surfactants, water-soluble organic solvents, and solid builders (inorganic builders and organic builders other than crystalline silicate compounds and aluminosilicate compounds) that are preferable for the liquid detergent composition of the present invention are as described above. In the composition of the present invention, solid components other than the solid builder can also be finely divided by the same method. When blending a bleach activator insoluble in the liquid phase among the solid components other than the solid builder, it may be subjected to wet grinding simultaneously with the other solid components, or may be added during the wet grinding and subjected to grinding. Or in the third step.

Examples of the wet pulverization method include a stone mill, a colloid mill, a caddy mill, a slasher mill, a high-speed disperser, a media mill, a roll mill, a kneader, an extruder, and a pulverizer having a liquid jet interaction chamber (for example, a micro milling machine). (Micro Fly Diizer manufactured by K.K.), an ultrasonic disperser, and the like. Among others, wet pulverization using a medium, for example, a method using a sand mill, a sand grinder, a wet vibration mill, an attritor, and the like are preferable from the viewpoint of pulverization efficiency. Known materials such as titania and zirconia can be used as the media.

In the case of pulverization using a sand mill, a medium having a diameter of 0.1 to 1.0 mm is particularly suitable. When the particle size of the solid builder as a raw material is particularly large, the particle size suitable for the wet pulverization in advance by a dry pulverization method, for example, pulverization to 2 to 300 microns, or pulverization using a medium having a large diameter, e.g. In some cases, subsequent to this, effective fine pulverization can be performed by using a medium having a smaller diameter.

At the time of wet pulverization, in order to increase the pulverization efficiency of the solid component, preferably, a mixture of the component (c) and another solid component (or approximately the component (c)) / dispersion medium (1 ) (Or may be approximately component (a))
(Weight ratio) = 30 / 70-60 / 40, and pulverization is performed.

In the wet pulverization, in order to increase the pulverization efficiency of the solid components, the mixture of the component (c) and another solid component (or approximately the component (c)) and the dispersion medium (1) ( Alternatively, the total volume of the (a) component may be approximately 0.1% of the gap volume of the media filled in a ball media mill (sand mill, sand grinder, wet vibration mill, attritor, etc.). It is 9 to 1.1 times, more preferably 0.95 to 1.05 times. Here, the 1.0-fold gap capacity of the medium means that the medium is charged while being vibrated, densely filled, then ion-exchanged water is gently injected at 20 ° C. and filled to the top of the medium. Use the volume of water to be replaced.

The end of the wet pulverization is when the change in the average particle size of the solid component is eliminated, but is preferably 3 minutes or more. More preferably, it is 5 minutes or more.

At the time of wet pulverization, in order to keep the viscosity of the system low and increase the pulverization efficiency, the component of the phase (a) can be added in several times. The component of the (a) phase added here is:
The components may be different from those of the first step. It is preferable to add a medium according to the capacity to be added so as to maintain the ratio of the total capacity to the gap capacity of the medium.

The average particle size of the finely divided solid component slurry thus obtained is preferably 500 μm or less, preferably 0.1 μm or less.
To 20 μm, more preferably 0.1 to 2 μm, particularly preferably 0.1 to 1.0 μm.

In some cases, the component of the phase (a) may be further added so as to obtain a desired compounding ratio. After mixing,
The media may be removed, but the media may be removed after other components are added and mixed in the third step.

In the third step, a solid component which is preferably not subjected to wet pulverization in the second step and other optional components which are soluble in a liquid are mixed and compounded. The solid component which is preferably not subjected to the wet pulverization in the second step may be previously subjected to an operation of reducing the particle diameter under mild conditions.

Production Method 2 In the first step, a surfactant, and if necessary, a water-soluble organic solvent and ion-exchanged water are mixed to obtain phase (a).
It is preferable to add a bleach activator, a peroxygen bleach component, an enzyme, a brightener, a fragrance, and the like in a fourth step described later.

In the second step, the mixture of the component (c) and other solid components that need to be ground is wet-ground in the phase (a). When the component (c) is finely divided, the calcium exchange rate increases with an increase in the surface area, so that the component becomes a more excellent detergent builder. However, this is known to cause a gradual chemical change due to water vapor and carbon dioxide in the air, resulting in a decrease in calcium exchange capacity. This phenomenon is promoted by an increase in surface area, so powder detergents and the like are used. It was difficult to incorporate a finely divided crystalline silicate compound or aluminosilicate compound into the mixture. Patent No. 2958
No. 506 discloses a method for producing a fine-particle solid builder by wet-pulverizing a solid builder such as a crystalline silicate compound or an aluminosilicate compound in a dispersion medium containing a surfactant. An excellent microcrystalline silicate compound or aluminosilicate compound having a high calcium exchange ability can be obtained. The surfactants, water-soluble organic solvents, and solid builders (inorganic builders and organic builders other than crystalline silicate compounds and aluminosilicate compounds) that are preferable for the liquid detergent composition of the present invention are as described above. In the composition of the present invention, solid components other than the solid builder can also be finely divided by the same method. When blending a bleach activator insoluble in the liquid phase among the solid components other than the solid builder, it may be subjected to wet grinding simultaneously with the other solid components, or may be added during the wet grinding and subjected to grinding. Or may be blended in the fourth step.

As the wet pulverization method, in particular, a wet pulverization method using a medium, for example, a method using a sand mill, a sand grinder, a wet vibration mill, an attritor, etc. is preferable from the viewpoint of the pulverization efficiency. Known materials such as titania and zirconia can be used as the media.

In the case of pulverization using a sand mill, a medium having a diameter of 0.1 to 1.0 mm is particularly suitable. When the particle size of the solid builder as the raw material is particularly large, the particle size suitable for the wet pulverization by a dry pulverization method in advance, for example, pulverized to 80 to 300 microns,
Alternatively, after pulverization is performed using a medium having a large diameter, for example, a diameter of 2 mm, effective fine pulverization may be performed by using a medium having a smaller diameter.

In order to enhance the grinding efficiency of the solid component, the total volume of the (a) phase and the mixture of the component (c) and other solid components (or approximately the (c) component) can be obtained during wet grinding. Is preferably 0.9 to 1.1 times, more preferably 0.95 to 1.05 times the gap capacity of the media filled in a ball media mill (sand mill, sand grinder, wet vibration mill, attritor, etc.). It is. Here, the 1.0-fold gap capacity of the medium means that the medium is charged while being vibrated and densely filled, and then ion-exchanged water is gently injected at 20 ° C. to fill the upper part of the medium. Use the volume of water to be replaced.

In order to increase the pulverization efficiency of the solid components during the wet pulverization, it is preferable to use the component (c) and a mixture of other solid components (or approximately the component (c)) /
(A) Phase (weight ratio) = 30/70 to 60/40.

The end of the wet pulverization is when the change in the average particle size of the solid component has ceased, but is preferably 3 minutes or more. More preferably, it is 5 minutes or more.

At the time of wet pulverization, in order to keep the viscosity of the system low and increase the pulverization efficiency, the component of the phase (a) can be added in several times. The component of the (a) phase added here is:
The components may be different from the dispersion medium obtained in the first step. It is preferable to add a medium according to the capacity to be added so as to maintain the ratio of the total capacity to the gap capacity of the medium.

The average particle size of the finely divided solid component slurry after the wet pulverization is preferably 500 μm or less, preferably 0.1 to 500 μm.
It is 20 μm, more preferably 0.1 to 2 μm, particularly preferably 0.1 to 1.0 μm.

As a third step, in another tank, a surfactant,
The component (b) is dissolved or uniformly dispersed in the phase (a) to which a water-soluble organic solvent and ion-exchanged water are added as required.
The component of the (a) phase used here may be different from the component of the dispersion medium in the first step.

The phase (a) containing the component (b) is added to the finely divided solid component slurry obtained in the second step, and mixing is further continued. (B) at an appropriate temperature during compounding,
For example, it can be heated from 50 ° C. to 60 ° C. Then, depending on the case, (a)
Some of the phases may be further added. After the mixing is finished, the media may be removed, or the media may be removed after other components are added and mixed in the fourth step.

In the fourth step, a solid component which is preferably not subjected to wet pulverization in the second step and other optional components which are soluble in a liquid are mixed and blended. The solid component which is preferably not subjected to the wet pulverization in the second step may be previously subjected to an operation of reducing the particle diameter under mild conditions.

The liquid detergent composition of the present invention can be prepared by the following processes:
Both can be produced, but production method 2 is more preferable because component (c) is easily miniaturized and better stability is obtained.

When a solid component having a sufficiently small particle size is used in advance by dry grinding or the like, a liquid detergent composition can be easily obtained by using a disperser such as a flow jet mixer. .

The liquid detergent composition of the present invention preferably has a viscosity of about 10-5000 mPa · s, more preferably 100-3000, from the viewpoint of improving the dispersion stability of the particles and preventing the liquid from scattering during use. mPa · s. The viscosity is 20
A 0 mL beaker is filled with 200 g of the present composition, and the No. 2 rotor is rotated for 30 r with a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.
/ Min speed condition (25 ° C.).

[0090]

EXAMPLES Synthesis Example 1: Polymeric dispersant (2) [N, N-
Dimethylacrylamide / 2-acrylamide-2-methylpropanesulfonate = 80/20 (molar ratio) random copolymer] 95 g of N, N-dimethylacrylamide, sodium 2-acrylamide-2-methylpropanesulfonate 55
g in 400 g of ion-exchanged water.
Stirred for 0 minutes. In addition, 2,2'-azobis- (2-
Amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) (1.6 g) was added, and the mixture was heated under a nitrogen atmosphere.
Stirring was continued for 6 hours while maintaining the temperature at 5 to 70 ° C. Thereafter, the temperature is returned to room temperature, and the aqueous solution is freeze-dried to give a polymer type dispersant (2).
I got As a result of GPC measurement of the obtained dispersant, the weight average molecular weight was 22,000 (in terms of polyethylene glycol). The GPC measurement conditions were as follows: column: two TSK GMPWXL manufactured by Tosoh Corporation, eluent: 0.2
M phosphate buffer / acetonitrile = 9/1, detector: differential refractometer, temperature: 40 ° C.

0.1 g of this polymer type dispersant (2) was precisely weighed and dissolved in 100 mL of a 0.1 M NH ₄ Cl—NH ₄ OH buffer solution having a pH of 10. Then, the solution was kept at 25 ° C.
10. Using a calcium ion solution of 20,000 ppm in terms of CaCO ₃ , titration was performed while measuring the potential. Estimate the concentration of calcium ions remaining in the solution from a calibration curve created by measuring the relationship between the amount of drop and the potential difference, and the relationship between the potential difference and a calcium chloride solution with a known concentration in advance. As a result of calculating the calcium ion trapping amount of (2), that is, the cation exchange capacity, it was 23 CaCO ₃ mg / g. For the potential measurement, a 920A ion meter manufactured by Orion and a 9320 type electrode were used as calcium electrodes.

Synthesis Example 2: Synthesis Example of Polymeric Dispersant (3) [Block Polymer of Polyethylene Glycol and Polyacrylic Acid (40/60 (Weight Ratio))] Poly [polyoxyethylene 4,4′-azobis ( 4-cyanopentanoate)] (VPE-0201, manufactured by Wako Pure Chemical Industries, Ltd.), 40 g of acrylic acid, and ion-exchanged water 3
After stirring for 10 minutes under a nitrogen atmosphere, the mixture was heated and kept at 65 to 70 ° C. for 6 hours. While cooling this with ice, a 6N aqueous solution of sodium hydroxide 110 mL
Was gradually added to neutralize, and about 80% of the carboxyl groups of this polymer were converted to sodium salts. This aqueous solution was freeze-dried to obtain a polymer type dispersant (3). As a result of GPC measurement of the obtained dispersant, the weight average molecular weight was 78,000 (in terms of polyethylene glycol). The GPC measurement conditions are the same as in Synthesis Example 1. Further, the cation exchange capacity of the polymer type dispersant (3) was calculated by the same method as in Synthesis Example 1, and as a result, was 157 CaCO ₃ mg / g.

Synthesis Example 3: Polymeric dispersant (4) [polyethylene glycol and poly (acrylic acid / maleic acid = 7)
0/30 (molar ratio)) (graft polymer of 50/50 (weight ratio))
000, manufactured by Wako Pure Chemical Industries, Ltd.) 50 g, maleic acid 20.
4 g was heated and dissolved in a nitrogen atmosphere, and the temperature was raised to 150 ° C. while stirring was continued. While maintaining the temperature at 145 to 150 ° C., 29.6 g of acrylic acid and di-t-
4.3 g of butyl peroxide was separately added dropwise over 1 hour, and stirring was continued for 3 hours while maintaining the temperature at 150 ° C.
Return to room temperature. 200 mL of ion-exchanged water was added to dilute the solution, and while cooling the mixture with ice, 100 mL of a 6N aqueous sodium hydroxide solution was gradually added to neutralize the solution. This aqueous solution was freeze-dried to obtain a polymer type dispersant (4). As a result of GPC measurement of the obtained dispersant, the weight average molecular weight was 4.5.
10,000 (polyethylene glycol equivalent). Note that G
The PC measurement conditions are the same as in Synthesis Example 1. Further, the cation exchange capacity of the polymer type dispersant (4) was calculated by the same method as in Synthesis Example 1, and as a result, 190 CaCO ₃ mg / g
Met.

Synthesis Example 4: Polymeric dispersant (5) [Poly (N, N-dimethylacrylamide / styrene = 90 /
10 (molar ratio)) and poly (diallyldimethylammonium chloride (50/50 (weight ratio)) graft polymer] 89.5 g of N, N-dimethylacrylamide and 10.5 g of styrene are dissolved in 1 L of acetone, and nitrogen is dissolved. 1 under the atmosphere
Stirred for 0 minutes. To this, 2,2'-azobis- (2-methylbutyronitrile) (V-59, manufactured by Wako Pure Chemical Industries, Ltd.)
3.9 g was added, the mixture was heated under a nitrogen atmosphere, and stirring was continued for 6 hours while maintaining the reflux of acetone. After returning to room temperature, 8
The precipitate was purified by reprecipitation with L hexane, and the polymer collected by filtration was dissolved in 600 mL of ion-exchanged water. Then, hexane was distilled off by a rotary evaporator to obtain an aqueous solution of poly (N, N-dimethylacrylamide / styrene). As a result of GPC measurement of the obtained polymer, the weight average molecular weight was 22,000 (in terms of polystyrene). The GPC measurement conditions were as follows: Column: TSK manufactured by Tosoh Corporation
GMHHR-H2, eluent: 1 mM dimethyllaurylamine / chloroform, detector: differential refractometer, temperature:
40 ° C.

500 g of an aqueous solution of the obtained poly (N, N-dimethylacrylamide / styrene) (polymer 71.4)
g) was heated to 80 ° C. under a nitrogen atmosphere. In addition, 8
While maintaining the temperature at 0 to 85 ° C, 119 g of a 60% aqueous solution of diallyldimethylammonium chloride (manufactured by Tokyo Chemical Industry) and a solution of 5.3 g of sodium persulfate dissolved in 60 mL of ion-exchanged water were separately added dropwise over 2 hours, and added dropwise. 85 more after the end
Stirring was continued for 6 hours while maintaining the temperature. Thereafter, the temperature was returned to room temperature, and the aqueous solution was freeze-dried to obtain a polymer type dispersant (5).
As a result of GPC measurement of the obtained dispersant, the weight average molecular weight was 39,000 (in terms of polyethylene glycol). The GPC measurement conditions were as follows: column: TSK manufactured by Tosoh Corporation.
α-M 2 tubes, eluent: 0.15 M sodium sulfate / 1% acetic acid aqueous solution, detector: differential refractometer, temperature: 40
° C. Further, the cation exchange capacity of the polymer type dispersant (5) was calculated by the same method as in Synthesis Example 1, and as a result, 8
CaCO ₃ mg / g.

Synthesis Example 5: Synthesis Example of Polymeric Dispersant (6) [Polyethylene Glycol (EO Addition Number: 9) Monomethacrylate / Methacrylic Acid = 50/50 (Weight Ratio) Copolymer] Polyethylene Glycol (Number of moles of added EO: 9) 50 g of monomethacrylic acid ester and 50 g of methacrylic acid were dissolved in 200 g of ethanol, and the mixture was stirred under a nitrogen atmosphere for 10 minutes. To this, 2,2'-azobis- (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 1
1 g was added, the mixture was heated under a nitrogen atmosphere, and stirring was continued for 6 hours while maintaining the temperature at 75 to 80 ° C. Thereafter, the temperature was returned to room temperature, the precipitate was purified by reprecipitation with hexane, and dried to obtain a polymer type dispersant (6). As a result of GPC measurement of the obtained polymer, the weight average molecular weight was 40,000 (in terms of polyethylene glycol).
The GPC measurement conditions are the same as in Synthesis Example 1. Further, the cation exchange capacity of the polymer type dispersant (6) was calculated by the same method as in Synthesis Example 1, and as a result, 125 CaC
O ₃ mg / g.

Synthesis Example 6: Polymer type dispersant (7) [Polyester
Tylene glycol (number of moles of EO added 9) monomethacryl
Acid ester / acrylic acid = 20/80 (weight ratio) copolymer
Of 200 g of ion-exchanged water was heated to 60 ° C. in a nitrogen atmosphere.
Place, polyethylene glycol (EO added mole)
Number: 9) Monomethacrylate (NK-ester M)
-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 g, acrylic acid 8
0 g dissolved in 80 g of ion-exchanged water and 2,2 '
-Azobis- (2-methylpropionamidine) dihydrochloride
1.6 g of salt (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) was ion-exchanged.
Keep the solution dissolved in 120 g of water replacement at 60 to 65 ° C.
Dropwise over 2 hours while maintaining the temperature at 65 ° C.
The stirring was continued for another 6 hours. Let it cool to room temperature
Then, while cooling with ice, a 6N aqueous sodium hydroxide solution 150
mL of the polymer to neutralize it.
About 80% of the hydroxyl groups were converted to sodium salts. Freeze this aqueous solution
The mixture was dried by drying to obtain a polymer type dispersant (7). The resulting dispersion
As a result of GPC measurement of the agent, the weight average molecular weight was 49,000 (po
(In terms of ethylene glycol). In addition, GPC measurement
The fixed conditions are the same as in Synthesis Example 1. Also, polymer type dispersion
The cation exchange capacity of agent (7) was determined in the same manner as in Synthesis Example 1.
168 CaCO_Three mg / g
Was.

Synthesis Example 7: Polymer type dispersant (8) [poly (acrylic acid / maleic acid = 90/10 (molar ratio)) and polydiallyldimethylammonium chloride (70/30)
(Weight Ratio)) Graft Polymer] Synthesis Example 11 g of maleic acid was dissolved in 200 g of ion-exchanged water,
Using an 8% aqueous sodium hydroxide solution, adjust the pH of this solution.
Was adjusted to 3.85. In a nitrogen atmosphere, the temperature was raised to 95 ° C.
A solution in which 4 g was dissolved in 16 g of ion-exchanged water and a solution in which 4.7 g of sodium persulfate were dissolved in 50 g of ion-exchanged water were separately dropped over 2 hours. Thereafter, the temperature was maintained at 98 ° C., and stirring was further continued for 6 hours. The temperature was returned to room temperature to obtain an aqueous solution of poly (acrylic acid / maleic acid). As a result of GPC measurement of the obtained polymer, the weight average molecular weight was 87,000 (in terms of polyethylene glycol). Note that GP
C measurement conditions are the same as in Synthesis Example 1.

The obtained poly (acrylic acid / maleic acid)
300 g of an aqueous solution (64 g of polymer) was added
The temperature was raised to 5 ° C. and kept at 65 to 70 ° C., and 46 g of a 60% aqueous solution of diallyldimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.0 g of sodium persulfate dissolved in 40 g of ion-exchanged water And were separately added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued for further 6 hours while maintaining the temperature at 70 ° C., and then the temperature was returned to room temperature. The aqueous solution was freeze-dried to obtain a polymer type dispersant (8). GP of the obtained dispersant
As a result of the C measurement, the weight average molecular weight was 1490,000 (in terms of polyethylene glycol). The GPC measurement conditions are the same as in Synthesis Example 4. Further, the cation exchange capacity of the polymer type dispersant (8) was calculated by the same method as in Synthesis Example 1, and as a result, was 224 CaCO ₃ mg / g.

Synthesis Example 8: Polymeric dispersant (9) [graft polymer of sodium polystyrene sulfonate and poly (acrylic acid / maleic acid = 60/40 (molar ratio)) (50/50 (weight ratio))] Synthesis Example of 480 g of an aqueous solution of sodium polystyrene sulfonate (P
S-35, 50 g of maleic acid was dissolved in Tosoh Corporation, 96 g of polymer), and the pH of the aqueous solution was adjusted to 3.85 using a 40% aqueous sodium hydroxide solution. Thereafter, the temperature was raised to 95 ° C. in a nitrogen atmosphere and kept at 95 to 98 ° C., and 46 g of acrylic acid was dissolved in 12 g of ion-exchanged water and 12.7 g of sodium persulfate was dissolved in 80 g of ion-exchanged water. Those were separately dropped over 2 hours, and after completion of the dropping, the mixture was further kept at 98 ° C. and stirred for 6 hours. Thereafter, the temperature was returned to room temperature, and while being cooled with ice, 200 mL of a 6N aqueous sodium hydroxide solution was gradually added to neutralize the solution.
About 80% of the carboxyl groups of this polymer were converted to sodium salts. This aqueous solution was freeze-dried to obtain a polymer type dispersant (9). As a result of GPC measurement of the obtained dispersant, the weight average molecular weight was 277,000 (in terms of polyethylene glycol). The GPC measurement conditions are the same as in Synthesis Example 1. Further, the cation exchange capacity of the polymer-type dispersant (9) was calculated by the same method as in Synthesis Example 1, and as a result, 19
1 CaCO ₃ mg / g.

Synthesis Example 9: Polymer type dispersant (10) [N,
N-dimethylacrylamide / acrylic acid = 50/50
(Weight Ratio) Copolymer] 50 g of N, N-dimethylacrylamide, 5 acrylic acid
0 g was dissolved in 250 g of ion-exchanged water, and while the aqueous solution was ice-cooled, 115 mL of a 6N aqueous sodium hydroxide solution was gradually added to adjust the pH of the solution to 6.5 to 7. After stirring the solution for 10 minutes under a nitrogen atmosphere, 1.6 g of 2,2′-azobis- (2-amidinopropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was added under a nitrogen atmosphere. Heated and kept stirring at 65-70 ° C for 6 hours. Thereafter, the temperature was returned to room temperature, and the aqueous solution was freeze-dried to obtain a polymer type dispersant (10). As a result of GPC measurement of the obtained dispersant,
The weight average molecular weight was 1870,000 (in terms of polyethylene glycol). The GPC measurement conditions are the same as in Synthesis Example 1. Further, the cation exchange capacity of the polymer type dispersant (10) was calculated by the same method as in Synthesis Example 1;
128 CaCO ₃ mg / g.

Synthesis Example 10: Polymeric dispersant (11) [polyethylene glycol (number of moles of EO added: 9) monomethacrylate / sodium styrenesulfonate = 2]
0/80 (weight ratio) copolymer] When 100 g of ion-exchanged water was heated to 60 ° C. in a nitrogen atmosphere, polyethylene glycol (mol number of added EO; 9) monomethacrylate (NK-ester) M
-90G, 20 g of Shin-Nakamura Chemical Co., Ltd.) and 80 g of sodium styrenesulfonate dissolved in 350 g of ion-exchanged water, and 2,2′-azobis- (2-methylpropionamidine) dihydrochloride (Wako Pure Chemical Industries, Ltd.) (V-50 manufactured by Co., Ltd.)
1.2 g dissolved in 100 g ion-exchanged water,
While maintaining the temperature at 60 to 65 ° C, the mixture was dropped separately over 2 hours. Thereafter, stirring was continued for 6 hours while maintaining the temperature at 65 ° C, and the temperature was returned to room temperature. This aqueous solution was freeze-dried to obtain a polymer type dispersant (11). As a result of GPC measurement of the obtained dispersant, the weight average molecular weight was 114,000 (in terms of polyethylene glycol). The GPC measurement conditions are the same as in Synthesis Example 1. Further, the cation exchange capacity of the polymer-type dispersant (11) was calculated by the same method as in Synthesis Example 1, and as a result, was 14 CaCO ₃ mg / g.

Synthetic Example 11: Synthetic Example of Polymeric Dispersant (12) [Polyethylene glycol (number of moles of EO added: 34) allyl ether / maleic acid = 20/80 (molar ratio) copolymer] Maleic anhydride 156 2.8 g, polyethylene glycol (EO addition mole number: 34) allyl ether 313.6 g
Was dissolved in 400 g of ion-exchanged water, and
C., and 60 g of a 48% aqueous sodium hydroxide solution was added. After the inside of the tank was replaced with nitrogen, the temperature was raised to 98 ° C and 35
42.8 g of aqueous hydrogen peroxide, 4.77% of sodium persulfate
g of an aqueous initiator solution was added dropwise to the reactor over 6 hours, and the temperature in the reactor was maintained at 98 ° C. for 4 hours. This aqueous solution was freeze-dried to obtain a polymer type dispersant (12). As a result of GPC measurement of the obtained dispersant, the weight average molecular weight was 1.
It was 80,000 (polyethylene glycol equivalent). In addition,
GPC measurement conditions are the same as in Synthesis Example 1. Further, the cation exchange capacity of the polymer type dispersant (12) was calculated by the same method as in Synthesis Example 1, and as a result, 121 CaCO ₃ mg
/ G.

Example 1 First Step: Mixing of 218 g of Nonionic Surfactant (1) (Sophthalanol 70, manufactured by Nippon Shokubai Co., Ltd.) and 73 g of 1,3-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) The solution was heated to 50 ° C., and the polymer type dispersant (1) [Aqualoc FC600S (manufactured by Nippon Shokubai Co., Ltd., polyethylene glycol (mol number of EO added: 10)) monomethacrylate / methacrylic acid was added thereto for 5 hours. Acid = 38/62 (molar ratio)
(A 40% aqueous solution of a copolymer); cation exchange capacity: 26 CaCO ₃ mg / g] 8.8 g.

Second step: crystalline silicate compound (1)
33 g of (SKS-6, layered sodium silicate manufactured by Hoechst, particle size: 60 to 80 μm) were suspended in 33 g of the liquid phase obtained in the first step, and a volume of 1 L filled with 500 g of zirconia beads having a diameter of 0.8 mm was filled. Using a batch type sand mill (manufactured by Imex Co., Ltd.), the disk rotation speed is 1500r.
The wet pulverization was performed for 5 hours at / min. At the time of wet pulverization, the total volume of the liquid phase and the crystalline silicate compound (1) was in a state corresponding to the pore volume of the zirconia beads filled in the batch type sand mill. A part of the crystalline silicate compound dispersion obtained by this pulverization operation is collected, diluted with the liquid produced in the first step, and the particle size is measured by a particle size distribution analyzer (LA-910, manufactured by Horiba, Ltd.). Upon measurement, the average particle size was 1.6 μm.

Further, 96 g of the liquid obtained in the first step was poured into the above-mentioned sand mill, and the disk rotation speed was 1500 rpm.
The mixture was mixed for 15 minutes at min and the media was removed through a 40 mesh sieve to obtain a dispersion.

Third step: The dispersion obtained in the second step is
Formula (IV)

[0108]

Embedded image

A slight amount of a bleach activator (1.2 g) and a fragrance were added, and the mixture was sufficiently stirred and dissolved at room temperature. Further, sodium percarbonate powder (having an average particle size of 16 μm and dispersed in the liquid produced in the first step, LA-910 manufactured by HORIBA, Ltd.)
1.65 g) was added thereto, sufficiently stirred at room temperature, and dispersed to obtain a liquid detergent composition.

Examples 2 to 10 Using the components shown in Table 1, various liquid detergent compositions were produced in the same manner as in Example 1.

Comparative Examples 1 to 4 Various liquid detergent compositions were produced in the same manner as in Example 1 using the components shown in Table 1.

Example 11 First step: Nonionic surfactant (2) (Emulgen 1
08, manufactured by Kao Corporation) and 49.5 g of a nonionic surfactant (3) (polyoxyethylene phenyl ether, manufactured by Nippon Emulsifier Co., Ltd .; PHG-30) was prepared.

Second step: crystalline silicate compound (2)
33 g of the crystalline silicate compound described in Example 1 of JP-A-5-184946 was suspended in 33 g of the liquid component obtained in the first step, and filled with 500 g of zirconia beads having a diameter of 0.8 mm. Using a 1L batch type sand mill (manufactured by Imex Co.), the disk rotation speed was 150
The wet pulverization was performed at 0 r / min for 3 hours. Next, 17 g of the liquid component obtained in the first step and 142 g of zirconia beads having a diameter of 0.8 mm were charged, and the disk rotation speed was set to 1500.
The wet pulverization was further performed at r / min for 2 hours. In all wet milling, the volume of the mixture of the crystalline silicate compound (2) and the liquid component corresponds to 1.0 times the pore volume of the used zirconia beads having a diameter of 0.8 mm.

A part of the crystalline silicate compound dispersion obtained by this pulverizing operation is collected, diluted with the liquid produced in the first step, and the particle size is measured by a particle size distribution analyzer (LA, manufactured by Horiba, Ltd.).
−910), the average particle size was 0.8 μm.
m.

Third step: 82 g of the liquid produced in the first step
Was heated to 50 ° C., and 1.7 g of the polymer type dispersant (1) was dissolved therein over 5 hours. The obtained liquid solution containing a polymer-type dispersant was poured into the above-mentioned sand mill, mixed at a disk rotation speed of 1500 r / min for 2 hours, and the media was removed through a 40-mesh sieve.

Fourth step: The dispersion obtained in the third step is
1.8 g of the bleaching activator represented by the above formula (IV) and a small amount of a fragrance were added and dissolved sufficiently by stirring at room temperature. Further, 2.5 g of sodium percarbonate powder (average particle size: 16 μm, dispersed in the liquid produced in the first step, measured by LA-910, manufactured by HORIBA, Ltd.) was added, and the mixture was sufficiently stirred at room temperature. By dispersing, a liquid detergent composition was obtained.

Example 12 First step: A mixed solution of 77.7 g of nonionic surfactant (2) and 23.3 g of nonionic surfactant (3) was prepared.

Second step: crystalline silicate compound (2) 3
3 g are suspended in 33 g of the liquid component obtained in the first step,
Using a batch type sand mill (manufactured by IMEX Co., Ltd.) having a capacity of 1 L filled with 500 g of zirconia beads having a diameter of 0.3 mm, wet grinding was performed at a disk rotation speed of 1500 r / min for 3 hours. Next, the liquid component 3 obtained in the first step
4 g and 283 g of zirconia beads having a diameter of 0.3 mm were charged, and wet grinding was performed at a disk rotation speed of 1500 r / min for 2 hours. Further, the liquid component 34 obtained in the first step
g and 283 g of zirconia beads having a diameter of 0.3 mm were charged, and wet grinding was performed at a disk rotation speed of 1500 r / min for 2 hours. In all wet milling, the volume of the mixture of the crystalline silicate compound (2) and the liquid component was 1.0 times the gap volume of the zirconia beads having a diameter of 0.3 mm used.
Equivalent to double.

A part of the crystalline silicate compound dispersion obtained by this pulverization operation is sampled, diluted with the liquid produced in the first step, and the particle size is measured by a particle size distribution analyzer (LA, manufactured by Horiba, Ltd.).
−910), the average particle size was 0.6 μm.
m.

Third step: Nonionic surfactant (3) 2
3.3 g was heated to 50 ° C., and 1.7 g of the polymer type dispersant (6) was dissolved therein over 5 hours. The obtained liquid solution containing a polymer-type dispersant was poured into the above-mentioned sand mill, mixed at a disk rotation speed of 1500 r / min for 2 hours, and the media was removed through a 40-mesh sieve.

Fourth step: The dispersion obtained in the third step is
A small amount of perfume was added and dissolved with sufficient stirring at room temperature.
Further, sodium percarbonate powder (having an average particle diameter of 16 μm and dispersed in the liquid produced in the first step, manufactured by HORIBA, Ltd., LA-
(Measured at 910) 2.5 g was added, and the mixture was sufficiently stirred at room temperature and dispersed to obtain a liquid detergent composition.

Example 13 First step: Nonionic surfactant (2) 31.25 g,
A mixed solution of 18.75 g of the nonionic surfactant (3) was prepared.

Second step: crystalline silicate compound (2) 3
3 g are suspended in 33 g of the liquid component obtained in the first step,
Using a batch type sand mill (manufactured by IMEX Co., Ltd.) having a capacity of 1 L filled with 500 g of zirconia beads having a diameter of 0.8 mm, wet grinding was performed at a disk rotation speed of 1500 r / min for 3 hours. Next, the liquid component 1 obtained in the first step
7 g and 142 g of zirconia beads having a diameter of 0.8 mm were charged, and wet grinding was performed at a disk rotation speed of 1500 r / min for 2 hours. In all wet milling, the volume of the mixture of the crystalline silicate compound (2) and the liquid component is 1.50 of the pore volume of the zirconia beads having a diameter of 0.8 mm used.
It corresponds to 0 times.

A part of the crystalline silicate compound dispersion obtained by this pulverizing operation is sampled, diluted with the liquid produced in the first step, and the particle size is measured by a particle size distribution analyzer (LA, manufactured by Horiba, Ltd.).
−910), the average particle size was 0.7 μm.
m.

Third step: Nonionic surfactant (3) 31
g was heated to 50 ° C., and 1.7 g of the polymer type dispersant (1) was dissolved therein over 5 hours. The obtained polymer-type dispersant-containing liquid solution was poured into the above-mentioned sand mill, and mixed at a disk rotation speed of 1500 r / min for 2 hours.
The media was removed through a mesh sieve.

Fourth step: The dispersion obtained in the third step is
1.8 g of the bleaching activator represented by the above formula (IV) and a small amount of a fragrance were added and dissolved sufficiently by stirring at room temperature. In addition, Zeolite (1) (Toyo Builder Co., Ltd.
8.3 g of the product dehydrated by firing at 0 ° C. for 1 hour) was subjected to wet grinding (average particle size 0.7 μm) in 51 g of the nonionic surfactant (2) in advance, and sodium percarbonate powder ( 2.5 g of an average particle diameter of 16 μm dispersed in the liquid produced in the first step and measured by LA-910 manufactured by HORIBA, Ltd. A composition was obtained.

Example 14 First step: 29.9 g of nonionic surfactant (3) was added to 50
And heated to 5 ° C. for 5 hours.
2.1 g was dissolved to obtain a polymer type dispersant solution. 48 g of the nonionic surfactant (2) and the above-mentioned polymer-type dispersant solution were mixed to prepare a polymer-type dispersant-containing liquid solution.

Second step: crystalline silicate compound (2) 2
0 g is suspended in 80 g of the liquid component obtained in the first step,
Using a batch type sand mill (manufactured by IMEX Co., Ltd.) having a capacity of 1 L filled with 670 g of zirconia beads having a diameter of 0.3 mm, wet grinding was performed at a disk rotation speed of 1500 r / min for 5 hours. In this case, the volume of the crystalline silicate compound (2) and the liquid component is 1.1 times the pore volume of the medium.
Equivalent to 5 times.

A part of the crystalline silicate compound dispersion obtained by this pulverizing operation was sampled, diluted with the liquid produced in the first step of Example 11, and the particle size was measured by a particle size distribution analyzer (Horiba Seisakusho) And LA-910), the average particle size was 3.4 μm.

Third step: The dispersion obtained in the second step was
The media was removed through a 0 mesh sieve.

Fourth step: The dispersion obtained in the third step is
A small amount of perfume was added and dissolved with sufficient stirring at room temperature.
Further, sodium percarbonate powder (having an average particle diameter of 16 μm and dispersed in the liquid produced in the first step, manufactured by HORIBA, Ltd., LA-
(Measured at 910) 2.5 g was added, and the mixture was sufficiently stirred at room temperature and dispersed to obtain a liquid detergent composition.

Example 15 First step: 31.25 g of nonionic surfactant (2)
A mixed solution of 18.75 g of the nonionic surfactant (3) was prepared.

Second step: crystalline silicate compound (2) 3
3 g are suspended in 50 g of the liquid component obtained in the first step,
Using a batch type sand mill (manufactured by Imex Co., Ltd.) having a capacity of 1 L filled with 500 g of zirconia beads having a diameter of 0.8 mm, wet grinding was performed at a disk rotation speed of 1500 r / min for 5 hours. In this case, the volume of the crystalline silicate compound (2) and the liquid component is 1.1 times the pore volume of the medium.
Equivalent to eight times.

A part of the crystalline silicate compound dispersion obtained by this pulverizing operation is collected, diluted with the liquid produced in the first step, and the particle size is measured by a particle size distribution analyzer (LA, manufactured by Horiba, Ltd.).
−910), the average particle size was 2.3 μm.
m.

Third step: Nonionic surfactant (3) 31
g was heated to 50 ° C., and 1.7 g of the polymer type dispersant (1) was dissolved therein over 5 hours. The obtained polymer-type dispersant-containing liquid component was poured into the sand mill, and mixed at a disk rotation speed of 1500 r / min for 15 minutes.
The media was removed through a 0 mesh sieve.

Fourth step: The dispersion obtained in the third step is
1.8 g of the bleaching activator represented by the above formula (IV) and a small amount of a fragrance were added and dissolved sufficiently by stirring at room temperature. Further, 8.2 g of zeolite (1) was added to a nonionic surfactant (2) 5
1 g pre-wet pulverized in 1 g, and sodium percarbonate powder (average particle diameter 16 μm, dispersed in the liquid produced in the first step, measured by LA-910, manufactured by HORIBA, Ltd.)
Add 5 g and stir well at room temperature to disperse this,
A liquid detergent composition was obtained.

Example 16 First step: Mixing of 204 g of nonionic surfactant (1) (Sophthanol 70, manufactured by Nippon Shokubai Co., Ltd.) and 80 g of 1,3-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) The liquid was heated to 50 ° C., and 16.4 g of the polymer type dispersant (7) obtained in Synthesis Example 6 was dissolved therein over 5 hours.

Second step: Toyo Builder (Toyo Soda Co., Ltd.)
50 g, which was fired at 450 ° C. for 1 hour and dehydrated
Was suspended in 50 g of the liquid phase obtained in the first step, and a 5 L batch type sand mill (manufactured by Imex Co., Ltd.) filled with 400 g of zirconia beads having a diameter of 0.8 mm was used at a disk rotation speed of 1500 r / min. Time wet grinding was performed.

A part of the zeolite dispersion obtained by this pulverization operation is sampled and diluted with the liquid produced in the first step, and the particle size of the zeolite is measured by a particle size distribution analyzer (LA, manufactured by Horiba, Ltd.).
−910), the average particle size was 0.8 μm.
m.

Further, 146 g of the liquid obtained in the first step was poured into the above-mentioned sand mill, and the disk rotation speed was 1500 rpm.
The mixture was mixed at / min for 15 minutes, and the media was removed through a 40 mesh sieve to obtain a dispersion.

Third step: The dispersion obtained in the second step is
1.8 g of the bleaching activator represented by the above formula (IV) and a small amount of a fragrance were added and dissolved sufficiently by stirring at room temperature. Further, 2.5 g of sodium percarbonate powder (average particle size: 16 μm, dispersed in the liquid produced in the first step, measured by LA-910 manufactured by HORIBA, Ltd.) was added, and the mixture was sufficiently stirred at room temperature to disperse. Then, a liquid detergent composition was obtained.

Examples 17 to 27 Using the components shown in Table 3, various liquid detergent compositions were produced in the same manner as in Example 16.

Comparative Examples 5 to 9 Using the components shown in Table 3, various liquid detergent compositions were produced in the same manner as in Example 16.

The volume separation rates of the liquid detergent compositions obtained in Examples 1 to 27 and Comparative Examples 1 to 9 were measured by the following method.
A cleaning test was performed. The results are shown in Tables 1, 2 and 3.

(1) Volume separation rate A graduated glass sedimentation tube was filled with the liquid detergent composition so as to have a depth of 30 cm, and the sample was sealed.
It was stored for 1 month in a room at 5 ° C. The boundary between the transparent liquid phase and the solid dispersion phase of the sample after storage was visually judged, and the thickness x (cm) of the transparent liquid phase formed in the upper layer after phase separation was measured. The volume separation rate y was determined by the following equation (V).

Y = (x / 30) × 100 (V) (2) Washing test 100 g of a mixture of carbon black 15%, cottonseed oil 60%, cholesterol 5%, oleic acid 5%, palmitic acid 5% and liquid paraffin 10% Is dissolved and dispersed in 8 L of perclene, and a cotton white cloth (width 2003 cloth) cut to 10 cm × 10 cm is immersed to adhere dirt. Then, the perchlen is dried and removed to obtain a sebum / carbon stained cloth ( An artificially stained cloth) was prepared.

A set of five sebum / carbon stained cloths was placed in 1 L of an aqueous detergent solution for evaluation, and a washing test was performed with a tergotometer under the following conditions. Cleaning time: 10 minutes Detergent composition: 0.8 g / 1 L of aqueous detergent solution for evaluation Hardness of water: 71.2 mg CaCO ₃ / L Temperature of water: 20 ° C. Rotation speed of tergotometer: 100 r / min Rinse: 20 ° C. tap water Rinse with running water for 5 minutes. The cleaning power is 550 of the original cloth before contamination and the contamination cloth before and after cleaning.
The reflectance in nm was measured using a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was determined by the following equation.

Cleaning rate (%) = {(reflectance after cleaning−reflectance before cleaning) / (reflectance of original cloth−reflectance before cleaning)} ×
100

[0149]

[Table 1]

[0150]

[Table 2]

[0151]

[Table 3]

* 1 Nonionic surfactant (1): Softanol 70 (manufactured by Nippon Shokubai Co., Ltd.) * 2 Nonionic surfactant (2): Emulgen 108 (manufactured by Kao Corporation) * 3 Nonionic Surfactant (3): polyoxyethylene phenyl ether (manufactured by Nippon Emulsifier Co., Ltd., PHG-3)
0) * 4 Anionic surfactant: alkyl having 10 to 1 carbon atoms
Sodium linear alkylbenzene sulfonate 4 * 5 Water-soluble organic solvent: 1,3-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) * 6 Polymeric dispersant (1): Aqualoc FC600S
[Nippon Shokubai Co., Ltd., polyethylene glycol (EO addition mol number: 10) monomethacrylate / methacrylic acid = 38/62 (molar ratio) copolymer (40% aqueous solution); cation exchange capacity: 26 CaCO ₃ mg / G]
* 7 Polymeric dispersant (2): Dispersant synthesized in Synthesis Example 1 * 8 Polymeric dispersant (3): Dispersant synthesized in Synthesis Example 2 * 9 Polymeric dispersant (4): Dispersant synthesized in Synthesis Example 3 * 10 Polymeric dispersant (5): Dispersant synthesized in Synthesis Example 4 * 11 Polymeric dispersant (6): Dispersant synthesized in Synthesis Example 5 * 12 Polymeric dispersant (7): Dispersant synthesized in Synthesis Example 6 * 13 Polymeric dispersant (8): Dispersant synthesized in Synthesis Example 7 * 14 Polymeric dispersant (9): Synthesis Dispersant synthesized in Example 8 * 15 Polymer type dispersant (10): Dispersant synthesized in Synthesis Example 9 * 16 Polymer type dispersant (11): Dispersant synthesized in Synthesis Example 10 * 17 Polymer type Dispersant (12): Dispersant synthesized in Synthesis Example 11 * 18 Polymer (1): polyethylene glycol (polyethylene glycol 2,000, manufactured by Wako Pure Chemical Industries, Ltd.); On exchange _{capacity: 9 CaCO 3 mg / g *} 19 polymer (2): Polyvinylpyrrolidone (K-30,
Cation exchange capacity: 12 CaC
O ₃ mg / g * 20 Polymer (3): polysodium methacrylate (weight average molecular weight: 9,500, manufactured by Aldrich); Cation exchange capacity: 175 CaCO ₃ mg / g * 21 Polymer (4): poly (Acrylic acid / maleic acid) (Sokalan CP-5, BASF); cation exchange capacity:
380 CaCO ₃ mg / g * 22 Bleach activator: bleach activator represented by the above formula (IV) * 23 Crystalline silicate compound (1): SKS-6 (manufactured by Hoechst) * 24 Crystallinity Silicate compound (2): JP-A-5-1849
No. 46, crystalline silicate compound described in Example 1 * 25 Zeolite (1): Toyobuilder (Toyo Soda Co., Ltd.)
Zeolite (2): Toyobuilder (Toyo Soda Co., Ltd.)
* 27 Evalase 16.0L-EX: Protease (Novo Nordisk Bio-Industry) * 28 Lipolase 100L: Lipase (Novo Nordisk Bio-Industry) From Tables 1, 2 and 3, the liquid detergent of the present invention The composition stably disperses a solid component mixture containing a crystalline silicate compound and / or an aluminosilicate compound by using a polymer type dispersant, and has a volume separation rate of 5% after one month.
It has been found that the following can be obtained, and that it has excellent detergency. In particular, when the total volume of the component (a) and the component (c) is 0.9 to 1.1 times the gap volume of the media filled in the ball media mill during production, the volume separation rate is further reduced. Can be.

[0153]

According to the liquid detergent composition of the present invention, fine solid particles containing a crystalline silicate compound and / or an aluminosilicate compound are added to a surfactant-containing liquid to increase the product viscosity. Without being dispersed stably by the polymer type dispersant, it is easily poured into the washing tub and quickly dissolved in the washing water. In addition, the high-molecular-weight dispersant having a high cation exchange capacity acts as a builder in washing water,
The cleaning composition can be made compact and has excellent detergency.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 2001-59705 (P2001-59705) (32) Priority date March 5, 2001 (2001.3.5) (33) Priority claim country Japan (JP) (72) Inventor Taku Oda 1334 Minato, Wakayama City, Wakayama Prefecture Inside Kao Co., Ltd. (72) Inventor Akira Ishikawa 1334 Minato, Wakayama City, Wakayama Prefecture Inside Kao Research Institute (72) Inventor, Takiguchi Sei Wakayama 1334 Minato, Wakayama-shi, Japan F-term in the Kao Research Institute (reference) 4H003 AB19 AC08 AC09 AC11 BA12 CA14 DA01 DA05 DA17 EA16 EA24 EA28 EB08 EB22 EB30 EC01 EC02 ED02 ED28 EE05 FA05 FA07 FA16 FA26 FA37

Claims (12)

[Claims] 1. A liquid phase [(a) phase], a polymer type dispersant [component (b)], and a crystalline silicate compound and / or an aluminosilicate compound [component (c)]. 2
A liquid detergent composition having a volume separation rate of 5% or less after storage at 5 ° C. for one month [however, the composition has a water content of 5% by weight or less and uses only an aluminosilicate compound in the component (c)] In case or when the water content in the composition exceeds 5% by weight, the component (b) has a cation exchange capacity of at least 120 CaCO ₃ mg / g. ]. 2. The composition according to claim 1, wherein the content of the (a) phase is from 30 to 9 in the composition.
The liquid detergent composition according to claim 1, which is 5% by weight. 3. The liquid detergent composition according to claim 1, wherein (a) the phase contains 10 to 100% by weight of a surfactant. 4. The composition according to claim 1, wherein the content of the component (b) is 0.1% in the composition.
The liquid detergent composition according to any one of claims 1 to 3, which is 10 to 10% by weight. 5. The composition according to claim 5, wherein the content of the component (c) is 3 to 6 in the composition.
The liquid detergent composition according to any one of claims 1 to 4, which is 9.9% by weight. 6. The liquid detergent composition according to claim 1, wherein the component (b) is a polymer composed of two or more polymer chains. 7. A polymer chain wherein component (b) has a solubility or uniform dispersibility in phase (a) (hereinafter referred to as polymer chain 1) and a polymer chain having a functional group having high affinity for component (c) ( The liquid detergent composition according to any one of claims 1 to 6, which is a block or graft polymer having polymer chains 2). 8. The crystalline silicate compound of the component (c),
The liquid detergent composition according to any one of claims 1 to 7, which is a compound represented by the general formula (I). In ^{_{(M 1 p M 2 q M}} 3 r O) (M 4 s M 5 t O) x (SiO 2) y (I) [ wherein, M ^1, M ² and M ³ respectively Na, K or H shown, M ⁴ and M ⁵ represents a Ca or Mg, respectively. p, q
And r are each a number from 0 to 2 (where p + q + r = 2);
s and t are numbers from 0 to 1 (s + t = 1), x
Represents a number of 0 to 1, and y represents a number of 0.9 to 3.5. ] 9. The aluminosilicate compound as the component (c) is a compound represented by the general formula (II).
9. The liquid detergent composition according to any one of the above items 8. ^{_{(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) (II) [ ^{wherein, M 1, M 2, M} 3, M ⁴ , M ⁵ , p, q, r, s and t have the same meaning as described above. u is a number from 0 to 1 and v is 0 to
The number 1 and w indicate a number from 0 to 0.6. ] 10. The liquid detergent composition according to claim 1, comprising a step of wet-milling the components (b) and (c) in the (a) phase to obtain a finely divided solid component slurry. The manufacturing method of things. 11. The method according to claim 1, further comprising a step of wet-milling the component (c) in the (a) phase to obtain a finely divided solid component slurry, and then adding the component (b). Of the liquid detergent composition of the present invention. 12. The wet pulverization wherein the total volume of the phase (a) and the component (c) and other solid components is 0.9 to 1.1 times the gap volume of the media filled in the ball media mill. Item 12. The method for producing a liquid detergent composition according to Item 10 or 11.