JP4489538B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition that is easy to use and has excellent solubility and detergency. 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. From this point of view, development of liquid detergents containing builder has been promoted.

  For example, a liquid detergent that is separated into two layers of a liquid surfactant and a builder aqueous solution adjusted to a concentration that is insoluble or hardly soluble in the surfactant, and is used by mixing evenly by shaking immediately before use. (For example, refer to Patent Documents 1 and 2). However, these have problems such as annoying to shake immediately before use, a large droplet size of the surfactant, and insufficient solubility at a low temperature.

  Moreover, the aqueous | water-based fluid detergent composition containing the effective amount of detergent builder which can be added by pouring is disclosed (for example, refer patent document 3). However, since this composition achieves storage stability by increasing thixotropy, the viscosity at a low shear rate becomes very high and can be added by pouring. There are problems such as sagging, and the solubility in water is inferior.

  Further, a non-aqueous liquid detergent composition in which a builder is dispersed in a nonionic surfactant is disclosed (see, for example, Patent Documents 4, 5, 6, 7, and 8). However, since the composition has a flash point, there is a problem that care must be taken for storage. There were also problems in usability and stability.

  Also disclosed is a liquid detergent composition in which lamellar droplets composed of a surfactant containing a peptized polymer having a specific structure are suspended in an aqueous continuous phase (see, for example, Patent Document 9). Although the viscosity also ranges from 30 to 1750 mPa · s, there is a disadvantage that the cleaning power is inferior, especially since inorganic salt builders such as alkaline agents are low in concentration.

  On the other hand, as a method for stably blending a solid builder component into a liquid detergent, refinement of the primary particle diameter has been studied. For example, a method of mechanically pulverizing (for example, see Patent Document 10) and a method for obtaining fine particles according to a specific preparation composition and reaction conditions have been studied (for example, see Patent Documents 11 and 12). However, these methods have problems in cleaning performance and production efficiency as a builder, and need to be improved.

Therefore, there has been a demand for a liquid detergent that achieves high detergency and has good solubility while taking advantage of the ease of use of the liquid detergent.
JP-A-8-20799 Japanese National Patent Publication No. 11-502898 JP 58-145794 A JP 54-16514 A JP 56-159297 A JP-A-60-230,000 JP 61-204300 A JP-A-2-240200 Japanese National Patent Publication No. 5-501574 Japanese Examined Patent Publication 62-46494 JP 60-127218 A JP-A-62-275016

  An object of the present invention is to provide a liquid detergent composition which is excellent in ease of use, solubility and detergency, and has good storage stability. More specifically, a liquid detergent composition that improves the detergency that has been a drawback of conventional liquid detergents without sacrificing storage stability and solubility while taking advantage of the ease of use of the liquid detergent. Is to provide.

  The present invention comprises (a) an anionic surfactant (hereinafter referred to as component (a)) 0.1 to 50% by mass, (b) an alkali metal carbonate, an alkali metal silicate, and an alkali metal sulfate. And at least one water-soluble inorganic salt selected from alkali metal chlorides (hereinafter referred to as component (b)), (c) water (hereinafter referred to as component (c)) 15 to 80% by mass, (d) Water-soluble stabilizing polymer having a weight average molecular weight of 3000 to 8 million [hereinafter referred to as component (d)] 0.1 to 10% by mass, (e) Water-miscible organic solvent having a weight average molecular weight of less than 3000 [hereinafter referred to as (e) Component)] containing 0.1 to 20% by mass, and there is a droplet containing a surfactant having a volume average particle size of 0.1 to 20 μm in the composition, and the surface activity described in JIS K 3362: 1998 The amount corresponding to the agent is 10 to 60% by mass, (b) The amount is equal to or greater than the amount by which at least a part of the surfactant is precipitated in the composition, and the mass ratio of (b) to (c) is (b) / (c) = 10/90 to 60/40, The present invention relates to a liquid detergent composition having a viscosity of 10 to 2000 mPa · s (B-type viscometer, 60 r / min, 60 seconds, 20 ° C.).

  According to the present invention, it is possible to obtain a liquid detergent composition that is excellent in ease of use, solubility and detergency, and has good storage stability. For example, the liquid detergent composition of the present invention dissolves quickly even in use situations where it takes a long time to dissolve with a conventional builder highly formulated liquid detergent, and can obtain a high detergency regardless of the use situation.

<(A) component>
The liquid detergent composition of this invention contains 0.1-50 mass% of anionic surfactant as (a) component. 0.5-40 mass% is preferable and 1-30 mass% is more preferable at the point of washing | cleaning performance, stability, and solubility.

As the component (a), the following (a1) to (a4) can be used.
(A1) Alkylbenzenesulfonate having an alkyl group having an average carbon number of 10 to 20.
(A2) having an alkyl group derived from a linear primary alcohol or linear secondary alcohol having an average carbon number of 10 to 20 or a branched alcohol, and having an average of 0.5 to 6 moles of ethylene oxide in one molecule An alkyl ether sulfate ester salt to which (hereinafter also referred to as EO) is added.
(A3) Alkyl or alkenyl sulfate ester salt having an average alkyl group or alkenyl group having 10 to 20 carbon atoms.
(A4) Fatty acid salt having an average carbon number of 8 to 20.

  The counter ion of these anionic surfactants is selected from the group consisting of cations such as sodium, potassium, magnesium, calcium and alkanolamine, and mixtures thereof. Monomethyldiethanolamine or dimethylmonoethanolamine may be used. In particular, it is preferable to contain (a4) in terms of stability and solubility.

  (A) A component may be mix | blended in a liquid detergent composition as a neutralized material, or may be neutralized, after mix | blending in a liquid detergent composition with an acid form.

<(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 a composition at 25 ° C. in an amount that causes at least a part of the surfactant to precipitate (salt out). The specific content of the component (b) is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and 10 to 25% by mass in terms of cleaning performance, stability and solubility in the composition. Is more preferable. In addition, about (b) component, water solubility means melt | dissolving 10 g / L or more in 25 degreeC ion-exchange water. The component (b) is preferably blended in an amount exceeding the amount that precipitates (salts out) at least a part of the anionic surfactant of the component (a) in water.

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

  Further, 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 more than one part is dissolved, and it is still more preferable that it is dissolved completely substantially.

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

<(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.

  In the present invention, the mass ratio of the component (b) and the component (c) is (b) / (c) = 10/90 to 60/40, and in terms of stability, 15/85 to 50/50 is Preferably, 20/80 to 45/55 is more preferable, and 25/75 to 40/60 is still more preferable.

<(D) component>
The liquid detergent composition of the present invention contains 0.1 to 10% by mass of a water-soluble stabilizing polymer having a weight average molecular weight of 3000 to 8 million as the component (d). In terms of stability and solubility, 0.2 to 8% by mass is preferable, 0.3 to 7% by mass is more preferable, and 0.5 to 5% by mass is still more preferable.

  In the present invention, the water-soluble stabilizing polymer means that a droplet having a volume average particle diameter of 0.1 to 20 μm present in the composition immediately after production of the composition containing the polymer is 50 ° C. for 1 month. Although the volume average particle diameter of 0.1 to 20 μm can be maintained after storage, the composition obtained by removing the polymer from the composition is a water-soluble polymer that cannot maintain the volume average particle diameter in the above range after storage. is there. Here, “water-soluble” means that 1 g / L or more dissolves in ion-exchanged water.

  Moreover, the weight average molecular weight of (d) component becomes like this. Preferably it is 3000-7 million, More preferably, it is 3000-6 million, Most preferably, it is 5000-6 million. Here, the weight average molecular weight is measured using gel permeation chromatography (GPC), and the average molecular weight is determined in terms of polyethylene glycol (PEG).

  The liquid detergent composition of the present invention has a viscosity (B-type viscometer, 60 r / min, 60 seconds, 20 ° C.) of 0.7 to 0.7 compared to a composition having a composition obtained by removing the component (d) from the composition. It is preferably 1.3 times, more preferably 0.8 to 1.2 times, and even more preferably 0.8 to 1.0 times.

  From the viewpoint of stability, the component (d) is preferably dissolved in the liquid detergent composition.

Component (d) is a polymer having a function of stably maintaining a state in which droplets (mainly containing a salted-out surfactant) are dispersed in the composition. Any can be used. Examples of the polymer having such a function include a segment (A) having an affinity for an aqueous phase and / or a segment (B) having an affinity for the droplet, wherein the segment (A) and ( (B) a polymer having 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). Of these, Type 1 and Type 2 polymers are preferred in view of stability and solubility, and Type 1 polymers are particularly preferred.
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 above water-soluble polymer as a stabilizing polymer are unknown, but it functions as an emulsifier for droplets in Type 1 polymers and thickens in water by dissolving in water in Type 2 polymers. It is thought that Type 3 polymer dissolves in the droplets to control its specific gravity and suppresses floating and sedimentation.

  In the case of a polymer chain, having affinity means that a polymer having a weight average molecular weight of about 2000 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 a 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. Here, the “target phase” refers to each phase generated when the composition of the present invention is mixed and centrifuged after removing the water-insoluble solid component such as inorganic builder particles and the component (d).

  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.

[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 means 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.

  Examples of the nonionic polymer chain include those having a structural unit derived from a monomer selected from the following monomer groups (B1-1) to (B1-8), or the following polymers (B1-9) to (B1). -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. The terminal of the alkyleneoxy group is not limited, and may have a hydroxyl group or a hydrocarbon group, and may be an ether bond such as a methoxy group, an ethoxy group, or a phenyl group. 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 a 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 type 1 polymer, the mass ratio of segment (a) to 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 polymer of Type 1 is preferably 5,000 to 1,000,000, more preferably 5,000 to 500,000.

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

1. Copolymer of ester (preferably monoester) of polyalkylene glycol and vinyl monomer having carboxy group or salt thereof, and vinyl monomer having carboxy group or salt thereof Polyalkylene glycol (meth) acrylate ester and carboxy group Alternatively, a copolymer with a vinyl monomer having a salt thereof is more preferable, and a copolymer of a polyalkylene glycol (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof is particularly preferable. 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 a copolymer thereof.

2. Copolymer of polyalkylene glycol ether having a reactive unsaturated group (radically polymerizable unsaturated group) and a vinyl monomer having a carboxy group or a salt thereof Polyalkylene glycol ether having a reactive unsaturated group and (meth) A copolymer of 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. Copolymer obtained by grafting a monomer having a carboxy group or a salt thereof onto polyalkylene glycol For example, radical polymerization of acrylic acid and maleic acid or a salt thereof in polyethylene glycol, polypropylene glycol or poly (ethylene glycol / propylene glycol) Preferred is a graft polymer obtained.

4). A (co) polymer of a vinyl monomer having a carboxy group or a salt thereof using a polyalkylene glycol macroazo initiator, preferably a block polymer obtained by radical polymerization of (meth) acrylic acid or a salt thereof.

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

6). 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 (meth) acrylic acid or a salt thereof and an alkyl group having 8 to 30 carbon atoms (meta ) A copolymer with an acrylic ester is preferred.

  1. ~ 6. In addition, vinyl monomers having a sulfonic acid group as part of the segment (a), such as styrene sulfonic acid and / or a salt thereof, 2-acrylamido-2-methylpropane sulfonic acid and / or a salt thereof are more preferable. May be replaced with (meth) allylsulfonic acid and / or a salt thereof, etc., and as a part of the segment (b), the above-mentioned (b1-1) to (b1-3), (b1-7), (Bro 1-8) may be substituted. 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, or a sulfonic acid group or a salt thereof in a structural unit, and these are the total amount of the segment (a) in the polymer. It is preferable that the ratio which occupies with respect to is 85-100 mass%, It is more preferable that it is 90-100 mass%, It is especially preferable that it is 95-100 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.

  It is preferable that the Type 2 polymer is uniformly dissolved in the aqueous phase and not uniformly dissolved in the droplets. Preferred examples of Type 2 polymers include vinyl monomers having carboxy groups or salts thereof and / or (co) polymers of vinyl monomers having sulfonic acid groups or salts thereof, such as acrylic acid and / or salts thereof, methacrylic acid and And / or a salt thereof, styrenesulfonic acid and / or a salt thereof, 2-acrylamido-2-methylpropanesulfonic acid and / or a salt thereof, and a (co) polymer of (meth) allylsulfonic acid and / or a salt thereof. . Further, as a component containing a small amount of the segment (b), the above (b1-1) to (b1-3), (b1-7), and (b1-8) may be further copolymerized. Furthermore, 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 3 polymer, the segment (b) is preferably a polymer having a polymer chain having an alkyleneoxy group as a constituent unit. The proportion of this to the total amount of segments (b) in the polymer is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. preferable. The mass ratio of the segment (b) and 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. About this, as a part of segment (b), (b1-1) to (b1-3), (b1-7), (b1-8) may be substituted. 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-methylpropane sulfonic acid and / or a salt thereof, more preferably ( It may be a copolymer obtained by further copolymerizing (meth) allylsulfonic acid and / or a salt thereof. Furthermore, 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. It may be a copolymer of acryloyloxy) ethyldimethylethylammonium chloride, 3-((meth) acrylamide) propyltrimethylammonium chloride, diallyldimethylammonium chloride and the like.

<(E) component>

  The liquid detergent composition of the present invention contains a water-miscible organic solvent having a weight average molecular weight of less than 3000 as component (e) in terms of stability and solubility. In particular, a water-miscible organic solvent having a hydroxyl group and / or an ether group is preferable. (E) As for content of a component, 0.1-20 mass% is preferable in a liquid detergent composition, 0.5-15 mass% is more preferable, 1-10 mass% is still more preferable.

  As the component (e), (i) alkanols such as ethanol, 1-propanol, 2-propanol and 1-butanol, (ii) glycols such as propylene glycol, butylene glycol and hexylene glycol, (iii) diethylene glycol, Polyglycols such as triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of about 200, polyethylene glycol having a weight average molecular weight of about 400, dipropylene glycol, tripropylene glycol, polypropylene glycol having a weight average molecular weight of about 2000, (iv ) Diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Lenglycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerin ether, 2-methylglycerin 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 Ethers, alkyl ethers such as diethylene glycol monobutyl ether, (v) 2-phenoxyethanol, diethylene glycol Aromatic ethers such as nophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having a weight average molecular weight of about 480, 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 (mono, di, tri Alkanolamines such as a mixture).

  The component (e) is effective as a viscosity modifier and gelation inhibitor of the composition, and the above (i) alkanols, (ii) glycols, (iv) alkyl ethers, (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 or more selected from (ii) and (v) Can be used to effectively adjust the viscosity of the composition and suppress gelation.

<Liquid cleaning composition>
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. The surfactant is a component (a), a nonionic surfactant of the component (g) described later, a cationic surfactant of the component (h), an amphoteric surfactant, and the like. A combination of the surfactant and the component (a) is preferable in terms of cleaning performance and solubility. Moreover, in 100 mass parts of surfactant equivalent, the sum total of (a) component and (g) component is 70-100 mass parts, Furthermore, it is preferable that it is 80-100 mass parts.

  Moreover, the liquid detergent composition of this invention has the droplet containing a surfactant with a volume average particle diameter of 0.1-20 micrometers in a composition. These droplets are mainly composed of a surfactant, water, a water-miscible organic solvent, or a surfactant and water. In addition, when a poorly soluble component, for example, an oil-soluble component such as silicone, a fluorescent dye, or the like is blended in the aqueous phase in which the component (b) is dissolved, these are also contained. This droplet preferably contains 1 to 100 parts by mass of 100 parts by mass of component (a). Such droplets are preferably present in the composition at the temperature of use, and are preferably present in the composition at least 20 ° C. More preferably, it exists over a temperature range of 5 ° C to 25 ° C.

  The droplet diameter can be determined by measuring an arbitrary 500 points with an optical microscope when the volume average particle diameter is 10 μm or more. It is preferable to obtain by measuring arbitrary 500 points by SEM. The volume average particle size of the droplets is 20 μm or less from the viewpoint of stability and solubility, and is 0.1 μm or more for obtaining productivity and an appropriate viscosity. Preferably it is 0.2-15 micrometers, More preferably, it is 0.2-10 micrometers.

  In the present invention, a stirrer such as a magnetic stirrer, pitched paddle, propeller blade, anchor, homomixer, homogenizer, disper, and line mixer, a media mill such as a sand mill, a vibration mill, an attritor, and a dyno mill, and a liquid jet interaction chamber are provided. A composition containing droplets having a volume average particle diameter in the above range by uniformly mixing each component using a pulverizer (for example, a micro fly dizer manufactured by Micro Fly Dix), an ultrasonic disperser, or the like Is obtained. In general, the volume average particle diameter can be controlled by the stirring speed.

  In the liquid cleaning composition of the present invention, the pH at 20 ° C. according to the method described in JIS K 3362: 1998 is preferably 6 to 12, more preferably 7 to 11, in terms of cleaning performance and damage. To 11 are more preferred, 9 to 11 are particularly preferred, and 10 to 11 are most preferred.

  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.

<Component (f)>
From the viewpoint of cleaning performance, it may further contain (f) a chelating agent having a molecular weight of 1000 or less (hereinafter referred to as component (f)) having a calcium capture amount of 200 to 600 CaCO ₃ mg / g and a calcium stability constant of 2 to 10. preferable.

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

  Examples of the component (f) 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)
0.1 mol / l NH ₄ of Cl-NH ₄ OH (pH10.0) to prepare a solution 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, a 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 A standard calcium ion solution is 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 diluted 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. The calcium ion concentration at the sample dropping amount A in FIG. 2 is the calcium ion trapping amount of the sample.

<(G) component>
The liquid detergent composition of the present invention preferably contains 40% by mass or less of a nonionic surfactant as component (g) in terms of improvement in cleaning performance and stability, and more preferably 1-40% by mass. Preferably, 5-35 mass% is further more preferable, and 10-30 mass% is especially preferable.

  In terms of cleaning performance and stability, the mass ratio of the component (a) to the component (g) is preferably 1/50 to 10/1, more preferably 1/50 to 1/1, and 1/50 to 1 /. 10 is more preferable.

  (G) As a component, what is shown by General formula (1) and / or (2) is preferable, and what is represented by General formula (2) is from the point of the ease of pouring of a liquid detergent composition. More preferred.

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

R ² O (EO) _k / (PO) _l H (2)
[Wherein, R ² represents an alkyl group and / or an alkenyl group, which is a residue obtained by removing a hydroxyl group from a primary and / or secondary alcohol having an average carbon number of 8 to 20, preferably 10 to 18. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. k is an average value and is a number from 5 to 15, and l is an average value and represents a number from 1 to 5. Note that EO and PO may be either random addition, block addition after adding EO, block addition such as PO, or vice versa. ]

  In (2), by using a nonionic surfactant represented by the following general formula (3), it is possible to obtain a high detergency against Eri / soaking and mouth dirt.

R ³ O (EO) _p (PO) _q (EO) _r H (3)
[Wherein R ³ represents an alkyl group and / or an alkenyl group, which is a residue having an average carbon number of 8 to 20, preferably 10 to 18, from which a hydroxyl group has been removed from a primary and / or secondary alcohol. EO and PO have the above meanings. 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 general formula (1), (2), (3), R < ¹ >, R < ² >, R < ³ > may be an alkyl group and / or alkenyl group derived from natural fats and oils.

  As the nonionic surfactant, an alkyl polysaccharide surfactant represented by the general formula (4) can also be used.

R ⁴ − (OR ⁵ ) _x G _y (4)
[Wherein, R ⁴ is a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkylphenyl group, R ⁵ is an alkylene group having 2 to 4 carbon atoms, and G is a carbon atom having 5 or 6 carbon atoms. Residues derived from reducing sugars, x is an average value and is a number from 0 to 6, and y is an average value and is a number from 1 to 10. ]

  An amine oxide represented by the general formula (5) can also be used.

[Wherein R ⁶ represents an alkyl group and / or alkenyl group, which is a residue obtained by removing a hydroxyl group from a primary and / or secondary alcohol having an average carbon number of 8 to 20, preferably 10 to 18, or A formula represented by R ⁹ C (═O) NH (CH ₂ ) _z — is shown. Here, R ⁹ represents an alkyl group and / or alkenyl group having an average carbon number of 8 to 20, preferably 12 to 18, and z represents an integer of 1 to 5. R ⁷ and R ⁸ are the same or different and represent CH ₃ , C ₂ H ₅ or C ₂ H ₄ OH. ]

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

  The liquid detergent composition of the present invention is selected from the group consisting of cationic surfactants and amphoteric surfactants in addition to the surfactants (a) and (g) as the component (h). You may contain 0-10 mass% of seeds or more, and also 1-10 mass%. Examples of amphoteric surfactants include alkylcarbobetaines, alkylsulfobetaines, alkylamidohydroxysulfobetaines, alkylamidoamine-type betaines, and alkylimidazoline-type betaines.

<Other ingredients>
The liquid detergent composition of the present invention comprises, as optional components, solubilizers such as p-toluenesulfonic acid and benzoate (also effective as a preservative); color transfer inhibitors such as polyvinylpyrrolidone; calcium chloride and sulfuric acid Enzyme stabilizers such as calcium, formic acid and boric acid (boron compounds); fluorescent dyes such as Tinopearl CBS-X (manufactured by Ciba Specialty Chemicals); silicone for imparting flexibility; silica as an antifoaming agent; Silicone; antioxidants such as butylhydroxytoluene and distyrenated cresol; other fluorescent dyes; bluing agents; fragrances; antibacterial preservatives; enzymes;

  A water-immiscible organic solvent may be used as long as the effect of the water-miscible organic solvent as the component (e) 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.

[I] Preparation of liquid detergent composition (I-1) Examples 1 to 14
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 Examples 1-2, 4-5
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. (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.

(I-3) Comparative Example 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. (10 mm, diameter 60 mm), stirring was carried out until it was uniformly transparent 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.

(I-4) Comparative Examples 6 and 7
In a 500 cc beaker (inner diameter 90 mm), the components excluding component (e) and citric acid were measured so that the total amount would be 300 g, and in a 20 ° C. water bath, stirring blades (SUS, 45 ° pitched paddle 4 blades, Stirring was performed with a blade having a width of 10 mm and a diameter of 60 mm until it became uniformly transparent. Next, citric acid was added at a rate of 3 g / min under the same stirring conditions to precipitate alkylbenzenesulfonic acid liquid crystal. Further, the component (e) was mixed and stirred for 30 minutes under the same stirring conditions to prepare a liquid detergent composition. These are systems in which the component (f) is dispersed in the LAS liquid crystal dispersion system.

[II] Evaluation The solubility of the liquid detergent composition prepared above and the cleaning ability of the collar stain were evaluated. 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, 2, 4, and 5 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, 2, 4, and 5 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) Collagen dirt cleaning power evaluation (Preparation of collar scarf cloth) A collar scarf cloth described in JIS K3362: 1998 is prepared.
(Cleaning conditions and evaluation method) The cleaning powers of the liquid detergent composition shown in Table 1 and the index detergent for determining cleaning power were compared in accordance with the cleaning power evaluation method for synthetic detergents for clothing described in JIS K 3362: 1998. The use concentration of the liquid detergent composition shown in Table 1 was 1.33 g / L.

  The determination of the cleaning power was “◎” when it was better than the index detergent, “◯” when it was equivalent to the index detergent, and “x” when it was inferior to the index detergent.

(II-4) Storage Stability Test The liquid detergent compositions of Examples 1 to 14 were stored at 50 ° C. for 1 month, but no transparent separation layer was observed in the upper layer portion. Further, the volume average particle diameter of the droplets after storage was in the range of 1 to 20 μm. In contrast, Comparative Examples 1, 2, 4, and 5 showed separation. This is probably because Comparative Examples 1 and 4 have a large droplet diameter, and the droplets are likely to coalesce with time. In Comparative Examples 2 and 5, since no stabilizing polymer is blended, it is considered that the coalescence of droplets over time cannot be suppressed.

(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)
・ Zeolite: Toyo Builder (Toyo Soda Co., Ltd.)
-POE monophenyl ether: polyoxyethylene monophenyl ether (EO average 3 mol addition)
Polymer (1): Polyethylene glycol monomethacrylate (EO average addition mole number 90) / methacrylic acid = 50/50 (mass ratio) copolymer (weight average molecular weight 50,000; measured by GPC, converted to polyethylene glycol)
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): 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 (5), 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 (6): 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 (6), 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).

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) 1-30% by mass of an anionic surfactant, (b) at least one water selected from alkali metal carbonates, alkali metal silicates, alkali metal sulfates, and alkali metal chlorides. Inorganic salt, (c) 15 to 80% by mass of water, (d) a segment (b) having affinity for the aqueous phase and a segment (b) having affinity for the droplet (b) / (b) = 0.1 to 10% by weight of a water-soluble stabilizing polymer having a weight average molecular weight of 3000 to 8 million having a mass ratio of 30/70 to 90/10, (e) a water-miscible organic solvent having a weight average molecular weight of less than 3000 Containing -20% by weight,
There are droplets containing a surfactant having a volume average particle size of 0.1 to 20 μm in the composition,
The surfactant equivalent described in JIS K 3362: 1998 is 10 to 60% by mass,
The amount of (b) is equal to or greater than the amount by which at least part of the surfactant is precipitated in the composition;
The mass ratio of (b) and (c) is (b) / (c) = 10 / 90-60 / 40,
The viscosity is 10 to 2000 mPa · s (B-type viscometer, 60 r / min, 60 seconds, 20 ° C.),
The segment (a) in (d) is a polymer chain having a carboxy group or a salt thereof in the structural unit,
The segment (b) in (d) is a nonionic polymer chain having an alkyleneoxy group selected from an ethyleneoxy group and a propyleneoxy group as a constituent unit, and the average degree of polymerization of the alkyleneoxy group is 40 to 200. A nonionic polymer chain that is
Liquid detergent composition. Furthermore (f) calcium trapping quantity 200~600CaCO ₃ mg / g and a calcium stability constant 2-10 is a molecular weight of 1,000 or less chelating agents liquid detergent composition according to claim 1, further comprising a. (G) according to claim 1 or 2 liquid detergent composition according the content of the nonionic surfactant is 1 to 40 mass%. The liquid detergent composition according to claim 3 , wherein the mass ratio of (a) to (g) is (a) / (g) = 1/50 to 10/1.

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