JP4481138B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition that is easy to use and excellent in detergency, finish feeling, and storage stability. In particular, the present invention relates to a liquid detergent composition suitable for aqueous washing of textile products.

  Liquid detergents are superior to powder detergents in terms of ease of use because they can be applied directly to soiled areas. However, there is also a general method in which the liquid detergent is simply dissolved in washing water without being applied to the dirt, and in this case, the cleaning power of the liquid detergent tends to be inferior to that of the powder detergent. This is because, as in the case of the powder detergent, when a builder component such as an alkali agent or a calcium scavenger is sufficiently blended in the composition, a problem occurs in the stability of the system.

In addition, attempts have been made to add clay minerals such as smectite for the purpose of improving the finished feeling such as imparting flexibility to the object to be cleaned, but unlike powder detergents, it causes problems in system stability and usability. It was. For example, a fabric softening heavy liquid detergent containing a specific anionic surfactant, a water-soluble builder salt, and a clay mineral is known (for example, see Patent Document 1). However, there is a problem in usability and the cleaning performance is not sufficient. Further, for example, a fabric softening heavy liquid cleaning agent containing a specific surfactant mixed system, a water-soluble inorganic builder, and a clay mineral is known (see, for example, Patent Document 2). Otherwise, sedimentation of clay minerals will occur, and there is a problem in usability.
Japanese Patent Laid-Open No. 61-157592 JP-A-3-172399

  An object of the present invention is to provide a liquid detergent composition that is excellent in ease of use, detergency, and finished feeling, and has good storage stability. More specifically, it is to provide a liquid detergent composition having improved detergency and finishing feeling without sacrificing storage stability and solubility while making use of the ease of use of the liquid detergent.

  The present invention comprises (a) a nonionic surfactant (hereinafter referred to as component (a)) 5 to 60% by mass, (b) an alkali metal carbonate, an alkali metal silicate, and an alkali metal sulfate. At least one water-soluble inorganic salt selected from salts and chlorides of alkali metal salts (hereinafter referred to as component (b)) 5 to 40% by mass, (c) water (hereinafter referred to as component (c)) 15 to 80 % By weight, (d) Clay mineral [hereinafter referred to as component (d)] 0.1-50% by weight, JIS K 3362: 1998 surfactant equivalent is 10-60% by weight, average The present invention relates to a liquid detergent composition having droplets having a particle diameter of 0.1 to 20 μm and a viscosity of 10 to 2000 mPa · s (B-type viscometer, 60 r / min, 60 seconds, 20 ° C.).

  Moreover, this invention has the process I which mixes (a) component, (b) component, and (c) component, and the process II which mixes the mixture obtained by this process I, and (d) component. The present invention also relates to a method for producing the liquid detergent composition of the present invention.

  The liquid detergent composition of the present invention has good storage stability while maintaining ease of use as a liquid, and a detergency equivalent to or better than the index detergent for determining detergency described in JIS K 3362: 1998 is obtained. In addition, the finish is excellent.

  In the liquid detergent composition of the present invention, the surfactant equivalent described in JIS K 3362: 1998 is 10 to 60% by mass, preferably 15 to 50% by mass in terms of cleaning performance and solubility, and 20 to 45%. More preferably, it is more preferably 20 to 40% by mass.

  Moreover, the liquid detergent composition of the present invention contains droplets having an average particle size of 0.1 to 20 μm. When the average particle size is 10 μm or more, the average particle size of the droplets can be obtained by measuring an arbitrary 500 points with an optical microscope. It is preferable to obtain by measuring arbitrary 500 points. In terms of stability, solubility, and productivity, the average particle diameter of the droplets is preferably 0.2 to 15 μm, and more preferably 0.2 to 10 μm. Here, the average particle diameter of the droplets represents the volume average diameter.

  The viscosity (B-type viscometer, 60 r / min, 60 seconds, 20 ° C.) of the liquid detergent composition of the present invention is preferably 30 to 2000 mPa · s, and preferably 50 to 1800 mPa · s in terms of stability and usability. Is more preferable. These viscosities were measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., VISCOMETER MODEL DVM-B) under the conditions of 3 or 4 rotors, a rotation speed of 60 r / min, and a measurement time of 60 seconds. It has been done.

<(A) component>
The liquid detergent composition of this invention contains 5-60 mass% of nonionic surfactant as (a) component. In view of cleaning performance and stability, the component (a) is preferably 8 to 40% by mass, more preferably 10 to 35% by mass, and still more preferably 15 to 30% by mass.

  In terms of cleaning performance and stability, the component (a) in the surfactant equivalent described in JIS K 3362: 1998 is preferably 100 to 40% by mass, more preferably 98 to 50% by mass, and 95 to 60% by mass. % Is more preferable.

  (A) As a component, what is shown by general formula (I) and / or (II) is preferable, and what is represented by general formula (II) is from the point of the ease of pouring of a liquid detergent composition. More preferred.

R ¹ O— (EO) _m —H (I)
[Wherein, R ¹ represents an alkyl group and / or alkenyl group which is a residue having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, from which a hydroxyl group has been removed from a primary and / or secondary alcohol. EO represents an ethyleneoxy group. m is an average addition mole number, and shows the number of 5-20. ]

_{^{R 2 O- (EO) k /}} (PO) l -H (II)
[Wherein, R ² represents an alkyl group and / or an alkenyl group, which is a residue having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, from which a hydroxyl group has been removed from a primary and / or secondary alcohol. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. k is the average added mole number of EO and is a number from 5 to 15, and l is the average added mole number of PO and is a number from 1 to 5. Note that EO and PO may be either random addition or block addition, and the addition order of EO and PO is not limited. ]

  Among those represented by the general formula (II), by using a nonionic surfactant represented by the following general formula (III), it is possible to obtain a high detergency against Eli and cuff dirt.

_{^{R 3 O- (EO) p (}} PO) q (EO) r -H (III)
[Wherein R ³ represents an alkyl group and / or an alkenyl group, which is a residue having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, from which a hydroxyl group has been removed from a primary and / or secondary alcohol. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. p, q, and r are average addition mole numbers, show the number used as p> 0, q = 1-4, and r> 0, and are p + q + r = 6-14 and p + r = 5-12. Preferably, p + q + r = 7 to 14, p + r = 6 to 12, and q = 1 to 2. ]

In the general formulas (I), (II), and (III), R ¹ , R ² , and R ³ can employ an alkyl group and / or an alkenyl group derived from natural fats and oils.

  As the nonionic surfactant, an alkyl polysaccharide surfactant represented by the general formula (IV) can also be used.

R ⁴ − (OR ⁵ ) _x −G _y (IV)
[Wherein, R ⁴ represents a linear or branched alkyl group having 8 to 18 carbon atoms, a linear or branched alkenyl group having 8 to 18 carbon atoms, or an alkyl (C 1 to C 18) phenyl group, R ⁵ 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, x is an average added mole number and a number of 0 to 6, y is an average degree of polymerization, and 1 to A number of 10 is indicated. ]

Amine oxides represented by general formula (V) can also be used.

[Wherein R ⁶ represents an alkyl group and / or alkenyl group which is a residue having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, from which a hydroxyl group has been removed from a primary and / or secondary alcohol, or R ⁹ C (= O) NH (CH 2) z - shows a formula represented by. Here, R ⁹ represents an alkyl group and / or alkenyl group having 8 to 20 carbon atoms, preferably 12 to 18 carbon atoms, and z represents an integer of 1 to 5. R ⁷ and R ⁸ represent CH ₃ , C ₂ H ₅ or C ₂ H ₄ OH, which may be the same or different. ]

  Furthermore, fatty acid alkanolamides, polyhydroxy fatty acid amides and the like can be blended.

<(B) component>
The liquid detergent composition of the present invention comprises at least one water-soluble substance selected from alkali metal carbonates, alkali metal silicates, alkali metal sulfates, and alkali metal chlorides as the component (b). The inorganic salt is preferably contained in an amount that causes the surfactant to precipitate (salt out). The specific content of the component (b) is 5 to 40% by mass in the composition, and 5 to 30% by mass is more preferable in terms of cleaning performance, stability and solubility, and 10 to 25% by mass. Is more preferable. In addition, about (b) component, water solubility means melt | dissolving 10 g / L or more in 25 degreeC ion-exchange water. When the composition of the present invention contains an anionic surfactant, the component (b) is preferably blended in an amount that exceeds the amount that precipitates (salts out) the anionic surfactant in water.

  As an alkali metal, sodium and potassium are preferable in terms of cleaning performance.

  From the viewpoint of stability, the component (b) is preferably dissolved in 98 parts by mass or more in 100 parts by mass of the component (b) in the liquid detergent composition of the present invention at 5 ° C., and 99 parts by mass. It is more preferable that it is dissolved as described above, and it is still more preferable that it is completely dissolved.

  In terms of cleaning performance, it preferably contains an alkali metal carbonate or an alkali metal silicate, and more preferably contains a carbonate.

  Further, in all the components (b) in the composition, at least one selected from carbonates of alkali metal salts is 50% by mass or more, more preferably 70% by mass or more, particularly 90% by mass or more, It is preferable in terms of cleaning power.

<(C) component>
The liquid detergent composition of this invention contains 15-80 mass% of water as (c) component.

  15-70 mass% is preferable at the point of washing | cleaning performance, stability, and solubility, 20-60 mass% is more preferable, and 30-50 mass% is still more preferable. From the viewpoint of stability, the mass ratio of the component (c) to the component (b) is preferably (b) / (c) = 10/90 to 60/40, more preferably 15/85 to 50/50. 20/80 to 45/55 are more preferable, and 25/75 to 40/60 are particularly preferable.

<(D) component>
The liquid detergent composition of this invention contains 0.1-50 mass% of clay minerals as (d) component. In terms of cleaning performance, usability (viscosity), emulsion stability, and finished feeling, 3 to 40% by mass is preferable, 5 to 30% by mass is more preferable, and 5 to 20% by mass is even more preferable.

  As component (d), talc, pyrophyllite, smectite (saponite, hectorite, saconite, stevensite, montmorillonite, beidellite, nontronite, etc.), vermiculite, mica (phlogopite, biotite, chinwald mica, muscovite mica) , Paragonite, ceradonite, sea chlorite, etc.), chlorite (clinochlore, chamosite, nimite, penantite, sudite, dombasite, etc.), brittle mica (clinintite, margarite, etc.), sulite, serpentine mineral (antigolite) Lizardite, chrysotile, amicite, cronstedite, burcherin, greenerite, garnierite), kaolin mineral (kaolinite, dickite, nacrite, halloysite, etc.). Among these, smectite is preferable and hectorite is more preferable in terms of emulsion stability and finished feeling.

The component (d), emulsion stability, in terms of the finish feeling, the following general formula _{[Si 8 (Mg a Li b} ) O 20 (OH) c F (4-c)] x- · (Me) x +
(0 <a ≦ 6, 0 <b ≦ 6, 4 <a + b <8, 0 ≦ c ≦ 4, x = 12-2a-b, Me: at least one of Na, K, Li and NH ₄ )
A clay mineral having The component (d) is naturally produced but can also be obtained as a synthetic product.

<(E) component>
The liquid detergent composition of the present invention preferably contains (e) a weak acid (an ionization degree of less than 0.5) in terms of cleaning performance and damage, and the content thereof is 0.05 in the composition. 10 mass% is preferable, 0.1-8 mass% is more preferable, 0.2-5 mass% is still more preferable.

  In terms of cleaning performance and damage, the mass ratio of the component (b) to the component (e) is preferably (b) / (e) = 99 / 1-80 / 20, more preferably 98 / 2-85 / 15. 98/2 to 90/10 are more preferable. As component (e), formic acid, citric acid, tartaric acid, succinic acid, adipic acid, acetic acid, phosphoric acid, sulfamic acid, glutaric acid, lactic acid, malic acid, boric acid, nonanoic acid, palmitic acid, oleic acid, linoleic acid In view of cleaning performance and damage, citric acid, malic acid and lactic acid are preferable, and citric acid and malic acid are more preferable.

<Component (f)>
In addition, the liquid detergent composition of the present invention preferably further contains a water-miscible organic solvent having a weight average molecular weight of less than 3000 as the component (f) in terms of stability and cleaning performance.

  The content of the component (f) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, particularly 1 to 10% by mass in the composition from the viewpoint of stability and solubility. preferable. Further, in terms of stability and productivity, the mass ratio (a) / (f) of component (a) to component (f) is preferably 99/1 to 40/60, more preferably 95/5 to 50/50. 90/10 to 60/40 is more preferable. Further, the water-miscible organic solvent is preferably a water-miscible organic solvent having a hydroxyl group and / or an ether group in terms of stability and washing performance.

  Examples of water-miscible organic solvents include (i) alkanols such as ethanol, 1-propanol, 2-propanol and 1-butanol, (ii) glycols such as propylene glycol, butylene glycol and hexylene glycol, and (iii) diethylene glycol. , Polyethylenes such as triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, dipropylene glycol, tripropylene glycol, polypropylene glycol having an average molecular weight of about 2000, (iv) diethylene glycol Monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Recall diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether 1,3-dimethylglycerin ether, 1-ethylglycerin ether, 1,3-diethylglycerin ether, triethylglycerin ether, 1-pentylglyceryl ether, 2-pentylglyceryl ether, 1-octylglyceryl ether, 2-ethylhexylglyceryl ether , Alkyl ethers such as diethylene glycol monobutyl ether, (v) 2-phenoxyethanol, diethylene glycol monobutyl Nyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, aromatic ethers such as 2-benzyloxyethanol, diethylene glycol monobenzyl ether, (vi) 2-aminoethanol, N-methylethanolamine N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanolamine, isopropanolamine mixture (mixture of mono-, di-, and tri) Of the alkanolamines.

  The water-miscible organic solvent is effective as a viscosity modifier and gelation inhibitor of the composition, and includes the above (i) alkanols, (ii) glycols, (iv) alkyl ethers, and (v) aromatic ethers. It is preferable to use two or more selected from the above, more preferably two or more selected from (ii), (iv) and (v), particularly preferably two selected from (ii) and (v) By using the above together, it is possible to effectively achieve viscosity adjustment and gelation suppression of the composition.

  A water-immiscible organic solvent may be used as long as the effect of the water-miscible organic solvent is not impaired. Examples of such organic solvents include paraffins such as octane, decane, dodecane and tridecane, olefins such as decene and dodecene, alkyl halides such as methylene chloride and 1,1,1-trichloroethane, and D-limonene. Examples include terpenes.

<(G) component>
The liquid detergent composition of the present invention preferably contains a water-soluble polymer compound having a weight average molecular weight of 3,000 to 8,000,000 as the component (g) in terms of stability and cleaning performance. (G) As for content of a component, 0.05-10 mass% is preferable in a composition.

  As the component (g), a water-soluble stabilizing polymer having the molecular weight [hereinafter referred to as the component (g1)] is particularly preferable from the viewpoint of stability. In the present invention, the water-soluble stabilizing polymer is a droplet containing a surfactant having a volume average particle size of 0.1 to 20 μm present in the aqueous phase immediately after the production of the composition containing the polymer. Even after storage at 50 ° C. for 1 month, the volume average particle diameter of 0.1 to 20 μm can be maintained, but the composition obtained by removing the polymer from the composition cannot maintain the volume average particle diameter in the above range after storage. Water-soluble polymer. Further, “water-soluble” means that 1 g / L or more dissolves in 25 ° C. ion exchange water.

  The weight average molecular weight of the component (g1) is preferably 4000 to 7 million, more preferably 4500 to 6 million, and still more preferably 5000 to 6 million in terms of stability and cleaning performance. Here, the weight average molecular weight is measured using gel permeation type liquid chromatography (GPC), and the average molecular weight is determined in terms of polyethylene glycol (PEG).

  The content of the component (g1) is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass in the composition from the viewpoint of stability, solubility, and cleaning performance. 5 mass% is still more preferable.

  The liquid detergent composition of the present invention has a viscosity (B-type viscometer, 60 r / min, 60 seconds, 20 ° C.) in terms of stability, solubility, and usability as compared with the composition to which (g1) component component is not added. ) Is preferably 0.7 to 1.3, more preferably 0.8 to 1.2, and still more preferably 0.8 to 1.0.

  Further, in terms of stability, solubility, and usability, the mass ratio of the component (a) to the component (g1) is preferably (a) / (g1) = 99.5 / 0.5 to 50/50, 99 / 1-80 / 20 are more preferable, and 99 / 1-90 / 10 are still more preferable.

  Furthermore, from the viewpoint of stability, the component (g1) is preferably dissolved in the liquid detergent composition.

  The component (g1) is a polymer having a function of stably maintaining a state in which droplets (mainly containing a salted-out surfactant) are dispersed in the aqueous phase, and the polymer having such a function. Any of them can be used. Examples of the polymer having such a function include a polymer having a segment (b) having an affinity for an aqueous phase and / or a segment (b) having an affinity for a droplet. ) A mass ratio of (A) / (B) = 30/70 to 90/10 (hereinafter referred to as Type 1), or (A) / (B) = 100/0 to 95/5 (Hereinafter referred to as Type 2), or (b) / (b) = 5/95 to 0/100 (hereinafter referred to as Type 3). Among these, in terms of stability and solubility, type 1 and type 2 polymers are preferable, and type 1 polymer is particularly preferable.

  The segment (a) is preferably a polymer chain, and the segment (b) is preferably a polymer chain or an organic group.

  The details of the mechanism of action of the water-soluble polymer as a stabilizing polymer are unclear, but the Type 1 polymer functions as an emulsifier for droplets, while the Type 2 polymer dissolves in the aqueous phase to dissolve the aqueous phase. It is considered that the Type 3 polymer dissolves in the droplets to control the specific gravity and suppress the floating and sedimentation.

  In the case of a polymer chain, having affinity means that a polymer having a weight average molecular weight of about 3000 to 50,000 having essentially the same structure as the polymer chain or a monomer having the polymer chain is dissolved or uniformly dispersed in the target phase. Specifically, the polymer or monomer is mixed in the target phase at a concentration of 5% by mass, stirred at 60 ° C. for 30 minutes, returned to room temperature (25 ° C.), and allowed to stand 1 After the time, it can be visually confirmed that the polymer or monomer is dissolved or uniformly dispersed because no precipitate or separated layer is formed.

  In the case of an organic group, having affinity means that any monomer having an organic group is dissolved or uniformly dispersed in the target phase. Specifically, the monomer is added in the target phase. After mixing at a concentration of 5% by mass, stirring at 60 ° C. for 30 minutes, returning to room temperature (25 ° C.), and after standing for 1 hour, the monomer is dissolved or homogeneous by visual observation that no precipitation or separation layer occurs. It can be confirmed that they are dispersed.

  In the above, the “target phase” refers to each phase generated when the water-insoluble solid component such as inorganic builder particles and the component (g1) are mixed and centrifuged from the composition of the present invention.

[Segment (I)]
The segment (a) is preferably a polymer chain having an anionic group or a salt thereof in the structural unit, more preferably a polymer chain having a carboxy group or a salt thereof in the structural unit, a sulfonic acid group, A phosphoric acid group, a phosphonic acid group or a salt thereof may be contained.

  Such a polymer chain is preferably a (co) polymer of a vinyl monomer having a carboxy group or a salt thereof (the (co) polymer refers to a single polymer or a copolymer). Examples of the monomer include (meth) acrylic acid [(meth) acrylic acid refers to acrylic acid, methacrylic acid or a mixture thereof] and salts thereof, styrene carboxylic acid and salts thereof, maleic acid monomer [maleic anhydride] Acid, maleic acid, maleic acid monoester, maleic acid monoamide or a mixture of two or more thereof] and salts thereof, itaconic acid and salts thereof, and the like, and one or more selected from these can be used.

  For the part having a sulfonic acid group or a salt thereof, a (co) polymer of a vinyl monomer having a sulfonic acid group or a salt thereof is preferable. Examples of the monomer include 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamido-2-alkyl (1 to 4 carbon atoms) propanesulfonic acid, vinylsulfone. Examples thereof include sulfonic acid monomers such as acid and styrene sulfonic acid, and one or more selected from these can be used.

  A vinyl monomer (co) polymer having a phosphoric acid group or a salt thereof is preferred at a site having a phosphoric acid group or a phosphonic acid group or a salt thereof. Examples of the monomer include (meth) acryloyloxyalkyl (C1-4) phosphoric acid, vinylphosphonic acid and the like.

  These salts include alkali metal, alkaline earth metal, ammonium, alkyl or alkenyl ammonium having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridinium having 1 to 22 carbon atoms, alkanol ammonium having 1 to 22 carbon atoms, Or a basic amino acid etc. are mentioned, An alkali metal salt like sodium and potassium is preferable.

[Segment (b)]
Examples of the segment (b) include (b 1) a nonionic polymer chain and (b 2) an organic group.

  As the nonionic polymer chain, a polymer chain having a structural unit derived from a monomer selected from the following monomer group (B1-1) to (Bro1-8), or the following polymer chain (Bro1-9) to (B) B-1-11) is preferred.

(B1-1) Vinyl ethers having an unsubstituted or substituted, saturated or unsaturated alkyl group or aralkyl group having 1 to 22 carbon atoms. For example, methyl vinyl ether, ethyl vinyl ether, 4-hydroxybutyl vinyl ether, phenyl vinyl ether and the like are preferable.

(B1-2) Substituted (meth) acrylamides which are unsubstituted or have a saturated or unsaturated alkyl group 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, N-t-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 are preferable.

(B 1-3) N-vinyl aliphatic amides. For example, N-vinylpyrrolidone, N-vinylacetamide, N-vinylformamide and the like are preferable.

(B 1-4) (meth) acrylic acid esters having an unsubstituted or substituted, saturated or unsaturated alkyl group or aralkyl group having 1 to 22 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- Methoxyethyl, polyethylene glycol mono (meth) acrylic acid ester and the like are preferable.

(Ro 1-5) Alkylene oxides. For example, ethylene oxide and propylene oxide are preferable.

(Ro 1-6) Cyclic imino ethers. For example, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline and the like are preferable.

(B 1-7) Styrenes. For example, styrene, 4-ethylstyrene, α-methylstyrene and the like are preferable.

(B 1-8) Vinyl esters. For example, vinyl acetate and vinyl caproate are preferable.

(Bro 1-9) Polyesters composed of a dihydric alcohol and a divalent carboxylic acid. For example, polyethylene glycol and terephthalic acid, or a polycondensate of 1,4-butanediol and succinic acid is preferable.

(B 1-10) Polyamides. For example, a ring-opening polymer of N-methylvalerolactam is preferable.

(Ro 1-11) Polyurethanes. For example, polyethylene glycol, hexamethylene diisocyanate, and a polyaddition product of N-methyl-diethanolamine or 1,4-butanediol are preferable.

  Among these, a polymer chain having an alkyleneoxy group obtained by polymerizing an alkylene oxide of (ro 1-5) as a structural unit is particularly preferable.

  In the case of a polymer chain having an alkyleneoxy group as a structural unit, in the polymer chain (b), the alkyleneoxy group is preferably an ethyleneoxy group and / or a propyleneoxy group, and the ethyleneoxy group and the propyleneoxy group may each be a homopolymer. It may be a block or random copolymer. The average degree of polymerization of the polymer chain (b) is preferably 40 to 200, and more preferably 80 to 150 from the stability of the liquid detergent composition. In addition, the terminal of the polymer chain having an alkyleneoxy group as a structural unit is not limited, and may have a hydroxyl group and a hydrocarbon group, for example, an ether bond such as a methoxy group, an ethoxy group, and a phenyl group It may be. The hydrocarbon group is preferably an alkyl group having 1 to 12 carbon atoms. More preferably, it is 1-3 alkyl groups.

(B2) Organic group The organic group is preferably a hydrocarbon group having 8 to 30 carbon atoms, more preferably 12 to 22 carbon atoms, and particularly preferably a linear or branched alkyl group having these carbon numbers. Or an alkenyl group. Such a hydrocarbon group is introduced by a monomer having the hydrocarbon group. Examples of such monomers include the following.

(B2-1) A (meth) acrylic acid ester having a saturated or unsaturated alkyl group or aralkyl group having 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms. For example, decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, stearyloxypolyethylene glycol monomethacrylate Acid ester etc. are mentioned.

(B2-2) Substituted (meth) acrylamide having 1 or 2 of a saturated or unsaturated alkyl group or aralkyl group having 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms, bonded to nitrogen. For example, N-lauryl (meth) acrylamide, N-dioctyl (meth) acrylamide, etc. are mentioned.

(B 2-3) Vinyl ether having a saturated or unsaturated alkyl group or aralkyl group having 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms. Examples thereof include lauryl vinyl ether, myristyl vinyl ether, palmityl vinyl ether, stearyl vinyl ether and the like.

  As the type 1 polymer, the segment (b) is a polymer chain having a carboxy group or a salt thereof in the structural unit, and the segment (b) is a nonionic polymer chain or a hydrocarbon group having 8 to 30 carbon atoms. Preferably, the segment (b) is a polymer chain having a carboxy group or a salt thereof in a structural unit, and the segment (b) is a polymer having a polymer chain having an alkyleneoxy group as a structural unit, preferable.

  In the polymer of Type 1, the mass ratio of the segment (A) to the segment (B) is (A) / (B) = 30/70 to 90/10, preferably 35/65 to 85/15, and 40/60 ~ 80/20 is more preferred.

  The water-soluble stabilizing polymer having segment (a) and segment (b) is preferably a block type or graft type polymer, and more preferably a graft type polymer.

  The method for synthesizing the block type or graft type polymer is not particularly limited, and a known method can be selected. Among them, a method for polymerizing vinyl monomers and the like using a macroazo initiator having an azo group in a polymer chain (macroazo initiator method), a polymer, using one or more liquids constituting a liquid detergent composition as a solvent A method using a compound having a polymerizable group at one end of the chain (macromonomer method), a radical polymerization of a monomer in the presence of a polymer, and a newly generated polymer chain coexisting in advance by a chain transfer reaction And a method in which another polymer terminal is reacted with a functional group in the polymer chain to cause grafting.

  Here, the weight average molecular weight of the Type 1 polymer is preferably 5,000 to 1,000,000, and more preferably 5,000 to 500,000.

  Preferred examples of Type 1 polymers include the following: 6. Is particularly preferred.

1. A copolymer of a polyalkylene glycol and a vinyl monomer having a carboxy group or a salt thereof (preferably a monoester) and a vinyl monomer having a carboxy group or a salt thereof, and derivatives thereof.

  Among these, a copolymer of a polyalkylene glycol (meth) acrylic acid ester and a vinyl monomer having a carboxy group or a salt thereof is more preferable, and a polyalkylene glycol (meth) acrylic acid ester and a (meth) acrylic acid or a salt thereof. A copolymer is particularly preferred. For example, a copolymer of polyethylene glycol mono (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof, poly (ethylene glycol / propylene glycol) mono (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof And the like are preferred.

2. A copolymer of a polyalkylene glycol ether having a reactive unsaturated group (an unsaturated group capable of radical polymerization) and a vinyl monomer having a carboxy group or a salt thereof, and derivatives thereof.

  A copolymer of a polyalkylene glycol ether having a reactive unsaturated group and (meth) acrylic acid or a salt thereof and / or a maleic monomer is preferred. Examples thereof include a copolymer of polyethylene glycol allyl ether and maleic acid (or a salt thereof).

3. A copolymer obtained by grafting a monomer having a carboxy group or a salt thereof to polyalkylene glycol and a derivative thereof.

  For example, a graft polymer obtained by radical polymerization of acrylic acid and maleic acid or a salt thereof in polyethylene glycol, polypropylene glycol or poly (ethylene glycol / propylene glycol) is preferred.

  1. ~ 3. Examples of the derivative include those having a hydrocarbon group such as a methoxy group, an ethoxy group, and a phenyl group at the terminal of the polyalkyleneoxy group to form an ether bond. As a hydrocarbon group, Preferably it is a C1-C12 alkyl group, More preferably, it is a 1-3 alkyl group.

4). A (co) polymer of vinyl monomers having a carboxy group or a salt thereof using a polyalkylene glycol macroazo initiator.

  A block polymer obtained by radical polymerization of (meth) acrylic acid or a salt thereof is preferable.

5. A graft polymer obtained by linking a polymer of a vinyl monomer having a carboxy group or a salt thereof and a polyalkylene glycol having a hydroxyl group at a terminal by a dehydration reaction.

  Preferably, a graft polymer obtained by linking poly (meth) acrylic acid or a salt thereof and polyethylene glycol having a hydroxyl group at a terminal by a dehydration reaction can be used.

6). A copolymer of a vinyl monomer having a carboxy group or a salt thereof and a vinyl monomer having a hydrocarbon group having 8 to 30 carbon atoms.

  Preferred is a copolymer of (meth) acrylic acid or a salt thereof and a (meth) acrylic acid ester having an alkyl group having 8 to 30 carbon atoms.

  1 above. ~ 6. In addition, a part of the segment (a) is preferably made of vinyl monomers having a sulfonic acid group, such as styrene sulfonic acid and / or its salt, 2-acrylamido-2-methylpropane sulfonic acid and / or its salt, May be substituted with a sulfonic acid group such as (meth) allylsulfonic acid and / or a salt thereof, and a part of the segment (b) may be replaced with the above (b1-1) to (b1-3), (b1 7) and a polymer chain having a structural unit derived from a monomer selected from (ro 1-8). Further, vinyl monomers having a cationic group, preferably 2-((meth) acryloyloxy) ethyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, 2-((meth) ethyl sulfate, within a range not impairing the effects of the present invention. Acrylicyloxy) ethyldimethylethylammonium chloride, 3-((meth) acrylamide) propyltrimethylammonium chloride, diallyldimethylammonium chloride and the like may be further copolymerized.

  As the type 2 polymer, the segment (a) is preferably a polymer chain having a carboxy group or a salt thereof in the structural unit, and the proportion of the polymer to the total amount of the segment (a) in the polymer is 85 to 85%. It is preferably 100% by mass, more preferably 90-100% by mass, and particularly preferably 95-100% by mass. The mass ratio of the segment (b) and the segment (b) is (b) / (b) = 100/0 to 95/5, but (b) / (b) = 100/0 is preferable.

The Type 2 polymer is preferably dissolved uniformly in the aqueous phase and not uniformly dissolved in the droplets containing the surfactant. Preferred examples of Type 2 polymers include (co) polymers of vinyl monomers having a carboxy group or a salt thereof, such as acrylic acid and / or a salt thereof, methacrylic acid and a salt thereof, styrenesulfonic acid and / or a salt thereof, 2 -(Co) polymer of acrylamido-2-methylpropanesulfonic acid and / or its salt, (meth) allylsulfonic acid and / or its salt. Further, as a component containing a small amount of the segment (b), a monomer selected from the above (b1-1) to (b1-3), (b1-7), and (b1-8) was further copolymerized. It may be a thing. Further, vinyl monomers having a cationic group, preferably 2-((meth) acryloyloxy) ethyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, 2-((meth) acryloyl ethylsulfate, as long as the effects of the present invention are not impaired. Oxy) ethyldimethylethylammonium chloride, 3-((meth) acrylamide) propyltrimethylammonium chloride, diallyldimethylammonium chloride and the like may be further copolymerized.

  The polymer of Type 3 is preferably a polymer in which the segment (b) has a polymer chain having an alkyleneoxy group as a structural unit. Moreover, it is preferable that the ratio which occupies with respect to the total amount of the segment (b) in a polymer is 85-100 mass%, It is still more preferable that it is 90-100 mass%, It is that it is 95-100 mass%. Particularly preferred. Further, the mass ratio of the segment (b) to the segment (b) is (b) / (b) = 5/95 to 0/100, but (b) / (b) = 0/100 is preferable.

  It is preferable that the Type 3 polymer is uniformly dissolved in the droplets and not uniformly dissolved in the aqueous phase. Preferable examples of Type 3 polymers include polyalkylene glycols such as polyethylene glycol and polypropylene glycol. For this, a part of the segment (b) is further replaced with a structural unit derived from a monomer selected from (b1-1) to (b1-3), (b1-7), and (b1-8). You may substitute for the polymer chain which has. Further, vinyl monomers having a sulfonic acid group as a component containing a small amount of segment (a), such as styrene sulfonic acid and / or a salt thereof, 2-acrylamido-2-methylsulfonic acid and / or a salt thereof, more preferably (meta ) Allylsulfonic acid and / or a salt thereof may be further copolymerized. Further, vinyl monomers having a cationic group, preferably 2-((meth) acryloyloxy) ethyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, 2-((meth) acryloyl ethylsulfate, as long as the effects of the present invention are not impaired. Oxy) ethyldimethylethylammonium chloride, 3-((meth) acrylamide) propyltrimethylammonium chloride, diallyldimethylammonium chloride and the like may be further copolymerized.

<(H) component>
From the viewpoint of cleaning performance, the liquid detergent composition of the present invention further comprises (h) a chelating agent having a molecular weight of 1000 or less and a calcium capture amount of 200 to 600 CaCO ₃ mg / g and a calcium stability constant of 2 to 10 [hereinafter, ( h) ”).

  In the liquid detergent composition of the present invention, the content of the component (h) is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 25% by mass.

  Examples of the component (h) include polyphosphate, aluminosilicate, citric acid, diglycolic acid, iminodisuccinic acid, S-aspartic acid-N, N-diacetic acid, serine diacetic acid, nitrilotriacetic acid, and the like. . In view of stability, inorganic chelating agents are preferred. Among these, tripolyphosphate and zeolite are preferable, and zeolite is particularly preferable.

  In the present invention, the calcium stability constant and the calcium capture amount are those obtained by the following method.

(Measurement method of calcium stability constant)
A 0.1 mol / liter NH ₄ Cl—NH ₄ OH (pH 10.0) solution is prepared as a buffer. All sample solutions are prepared using this buffer. For measuring the Ca ²⁺ concentration, an ion meter 920A manufactured by Orion Co., Ltd. and a Ca ²⁺ ion electrode are used. First, a relationship between the calcium chloride concentration and the electrode potential is obtained, and a calibration curve is created. 5.36 × 10 ^-2 mol / l solution of calcium chloride and 5.36 × 10 ^-4 mol / l solution of a chelating agent sample are prepared. Add 1 ml of calcium chloride solution to 100 ml of chelating agent sample solution and stir for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. Assuming that the chelating agent forms a chelate complex with Ca ²⁺ and 1: 1, the calcium stability constant (Ca stability constant) is obtained from the following formula.

(Measurement method of calcium capture amount)
All solutions are prepared using the following buffers. In addition, a calcium ion electrode was appropriately used.
Buffer solution: 0.1M-NH ₄ Cl-NH ₄ OH buffer (pH 10.0)
(1) Preparation of calibration curve Various standard calcium ion solutions are prepared, and a calibration curve showing the relationship between the logarithm of the calcium ion concentration and the potential as shown in FIG. 1 is prepared.
(2) Measurement of calcium ion trapping amount
About 0.1 g of sample (chelating agent) is weighed into a 100 ml volumetric flask, and a 100 ml solution is prepared with the above buffer solution. To this, a CaCl ₂ aqueous solution (pH 10.0) corresponding to 20000 ppm (calculated in terms of CaCO ₃ ) is dropped from a burette (a blank is also measured).
The dropping is carried out by adding 0.1 to 0.2 ml of an aqueous CaCl ₂ solution, reading the potential at that time, and obtaining the calcium ion concentration from the calibration curve in FIG. Based on this, a graph showing the relationship between the calcium ion concentration and the dropping amount of the CaCl ₂ aqueous solution is prepared, and FIG. 2 is obtained. The calcium ion concentration at the sample dropping amount A in FIG. 2 is the calcium ion trapping amount of the sample.

<Other ingredients>
In the present liquid detergent composition, as the surfactant, in addition to the nonionic surfactant of the component (a), an anionic surfactant, a cationic surfactant, And may contain amphoteric surfactants such as alkylcarbobetaines, alkylsulfobetaines, alkylamidohydroxysulfobetaines, alkylamidoamine-type betaines, alkylimidazoline-type betaines, and in terms of cleaning performance and solubility, component (a) In addition to the nonionic surfactant, it is preferable to further contain an anionic surfactant.

As the anionic surfactant, the following (i) to (d) can be used, but it is preferable to contain (d) in terms of stability and solubility.
(A) Alkylbenzenesulfonate having an alkyl group having an average carbon number of 10 to 20.
(B) An average of 0.5 to 6 moles of ethylene oxide per molecule having an alkyl group derived from a linear primary alcohol or linear secondary alcohol having an average carbon number of 10 to 20, or an alkyl group derived from a branched alcohol. An alkyl ether sulfate ester salt to which (hereinafter referred to as EO) is added.
(C) Alkyl or alkenyl sulfate ester salts having an average alkyl group or alkenyl group having 10 to 20 carbon atoms.
(D) Fatty acid salts having an average carbon number of 8-20.

  Examples of counterions of these anionic surfactants include cations such as sodium, potassium, magnesium, calcium and alkanolamine, monomethyldiethanolamine, dimethylmonoethanolamine, and mixtures thereof.

  The anionic surfactant may be blended in the liquid detergent composition as a neutralized product, or may be neutralized after blending in the liquid detergent composition in the acid form.

  Examples of the cationic surfactant include mono long-chain alkyl or alkenyl quaternary ammonium salts.

  Examples of amphoteric surfactants include alkylcarbobetaines, alkylsulfobetaines, alkylamidohydroxysulfobetaines, alkylamidoamine-type betaines, and alkylimidazoline-type betaines.

  In addition, a water-soluble inorganic salt other than the component (b) may be added to the liquid cleaning composition. Examples of the water-soluble inorganic salt other than the component (b) include alkali metal, ammonium, alkylammonium chloride, bromide, sulfate and the like.

  In addition, a scavenger for polyvalent metal ions such as zeolite, amorphous aluminosilicate, sodium tripolyphosphate, sodium pyrophosphate, aminocarboxylate, etc. may be added to the liquid detergent composition. In view of cleaning performance, the content in the composition is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.

  Further optional components include solubilizers such as p-toluenesulfonic acid and benzoate (also effective as preservatives); color transfer inhibitors such as polyvinylpyrrolidone; enzyme stabilizers such as calcium chloride and calcium sulfate Fluorescent dyes such as Tinopearl CBS-X (manufactured by Ciba Specialty Chemicals); Silicones for imparting flexibility; Silica and silicone as antifoaming agents; Antioxidants such as butylhydroxytoluene and distyrenated cresol; Fluorescence Examples include dyes, fragrances, antibacterial preservatives, enzymes, and coloring agents.

  Moreover, the liquid detergent composition of the present invention preferably has a pH of 6 to 12 and more preferably 7 to 11 at 20 ° C. according to the method described in JIS K 3362: 1998 from the viewpoint of cleaning performance and damage. 8-11 are more preferable, 9-11 are especially preferable, and 10-11 are the most preferable.

<Manufacturing method>
The liquid detergent composition of the present invention is a step I of mixing the component (a), the component (b), and the component (c), and a step of mixing the mixture obtained by the step I and the component (d). It is preferable to manufacture by the manufacturing method which has II. The liquid detergent composition obtained by such a production method is more preferable in terms of storage stability.

[I] Preparation of liquid detergent composition (I-1) Examples 1 to 5 and Comparative Examples 2 to 3
In a 500 cc beaker (inner diameter: 90 mm), weigh out all the components of the composition shown in Table 1 so that the total amount is 300 g. In a stirring part (manufactured by Tokushu Kika Co., Ltd.), stirring was performed at 9000 r / min for 10 minutes to prepare a liquid detergent composition.

(I-2) Comparative Example 1
In a 500 cc beaker (inner diameter: 90 mm), weigh out all the components shown in Table 1 in a 500 cc beaker (inner diameter: 90 mm). (10 mm, diameter 60 mm), stirring was performed at 300 r / min for 10 minutes to prepare a liquid detergent composition. In addition, the position of the blade | wing was made into the location of 1/3 of liquid height from the bottom part of a beaker.

[II] Evaluation The liquid detergent composition prepared above was evaluated for the solubility, the cleaning ability of the collar stain, the storage stability, and the finish (flexibility). Moreover, the volume average particle diameter of the droplets in the composition was measured by the following method. The results are shown in Table 1. Since the compositions of Comparative Examples 1 and 2 were separated into two layers, they were shaken by hand immediately before use.

(II-1) Volume average particle diameter of droplets After the composition is rapidly frozen by the metal contact method, a cross section is prepared with a cryomicrotome using a diamond knife for an optical microscope, and the sample cross section is observed with a Cryo-SEM. And the volume average particle size of the droplets was measured. As the apparatus, a field emission scanning electron microscope (manufactured by Hitachi, S-4000), a cryounit (manufactured by Hitachi, Ltd.), an ultramicrotome (manufactured by LKB, LKB2188 Ultrotome Nova), and a cryounit (manufactured by LKB) were used. In the table, the volume average particle diameters of Comparative Examples 1 and 2 are for compositions shaken by hand immediately before use.

(II-2) Solubility test (1) A 0.05 g sample is placed on the hole portion of a 1-hole hole slide glass (manufactured by MATSUNAMI).
(2) Set the slide glass on the top of the SUS cylinder (diameter 5cm, height 20cm), and fix it with rubber bands to prevent it from moving. At this time, one end of the slide glass is brought into contact with the end of the cylinder.
(3) A stirrer piece (diameter 8 mm, length 40 mm) is put into a 2 L beaker (manufactured by IWAKI), placed on a magnetic stirrer (Shimadzu magnetic stirrer SST172), and 1.5 L of 5 ° C. tap water is added.
(4) Slowly sink the one prepared in (2) into the water of (3). At that time, care should be taken not to flow by the water flow generated by the sample on the glass slide. Place the cylinder so that it is almost in contact with the inner wall of the beaker, and set the preparation so that it faces the center.
(5) Start stirring at 500 r / min, and measure the time until all the samples on the slide flow out into the liquid. The measurement is performed 5 times, and the average value is taken as the elution time.

  The determination of solubility was defined as “◯” for less than 2 minutes, “Δ” for 2 minutes or more and less than 4 minutes, and “x” for 4 minutes or more. If the solubility is “×”, for example, a weak water course of a washing machine (if you want to wash clothes when you do not want to damage clothes) or a short course (if you want to wash quickly) When high solubility is required, it can be considered that it takes time to dissolve the composition, resulting in poor detergency.

(II-3) Collar dirt cleaning power evaluation (preparation of collar red cloth)
A collar lining cloth described in JIS K3362: 1998 is prepared.
(Cleaning conditions and evaluation method)
In accordance with the method for evaluating the cleaning power of a synthetic detergent for clothing described in JIS K 3362: 1998, the cleaning power of the liquid detergent composition in Table 1 and the index detergent for determining cleaning power were compared and evaluated according to the following criteria. The use concentration of the liquid detergent composition shown in Table 1 was 1.33 g / L.
◎: Superior to index detergent ○: Equivalent to index detergent ×: Inferior to index detergent

(II-4) Storage stability test 10 g of the liquid detergent composition was put into a flat bottom test tube having an inner diameter of 15 mm and a height of 120 mm, the upper part was sealed with a silicone cap, stored at room temperature for 3 months, and then separated according to the following formula: The rate was calculated and the stability was evaluated according to the following criteria.
Separation rate (%) = [(thickness of transparent separation layer) / (height of the entire liquid)] × 100
○: Separation rate is less than 5% △: Separation rate is 5% or more and less than 10% ×: Separation rate is 10% or more

(II-5) Finished evaluation (flexibility) test (II-5-1) Preparation of pre-treated cloth Using a fully automatic washing machine (NA-F50K1 manufactured by Matsushita), cotton towel, cotton knitted underwear, acrylic A jersey was put in, and an index detergent for determining cleaning power described in JIS K 3362: 1998 was added according to the standard usage amount, and washing was performed on a standard course. This washing cycle was repeated 5 times, and a treated cloth dried with a dryer was used as a test cloth.

(II-5-2) Evaluation method Using the above washing machine, put 2 cotton towels, 2 cotton underwear, 2 acrylic jerseys, and 40 ml of the liquid detergent composition shown in the table. Laundry was done. Each test cloth after washing was dried indoors (25 ° C., 45% RH) for one day.

(II-5-3) Judgment method Each test cloth was judged according to the following criteria by sensory evaluation of five panelists based on the pretreated fabric.
Clearly softer than standard test cloth: +2 points Slightly softer than standard test cloth: +1 point Equivalent to standard test cloth: 0 points Slightly harder than standard test cloth: -1 point Clearer than standard test cloth Hard: -2 points Evaluation was made according to the following criteria by the average value of the total points of 6 clothing totals determined by each panel.
The average of the total points of 6 clothing totals is 8 points or more: ○
The average value of the total score of 6 clothing items is 0 or more and less than 8: △
The average value of the total score of 6 clothing items is less than 0: ×

(Note) The components in the table are as follows.
・ Nonionic surfactant (1): An average of 8 moles of EO added to a primary alcohol having 10 to 14 carbon atoms ・ Nonionic surfactant (2): EO to a secondary alcohol having 12 to 14 carbon atoms Nonionic surfactant (3): 7 to 10 carbon atoms on average, 10 moles of EO on average, 2 moles of propylene oxide (hereinafter referred to as PO) on average, and EO on average Non-ionic surfactant (4): A secondary alcohol having 12 to 14 carbon atoms with an average of 9 mol of EO and PO of 1 mol on the average. Anion Surfactant (1): Polyoxyethylene alkyl ether sulfate ester salt (linear alkyl having 10 to 14 carbon atoms, EO average addition mole number 3, sodium salt)
-Anionic surfactant (2): C10-14 linear alkylbenzene sulfonic acid-Anionic surfactant (3): Fatty acid, LUNAC L-55 (manufactured by Kao Corporation)
・ Clay mineral: Bentonite, Round rosyl DGA212 (manufactured by Zude Chemi)
Polymer (1): methoxypolyethylene glycol (EO average addition mole number 90) monomethacrylate / methacrylic acid = 50/50 (mass ratio) copolymer (weight average molecular weight 46,000; measurement by GPC, polyethylene glycol Conversion)
As the polymer (1), the polymer solution (1) synthesized in Synthesis Example 1 below was used. Moreover, in blending into the liquid detergent composition, the content of the polymer in the polymer solution was determined on the assumption that the polymerization reaction had proceeded completely, and blended in terms of the mass of the polymer.

<Synthesis Example 1>
When 122 g of ion-exchanged water and 122 g of propylene glycol were heated to 80 ° C. in a nitrogen atmosphere, methoxypolyethylene glycol (EO addition mole number 90) monomethacrylate (NK-ester M-900G, Shin-Nakamura Chemical Co., Ltd.) 150 g, 150 g of methacrylic acid, 4.2 g of 2-mercaptoethanol dissolved in a mixture of 50 g of ion-exchanged water and 100 g of propylene glycol, 4.2 g of sodium persulfate and 1.7 g of 35% hydrogen peroxide water What was melt | dissolved in the ion-exchange water 50g was dripped separately over 2 hours, keeping at 80-85 degreeC, and stirring was further continued for 4 hours, keeping at 80 degreeC after that. This was cooled to obtain a polymer solution (1).

  The weight average molecular weight of the obtained polymer was 46,000 (in terms of polyethylene glycol). Here, the molecular weight was measured by gel permeation chromatography (GPC), and the following conditions were used. Both eluents and added salts were prepared from grades for liquid chromatography.

Column: Two pieces of G4000PWXL + G2500PWXL manufactured by Tosoh Corporation
Eluent: 0.2M phosphate buffer (pH 6.9) / acetonitrile = 9/1 (volume ratio),
Detector: differential refractometer,
Temperature: 40 ° C
Standard: Polyethylene glycol measurement concentration: 5 mg / ml,
Injection volume: 100 μl

Polymer (2): polyacrylic acid (weight average molecular weight 15,000; measured by GPC, converted to polyethylene glycol)
Polymer (3): polymer compound synthesized by the method of Synthesis Example 1 in paragraph 4 of page 4 of JP-A-10-60476 (weight average molecular weight 10,000; measured by GPC, converted to polyethylene glycol)
-Polymer (4): Polyethylene glycol (weight average molecular weight 10,000)

Polymer (5): Polyethylene glycol (EO addition mole number 94) allyl ether / acrylic acid = 60/40 (mass ratio) copolymer (weight average molecular weight 61,000; measured by GPC, converted to polyethylene glycol)
As the polymer (5), the polymer solution (2) synthesized in Synthesis Example 2 below was used. Moreover, in blending into the liquid detergent composition, the content of the polymer in the polymer solution was determined on the assumption that the polymerization reaction had proceeded completely, and blended in terms of the mass of the polymer.

Synthesis example 2
(2-1) 350 parts by mass of ethylene glycol monoallyl ether (manufactured by Nippon Emulsifier Co., Ltd.) and 3.9 parts by mass of potassium hydroxide are placed in the autoclave, and the air in the system is replaced with nitrogen and sealed. The mixture was heated with stirring to keep the internal temperature at 130 ° C. and the internal pressure at 0.08 MPa. Here, introduction of EO was started, and it was gradually introduced so that the internal temperature did not exceed 150 ° C. and the internal pressure did not exceed 0.4 MPa. After no increase in internal temperature due to heat generation was observed, the introduction of EO was continued while maintaining the internal temperature at 150 ° C. and the internal pressure at 0.4 MPa, and finally 5736 parts by mass of EO was introduced over approximately 4.5 hours. did. Subsequently, stirring was continued for about 30 minutes while maintaining the internal temperature at 150 ° C. Thereafter, the internal temperature was lowered to 80 ° C., the product was extracted, and cooled to room temperature to obtain a white waxy solid. When GPC measurement was performed, the weight average molecular weight was 2530. The addition polymerization reaction of EO and PO was performed in an autoclave made of stainless steel. Potassium hydroxide used for the catalyst is an industrial grade plate-like pellet having a purity of about 96% by mass (others are mainly moisture).

(2-2) When polyethylene glycol (EO addition mole number 94) allyl ether 72 g obtained in (2-1) above, ion-exchanged water 30 g, and propylene glycol 70 g were heated to 80 ° C. in a nitrogen atmosphere, While maintaining 48 g of acrylic acid in 37 g of ion-exchanged water and what dissolved 4.88 g of sodium persulfate and 3.99 g of 35% hydrogen peroxide in 30 g of ion-exchanged water at 80 to 85 ° C., The solution was dropped separately over 30 minutes, and then stirred for another 3 hours while maintaining the temperature at 80 ° C. This was cooled to obtain a synthetic polymer solution (2). As a result of GPC measurement of the obtained synthetic polymer, the weight average molecular weight (measurement method is the same as in Synthesis Example 1) was 61,000 (in terms of polyethylene glycol).

・ Zeolite: Toyo Builder (Toyo Soda Co., Ltd.)
-POE monophenyl ether: polyoxyethylene monophenyl ether (EO average 3 mol addition)
Enzyme: Everase 16.0L-EX (protease, Novozyme)
・ Fluorescent dye: Chino Pearl CBS-X (manufactured by Ciba Specialty Chemicals)
In addition, pH (JIS K 3362: 1998, 20 degreeC) of the composition in a table | surface was all 6-12.

It is a calibration curve for calculating | requiring calcium ion concentration from an electric potential. It is a graph showing a dropping amount of related calcium ion concentration and the CaCl ₂ aqueous solution.

Claims (4)

(A) a nonionic surfactant 5-60% by weight, (b) alkali metals carbonates, at least one water-soluble inorganic salt 5-40 wt% selected sulfates or these A alkali metals, ( c) 15 to 80% by mass of water, (d) 5 to 30 % by mass of clay mineral , (g1) 0.05 to 10% by mass of a water-soluble stabilizing polymer having a weight average molecular weight of 3000 to 8 million ,
The amount of the surfactant corresponding to JIS K 3362: 1998 is 10 to 60% by mass, and there are droplets having an average particle size of 0.1 to 20 μm.
The viscosity is 10 to 2000 mPa · s (B-type viscometer, 60 r / min, 60 seconds, 20 ° C.) ,
In (b), at least one selected from alkali metal carbonates is 50% by mass or more,
(G1) is a segment (a) selected from a polymer chain having an anionic group or a salt thereof in a structural unit and a segment selected from a polymer chain having an alkyleneoxy group obtained by polymerizing alkylene oxide as a structural unit A polymer having a mass ratio of (a) and (b) of (b) / (b) = 30/70 to 90/10, segments (b) and (b) The mass ratio of (A) / (B) = 100/0 to 95/5, and the mass ratio of the segments (A) and (B) is (A) / (B) = 5 / 95-0 / A polymer selected from 100 polymers,
Liquid detergent composition. The liquid detergent composition according to claim 1, wherein the liquid detergent composition is produced by stirring with a homomixer . The liquid detergent composition according to claim 1 or 2 , which is optically isotropic. The liquid detergent composition according to any one of claims 1 to 3 , which comprises a step of stirring a component containing (a), (b), (c), (d) and (g1) with a homomixer . Manufacturing method.

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