JP7138516B2 - Liquid detergent composition and method for producing liquid detergent composition - Google Patents

Description

Application of Patent Law Article 30, Paragraph 2 June 23-24, 2018 Samples were distributed at the Japan Textile Consumer Science Society held at Kinjo Gakuin University.

TECHNICAL FIELD The present invention relates to a liquid detergent composition and a method for producing a liquid detergent composition.

Liquid detergent compositions are widely used as household laundry detergents. In laundry detergents, structural viscosity can be imparted to the liquid detergent composition in order to suppress sedimentation or floating (improve dispersion stability) of functional-imparting particles such as perfume-containing capsule particles (capsule perfume). Are known.
For example, Patent Literature 1 proposes a liquid detergent composition containing a concentrated dispersion of function-imparting particles in a liquid phase. The invention of Patent Document 1 attempts to provide a thixotropic liquid detergent composition that does not separate even during long-term storage (excellent storage stability).

JP-A-1-268798

However, the liquid detergent composition of Patent Literature 1 tends to have a high viscosity and is difficult to discharge from the container or to refill, resulting in inferior usability.
In addition, the functionalization particles may settle or float.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent composition that improves the dispersion stability of function-imparting particles and is excellent in storage stability and usability.

As a result of intensive studies, the present inventors have found that the thixotropic index (TI value) and the specific gravity of the liquid detergent composition are set within specific ranges by blending specific amounts of surfactant and structural viscosity-imparting agent. We have found that the above problem can be solved.
That is, the present invention has the following aspects.

[1] Component (A): a surfactant and component (B): a structural viscosifying agent, and the content of component (A) is 15 to 60% by mass relative to the total mass. , a liquid detergent composition having a thixotropic index of 1.5 to 5 and a specific gravity of 1.0 to 1.5.
[2] The liquid detergent composition according to [1], which has a viscosity of 50 to 500 mPa·s at 25°C.
[3] The liquid detergent composition according to [1] or [2], which has a pH of 5-9.

[4] The liquid detergent composition according to any one of [1] to [3], which has a degassing step of subjecting the dispersion containing the (A) component and the (B) component to a degassing treatment. manufacturing method.

According to the liquid detergent composition of the present invention, the dispersion stability of the function-imparting particles is improved, and the storage stability and usability are excellent.

BRIEF DESCRIPTION OF THE DRAWINGS It is a front view which shows an example of the plastic bottles which accommodate the liquid detergent composition of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a front view which shows an example of the bag-like container for refilling which accommodates the liquid detergent composition of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a front view which shows an example of the bag-like container for refilling which accommodates the liquid detergent composition of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a front view which shows an example of the bag-like container for refilling which accommodates the liquid detergent composition of this invention. FIG. 5 is a perspective view showing an example of the bag-like container for refilling of FIG. 4;

[Liquid detergent composition]
The liquid detergent composition of the present invention is a composition containing component (A) and component (B).
As used herein, the thixotropy index (TI value) is given by the following formula.
TI value = (viscosity after 5 minutes at 6 rpm)/(viscosity after 1 minute at 60 rpm)
Viscosity was measured by adjusting the object to be measured to 25° C. and measuring rotor No. 1 with a Brookfield viscometer. 2 (mPa·s).
In this specification, the thixotropic property is synonymous with structural viscosity, and is a property exhibited by a substance intermediate between a plastic solid such as a gel and a non-Newtonian liquid such as a sol, and the viscosity changes with the passage of time. refers to nature. A thixotropic liquid detergent composition has a property that its viscosity increases when the shearing force is small, and the viscosity decreases when the shearing force is large. That is, the thixotropic liquid detergent composition has a high viscosity when left standing (storage) and exhibits excellent dispersion stability of the function-imparting particles. Excellent usability.

The TI value is an index representing thixotropy. For a Newtonian fluid (eg, water) that does not change viscosity with changes in shear rate, the TI value is one.
When the TI value is greater than 1, the liquid becomes more viscous and thixotropic at low shear than at high shear.
The TI value of the liquid detergent composition is 1.5 to 5, preferably 1.5 to 3, more preferably 1.8 to 2.5.
When the TI value of the liquid detergent composition is at least the above lower limit, excellent thixotropic properties are obtained, and the dispersion stability of the function-imparting particles is excellent. Usability is excellent in TI value of liquid cleaning composition being below the said upper limit. When the TI value is high, when air is mixed in the liquid detergent composition during manufacture of the liquid detergent composition, refilling from the refillable container to the main container, use, etc., air bubbles tend to be difficult to escape. When air bubbles are mixed in, not only does the specific gravity of the liquid detergent composition decrease, but foam adheres to the mouth of the container when filling the container during manufacturing or when refilling from a refillable container, which may impair manufacturing efficiency and usability. There is

The specific gravity of the liquid detergent composition is 1.0 to 1.5, preferably 1.0 to 1.4, more preferably 1.0 to 1.2.
When the specific gravity of the liquid detergent composition is at least the above lower limit, the time required for refilling work can be shortened, resulting in excellent usability. When the specific gravity of the liquid detergent composition is equal to or less than the above upper limit, the functionality-imparting particles are excellent in dispersion stability and storage stability.
Each component blended in the liquid detergent composition of the present invention will be described below.

<(A) Component>
(A) Component is a surfactant. The liquid detergent composition of the present invention increases detergency by containing the (A) component.
Component (A) includes nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like. Any one of these may be used alone, or two or more thereof may be used in combination.
As the component (A), it is preferable to use a combination of a nonionic surfactant and an anionic surfactant in terms of excellent detergency.

(Nonionic surfactant)
A nonionic surfactant is a surfactant mainly used to impart detergency to a liquid detergent composition.
Examples of nonionic surfactants include polyoxyalkylene type nonionic surfactants, alkylphenols, alkylene oxide adducts such as fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, and polyoxyethylene polyoxypropylene block copolymers. , fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or alkylene oxide adduct thereof, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, hydrogenated castor oil alkylene oxide adduct, sugar fatty acid ester, N- Alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like can be mentioned. Any one of these may be used alone, or two or more thereof may be used in combination.
Among the above nonionic surfactants, polyoxyalkylene-type nonionic surfactants are preferred from the viewpoint of maintaining the appropriate viscosity of the liquid detergent composition and having excellent storage stability.

Examples of polyoxyalkylene-type nonionic surfactants include compounds represented by the following general formula (a1) (hereinafter also referred to as "compound (a1)"), compounds represented by the following general formula (a2) ( hereinafter referred to as "compound (a2)") and the like. Any one of these may be used alone, or two or more thereof may be used in combination.

R ¹ —CO—(OR ² ) _m —OR ³ (a1)
R ⁴ —O—[(EO) _s /(PO) _t ]H (a2)

In general formula (a1), R ¹ is a hydrocarbon group having 9 to 13 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms. m is the average number of repetitions of OR ² and ranges from 5 to 25;
In general formula (a2), R ⁴ is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. s indicates the average number of repetitions of EO and is a number from 5 to 20, and t indicates the average number of repetitions of PO and is a number from 0 to 4.

- compound (a1)
The hydrocarbon group for R ¹ in compound (a1) may be linear or branched. The hydrocarbon group for R ¹ in compound (a1) may contain a cyclic structure.
R ¹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
The number of carbon atoms in the hydrocarbon group for R ¹ is 9-13, preferably 10-13, more preferably 11-13. When the number of carbon atoms in R ¹ is 9 or more, the detergency is enhanced. When the number of carbon atoms in R ¹ is 13 or less, storage stability is improved, and gelation is particularly easily suppressed.
Compound (a1) may be a mixture of single chain lengths or a mixture of multiple chain lengths. R ¹ is derived from the raw material fatty acid (R ¹ —COOH).

R ² in compound (a1) is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group.
The m OR ^2s may be the same or different from each other. That is, the number of alkylene groups in one molecule of compound (a1) may be one or a combination of two or more. Among them, it is preferable that m OR ² are all oxyethylene groups or groups in which oxyethylene groups and oxypropylene groups are mixed, because they foam well during washing and are inexpensive.

When two or more alkylene groups for R ² are combined, the addition method for OR ² is not particularly limited. For example, when an oxyethylene group and an oxypropylene group are mixed, the addition method may be random addition or block addition. Examples of block addition methods include a method of adding ethylene oxide and then propylene oxide, a method of adding propylene oxide and then adding ethylene oxide, and a method of adding ethylene oxide and then adding propylene oxide and then adding ethylene oxide. mentioned.

R ³ in compound (a1) is an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. When the number of carbon atoms in R ³ is 1 or more, the dispersion stability of the function-imparting particles during storage at low temperature (eg, 5° C.) is likely to be improved. When the number of carbon atoms in R ³ is 4 or less, the solubility in water of the liquid detergent composition under low temperature conditions is further increased.
The alkyl group for R ³ may be linear or branched. Examples of R ³ include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. Among them, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

m in compound (a1) is the average repeating number of OR ² and is a number from 5 to 25. When m is 5 or more, the detergency, especially the detergency against sebum stains, is improved. When m is 25 or less, the water solubility of the liquid detergent composition is improved.
When m OR ² are all oxyethylene groups, m is preferably 5-20, more preferably 12-18.
When oxyethylene groups and oxypropylene groups are mixed in m OR ² , m is preferably 12-21. In this case, the average number of repeating oxypropylene groups is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. When the average repeating number of oxypropylene groups is 5 or less, detergency and storage stability of the liquid detergent composition are less likely to deteriorate.

In the compound (a1), the narrow ratio represented by the following formula (S) is preferably 20% by mass or more. The narrow ratio of compound (a1) indicates the ratio of the distribution of compounds ⁽ alkylene oxide adducts) having different numbers of repeating OR2. The higher the narrow rate, the easier it is to obtain good detergency. The upper limit of the narrow rate is substantially 80% by mass.

ナロー率は、２０～５０質量％がより好ましく、保存安定性と水に対する溶解性がより向上することから、３０～４５質量％がさらに好ましい。ナロー率が２０質量％以上、特に３０質量％以上であると、化合物（ａ１）由来の原料臭気の少ない液体洗浄剤組成物が得られやすくなる。これは、化合物（ａ１）の製造後に化合物（ａ１）と共存する、化合物（ａ１）の原料である脂肪酸エステルと、前記一般式（ａ１）中のｍが１又は２のアルキレンオキサイド付加体の量が少なくなるためである。

The narrow rate is more preferably 20 to 50% by mass, and further preferably 30 to 45% by mass because storage stability and solubility in water are further improved. When the narrow ratio is 20% by mass or more, particularly 30% by mass or more, it becomes easy to obtain a liquid detergent composition with little raw material odor derived from the compound (a1). This is the amount of the fatty acid ester, which is the raw material of the compound (a1), and the alkylene oxide adduct in which m is 1 or 2 in the general formula (a1), which coexist with the compound (a1) after the production of the compound (a1). This is because the

Among the compounds contained as impurities in the compound (a1), the ratio of the total of the fatty acid ester as the raw material of the compound (a1) and the alkylene oxide adduct in which m is 1 or 2 in the formula (a1) is It is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, relative to the total mass of compound (a1). When this ratio is 0.5% by mass or less, it becomes easier to obtain a liquid detergent composition with less raw material odor of the surfactant.

In the above formula (S), m _max represents the repeating number (addition mole number) of OR ² of the alkylene oxide adduct present most abundantly in the entire compound (a1). i indicates the repetition ^number of OR2. Yi represents the ratio (% by mass) of the alkylene oxide adduct having i added moles of alkylene oxide present in the entire compound (a1).

The narrow ratio can be controlled, for example, by the method for producing compound (a1).
The method for producing the compound (a1) is not particularly limited, and for example, a method of addition-polymerizing an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (see JP-A-2000-144179). ) can be easily manufactured.

Preferred examples of such surface-modified composite metal oxide catalysts include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ²⁺ etc.) is added to the composite metal oxide catalyst whose surface is modified with a metal hydroxide or the like, or a hydro whose surface is modified with one or more selected from metal hydroxides and metal alkoxides. A calcined catalyst of talcite and the like can be mentioned.
In the surface modification of the composite metal oxide catalyst, the mixing ratio of one or more selected from metal hydroxides and metal alkoxides with respect to 100 parts by weight of the composite metal oxide is preferably 0.5 to 10 parts by weight. , more preferably 1 to 5 parts by mass.

As a method for producing the compound (a1), there is also a method of adding an alkylene oxide to a fatty acid alkyl ester using an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxyacid. The above alkoxylation catalysts are disclosed in Japanese Patent No. 4977609, International Publication No. 1993/004030, International Publication No. 2002/038269, International Publication No. 2012/028435, and the like. Examples of the alkoxylation catalyst include alkoxylation catalysts prepared from a mixture of one or more selected from alkaline earth metal salts of carboxylic acids and alkaline earth metal salts of hydroxycarboxylic acids and sulfuric acid. .

- compound (a2)
The hydrocarbon group for R ⁴ in compound (a2) may be linear or branched. The hydrocarbon group for R ⁴ in compound (a2) may contain a cyclic structure.
R ⁴ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
R ⁴ has 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, more preferably 12 to 14 carbon atoms. If the number of carbon atoms in R ⁴ is 10 or more, detergency will be further enhanced. When the number of carbon atoms in R ⁴ is 20 or less, storage stability is improved, and gelation is particularly easily suppressed.
Compound (a2) may be a mixture of single chain lengths or a mixture of multiple chain lengths.
R ⁴ is derived from the raw material alcohol (R ⁴ —OH). Raw material alcohols include alcohols derived from natural fats and oils such as coconut oil, palm oil, or beef tallow, or synthetic alcohols derived from petroleum.

In general formula (a2), s represents the average repeating number of EO and is a number of 5 to 20, preferably 12 to 18, more preferably 12 to 16. When s is within the above range, the detergency of the liquid detergent composition, particularly the detergency against sebum stains, is further improved.
t represents the average repetition number of PO and is a number from 0 to 4, preferably from 0 to 3, particularly preferably 0. When t is within the above range, gelation of the liquid detergent composition is likely to be suppressed, and good foam removal properties are likely to be obtained during rinsing.

In the compound (a2), [(EO) _s /(PO) _t ] indicates that EO and PO may be added blockwise or randomly. Examples of addition methods when EO and PO are added in blocks include a method of adding ethylene oxide and then propylene oxide, a method of adding propylene oxide and then adding ethylene oxide, and a method of adding ethylene oxide and then propylene oxide. and then adding ethylene oxide. In particular, since the rinsability in washing with a fully automatic washing machine is better, a method of adding ethylene oxide after adding ethylene oxide and then adding propylene oxide (terminals are -O-CH ₂ CH ₂ O-H and to be) is preferred.

In the compound (a2), the addition mole number distribution of the alkylene oxide (ethylene oxide, propylene oxide) is not particularly limited, and can be controlled by the production method of the compound (a2) or the like. For example, when an alkylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the added mole number tends to be relatively wide. In addition, specific alkoxyl compounds such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ and Mn ²⁺ described in JP-B-6-15038 are added When an alkylene oxide is added to a hydrophobic raw material using a polymerization catalyst, it tends to result in a relatively narrow addition mole number distribution.

Commercially available products of compound (a2) include, for example, the following compounds.
・Lion Co., Ltd. brand name Rheox CL-70 (a mixture of a carbon number alcohol and a carbon number 14 alcohol) or Sasol Corporation brand name Safol 23 (a mixture of a carbon number 12 alcohol and a carbon number 13 alcohol) compound obtained by adding EO equivalent to 12 mol or 15 mol to an alcohol such as a mixture).
- A compound obtained by adding 9 mol, 12 mol or 15 mol equivalent of EO to a natural alcohol such as "CO-1214" or "CO-1270" manufactured by P&G.
・ Compounds obtained by adding 9 mol, 12 mol or 15 mol equivalent of EO to a secondary alcohol having 12 to 14 carbon atoms (trade names “SOFTANOL 90”, “SOFTANOL 120”, “SOFTANOL 150” manufactured by Nippon Shokubai Co., Ltd. ”).

As the nonionic surfactant, one or more selected from the compound (a1) and the compound (a2) is preferable in terms of detergency against sebum stains and resistance to gelation in a high concentration range. Among these, it is more preferable to use compound (a1) or a combination of compound (a1) and compound (a2).
Among those mentioned above, the compound (a1) is preferably a polyoxyethylene fatty acid alkyl ester in which R ² is an ethylene group, and among these, a polyoxyethylene fatty acid methyl ester in which R ³ is a methyl group (hereinafter also referred to as "MEE") ) is particularly preferred.
As the compound (a2), among those mentioned above, a secondary alcohol ethoxylate obtained by adding EO to a secondary alcohol (for example, Softanol series manufactured by Nippon Shokubai Co., Ltd.) is particularly preferable.
Since these have a small gelation region even at high concentrations, gelation is less likely to occur when blended at high concentrations.
Further, these may be used in combination with a primary alcohol ethoxylate obtained by adding ethylene oxide to a primary alcohol.

The nonionic surfactant content is preferably 10 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 30% by mass, relative to the total mass of the liquid detergent composition. Sufficient detergency is obtained as content of a nonionic surfactant is more than the said lower limit. When the content of the nonionic surfactant is equal to or less than the above upper limit, thickening is suppressed, and the storage stability of the liquid cleaning composition can be maintained more satisfactorily.

The content of the nonionic surfactant is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 80% by mass, based on the total mass of component (A). In particular, when the content of the nonionic surfactant is 80% by mass or less with respect to the total mass of the component (A), the storage stability becomes better.

(Anionic surfactant)
Anionic surfactants include anionic surfactants with _SO3 or _SO4 groups. Examples of anionic surfactants having SO ₃ or SO ₄ groups include straight-chain alkylbenzenesulfonic acids or salts thereof; α-olefinsulfonates; straight-chain or branched-chain alkyl sulfates; alkenyl ether sulfate; alkanesulfonate having an alkyl group; α-sulfofatty acid ester, and the like.
Salts of these anionic surfactants include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanolamine and diethanolamine.

As the straight-chain alkylbenzenesulfonic acid or salt thereof, those having a straight-chain alkyl group with 8 to 16 carbon atoms are preferable, and those with 10 to 14 carbon atoms are more preferable.
As the α-olefin sulfonate, those having 10 to 20 carbon atoms are preferred.
As the alkyl sulfate, those having 10 to 20 carbon atoms are preferred.
The alkyl ether sulfate or alkenyl ether sulfate has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and is added with an average of 1 to 10 mol of ethylene oxide (i.e., polyoxyethylene alkyl ether sulfate or polyoxyethylene alkenyl ether sulfate) is preferred.
The number of carbon atoms in the alkanesulfonate is preferably 10-20, more preferably 14-17. Among them, those in which the alkyl group is a secondary alkyl group (secondary alkanesulfonate) are particularly preferred.
The α-sulfo fatty acid ester salt preferably has 10 to 20 carbon atoms.
Among these anionic surfactants, linear alkylbenzene sulfonic acid or its salt, alkanesulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate are preferred in terms of excellent detergency and storage stability. Linear alkylbenzenesulfonic acids or salts thereof, and polyoxyethylene alkyl ether sulfates are more preferable.
Among these, straight-chain sodium alkylbenzenesulfonate (LAS) is particularly preferred in terms of high handleability and excellent anti-soil redeposition performance.

Other anionic surfactants include, for example, higher fatty acid salts (salts of fatty acids having 8 to 22 carbon atoms), alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates. , Carboxylic acid type anionic surfactants such as acylaminocarboxylates; Phosphate ester type anionic surfactants and the like are included.

Examples of higher fatty acids include single fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, and behenic acid, coconut oil fatty acid, beef tallow fatty acid, and the like. and mixed fatty acids.
Salts of these higher fatty acids include alkali metal salts such as sodium salts and potassium salts; ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, 2-amino-2-methylpropanol salts, 2-amino- Examples include alkanolamine salts such as 2-methylpropanediol, basic amino acid salts such as lysine and arginine, and the like.
These anionic surfactants may be used alone or in combination of two or more.

The content of the anionic surfactant is preferably 2 to 20% by mass, more preferably 5 to 20% by mass, even more preferably 8 to 15% by mass, relative to the total mass of the liquid detergent composition. When the content of the anionic surfactant is at least the above lower limit, the anti-soil redeposition effect and the dispersion stability of the component (A) are sufficiently exhibited. When the content of the anionic surfactant is equal to or less than the above upper limit, it is easy to prevent the container containing the liquid cleaning composition from being dented.

The content of the anionic surfactant is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 20 to 80% by mass, based on the total mass of component (A). If the content of the anionic surfactant is at least the above lower limit, the detergency will be better. When the content of the anionic surfactant is equal to or less than the above upper limit, the storage stability becomes better.

The content ratio of the anionic surfactant and the nonionic surfactant (hereinafter also referred to as "anion/nonionic ratio") is preferably 0.04 to 2.0, more preferably 0.13 to 2.0. Preferably, 0.27 to 1.0 is more preferable. When the anion/nonion ratio is at least the above lower limit, the detergency is likely to be improved. When the anion/nonion ratio is equal to or less than the above upper limit, storage stability is likely to be improved.

(cationic surfactant)
Examples of cationic surfactants include cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts.
In addition, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristate dimethylaminopropylamide, palmitate dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide , long-chain aliphatic amidoalkyl tertiary amines such as dimethylaminopropylamide oleate, or salts thereof; diethanolaminopropylamide palmitate, diethanolaminopropylamide stearate, and the like.
These cationic surfactants may be used alone or in combination of two or more.

(Amphoteric surfactant)
Examples of amphoteric surfactants include alkylbetaine type, alkylamidobetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidocarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactants. is mentioned.
These amphoteric surfactants may be used alone or in combination of two or more.

The content of component (A) is 15 to 60% by mass, preferably 20 to 50% by mass, more preferably 30 to 40% by mass, relative to the total mass of the liquid detergent composition. (A) Liquid cleaning composition tends to have structural viscosity as content of a component is more than the said lower limit. (A) Storage stability of a liquid cleaning composition increases more as content of a component is below the said upper limit.

<(B) Component>
Component (B) is a structural thickening agent. In this specification, the structural viscosity-imparting agent imparts structural viscosity to the liquid detergent composition. By containing the component (B), the liquid detergent composition according to the present invention can improve the dispersibility of the function-imparting particles and easily improve the storage stability.
Component (B) includes component (B-1), component (B-2), and component (B-3), which will be described later.

((B-1) component)
The component (B-1) is an acrylic acid-based having a repeating unit derived from a monomer represented by the following general formula (b1) and a repeating unit derived from a monomer represented by the following general formula (b2) It is a polymer.
The (B-1) component plays the role of a structural thickening agent. The liquid detergent composition is structured by containing the component (B-1). Therefore, for example, when the liquid detergent composition contains insoluble particles (functionality-imparting particles) described later, the insoluble particles can be uniformly dispersed in the liquid detergent composition, and the state can be maintained. In addition, the storage stability and redeposition prevention property of the liquid detergent composition are also enhanced.

^In general ^formula (b1), R5 is a hydrogen atom or a methyl group, and R6 is a hydrogen atom.
In general formula (b2), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 40 carbon atoms.

Examples of monomers represented by general formula (b1) include acrylic acid and methacrylic acid.
These monomers represented by formula (b1) may be used singly or in combination of two or more.

In general formula (b2), ^R7 is a hydrogen atom or a methyl group, preferably a hydrogen atom.
In general formula (b2), the alkyl group for R ⁸ may be linear or branched. The alkyl group for R ⁸ may contain a cyclic structure.
The number of carbon atoms in the alkyl group for R ⁸ is 1-40, preferably 1-20, more preferably 1-10.

Examples of monomers represented by formula (b2) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, and icosyl acrylate. and methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, decyl methacrylate, dodecyl methacrylate, and icosyl methacrylate.
These monomers represented by formula (b2) may be used singly or in combination of two or more.

Component (B-1) is preferably crosslinked. Note that the component (B-1) may be non-crosslinked.
Examples of the crosslinked component (B-1) include those crosslinked by a crosslinking agent (crosslinked polymer).

Examples of the cross-linking agent include allyl ether compounds.
Examples of allyl ether compounds include allyl ethers, sugar allyl ethers, sugar alcohol allyl ethers, and the like.
Examples of sugars in sugar allyl ethers include sucrose and the like.
Examples of sugar alcohols in allyl ethers of sugar alcohols include pentaerythritol.

(B-1) component is a repeating unit other than repeating units derived from the monomer represented by the general formula (b1) and the repeating unit derived from the monomer represented by the general formula (b2) (other repeating units ).
Other repeat units include repeat units derived from other monomers.
Other monomers are not particularly limited as long as they are copolymerizable with the monomer represented by general formula (b1) and the monomer represented by general formula (b2), and one or more of them can be used.
Component (B-1) may be used alone or in combination of two or more.

(B-1) Commercially available products of the component include, for example, the following.
Commercial products of the cross-linking type (B-1) include, for example, Lubrizol's cross-linking copolymer composed of two or more monomers selected from alkyl acrylate, alkyl methacrylate, acrylic acid and methacrylic acid. trade name "Carbopol Aqua 30"; Lubrizol from two or more monomers selected from alkyl acrylates (C1 to C4 and C8), alkyl methacrylates (C1 to C4 and C8), acrylic acid and methacrylic acid "Carbopol Aqua SF-1" which is a crosslinked copolymer; from two or more monomers selected from alkyl acrylate (C10 to C30), alkyl methacrylate (C10 to C30) and acrylic acid manufactured by Lubrizol trade name "Carbopol EZ-4" which is a cross-linked copolymer; trade name "ACUSOL 830" which is a cross-linked copolymer composed of alkyl acrylate and acrylic acid or methacrylic acid manufactured by DOW; be done.
Here, C1, C8, C30, etc. represent the number of carbon atoms of the alkyl group in the alkyl acrylate.
Examples of commercial products of the non-crosslinked type component (B-1) include copolymers made of two or more monomers selected from alkyl acrylate, alkyl methacrylate, acrylic acid and methacrylic acid manufactured by Lubrizol. Trade name "Novethix HC200" etc. are mentioned.

((B-2) component)
Component (B-2) is a structural viscous agent for polyurea-based resins. A polyurea-based resin is a polymer mainly composed of urea bonds formed by a chemical reaction between isocyanate and amino groups.
Component (B-2) is obtained by chemically reacting polyisocyanate and polyamine.
As the component (B-2), a synthesized product or a commercially available product may be used.

(B-2) Examples of commercial products of the component include BYK-410, BYK-411, BYK-420, BYK-425, BYK-428, BYK-7411ES, BYK-7420ET and BYK-D410 manufactured by Big Chemie. mentioned.
Component (B-2) may be used alone or in combination of two or more.

((B-3) component)
Component (B-3) is a triglyceride represented by the following general formula (b3). Component (B-3) can also impart structural viscosity to the liquid detergent composition. In addition, since the liquid cleaning composition contains the component (B-3), the rinsability can be improved and the flexibility of the object to be cleaned can be easily maintained.

In general formula (b3), Z ¹ to Z ³ are each independently a hydrogen atom, hydroxyl group or carboxy group. In general formula (b3), a to f are numbers representing repeating methylene groups, and a+b=7 to 19, c+d=7 to 19, and e+f=7 to 19.

In general formula (b3), a+b is 7 to 19, preferably 11 to 15, more preferably 13 to 15. When a+b is at least the above lower limit, the volume of the hydrophobic group portion becomes sufficiently bulky, giving the object to be washed a dry feel and good rinsability. When a+b is equal to or less than the above upper limit, it is possible to prevent a decrease in the effect of imparting a dry feel and rinsability due to excessive bulkiness of the hydrophobic group portion.
In general formula (b3), c+d is 7 to 19, preferably 11 to 15, more preferably 13 to 15. When c+d is at least the above lower limit, the volume of the hydrophobic group portion becomes sufficiently bulky, giving the object to be washed a dry feel and good rinsability. When c+d is equal to or less than the above upper limit, it is possible to prevent the effect of imparting a dry feel and the rinsability from being lowered due to the volume of the hydrophobic group portion becoming too bulky.
In general formula (b3), e+f is 7 to 19, preferably 11 to 15, more preferably 13 to 15. When e+f is at least the above lower limit, the volume of the hydrophobic group portion becomes sufficiently bulky, giving the object to be washed a dry feel and good rinsability. When e+f is equal to or less than the above upper limit, it is possible to prevent a decrease in the effect of imparting a dry feel and rinsability due to excessive bulkiness of the hydrophobic group portion.

As the component (B-3), compounds in which at least one of Z ¹ to Z ³ in the general formula (b3) is a hydroxyl group are preferred. Compounds in which at least one of Z ¹ to Z ³ is a hydroxyl group include, for example, hydrogenated castor oil.
Commercial products of hydrogenated castor oil include "Caster Wax A Flakes" (trade name) manufactured by NOF Corporation.
Component (B-3) may be used alone or in combination of two or more.

Component (B) is preferably component (B-1) or component (B-3), more preferably component (B-1).
When component (B-1) is contained, it is preferable to use it together with component (C), which will be described later.

The content of component (B) is preferably 0.1 to 5% by mass, more preferably 0.5 to 2.5% by mass, relative to the total mass of the liquid detergent composition. (B) It is easy to improve the liquid stability (a liquid cleaning composition does not isolate|separate or becomes cloudy) of a liquid cleaning composition as content of a component is more than the said lower limit. (B) Thickening is suppressed as content of a component is below the said upper limit, and the storage stability of a liquid cleaning composition can be maintained more favorably.

<Optional component>
The liquid detergent composition according to the present invention may contain optional components as long as the storage stability and usability of the liquid detergent composition are not impaired. As optional components, optional components that are commonly used in liquid detergent compositions for clothes and the like can be used.
Optional components include, for example, cationic polymer (component (C)), solvent, organic solvent, viscosity reducer (solubilizer), chelating agent (metal ion scavenger), antioxidant, preservative, and cleaning performance improvement. agents/stability improvers, colorants, fragrances, insoluble particles (functionality-imparting particles), extracts of natural products, antifoaming agents, pH adjusters, and the like.

((C) component)
Component (C) comprises one or more repeating units selected from repeating units represented by the following general formula (c1) and repeating units represented by the following general formula (c2), and the following general formula (c3): It is a polymer (cationic polymer) having a repeating unit represented by

In general formula (c1), R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X 1 ^- is a counterion.
In general formula (c2), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X 1 ^- is a counterion.

In general formula (c3), R ¹³ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or 1 -3 hydroxyalkyl groups.

At least one type of repeating unit selected from the repeating unit represented by the general formula (c1) and the repeating unit represented by the general formula (c2) is a dialkyl represented by the following general formula (c4). It is a repeating unit derived from a diallylammonium salt monomer.

In general formula (c4), R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ^- is a counter ion.

In general formulas (c1), (c2) and (c4) above, X 1 ⁻ is a counter ion. Examples of counter ions include halide ions such as chloride ion and bromide ion; inorganic acid ions such as sulfate ion, nitrate ion and sulfite ion; organic acid ions such as methyl sulfate ion, acetate ion and lactate ion; be done.

The weight average molecular weight of component (C) is generally 1,000 to 5,000,000, preferably 3,000 to 2,000,000, more preferably 10,000 to 2,000,000. In addition, the mass average molecular weight in this specification means the value obtained by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.

The form of polymerization of component (C) is not particularly limited, and may be block polymerization, random polymerization or graft polymerization.
(C) One or more selected from repeating units (c1) and (c2) in component (hereinafter also referred to as “repeating unit ((c1) + (c2))”) and repeating unit (c3) The content ratio is not particularly limited, but the molar ratio of the repeating unit ((c1) + (c2)) to the repeating unit (c3) (repeating unit ((c1) + (c2)): , a ratio of 1:9 to 7:3 is preferred, and a ratio of 2:8 to 6:4 is more preferred.

Component (C) is preferably a polymer having a repeating unit derived from a diallyldialkylammonium salt and a repeating unit derived from acrylamide, and more preferably a diallyldimethylammonium chloride/acrylamide copolymer.
As these polymers, synthetic products or commercial products may be used.

Component (C) can be produced by conventional radical polymerization. For example, it can be produced by polymerizing a monomer constituting component (C), such as diallyldimethylammonium chloride or acrylamide, by a polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization. Moreover, in the polymerization, it is preferable to use a polymerization initiator that is used for normal radical polymerization. Examples of polymerization initiators that can be used include peroxides such as benzoyl peroxide and potassium persulfate; and azo compounds such as azobisisobutyronitrile and azobiscyanovaleric acid.

Commercially available products of the above polymers include, for example, Lubrizol trade names "Marquat 550", "Marquat 740", "Marquat 2200", "Noverite 300" and "Noverite 302".

These (C) components may be used individually by 1 type, and may use 2 or more types together.
The content of component (C) is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 3.0% by mass, more preferably 0.2 to 5.0% by mass, relative to the total mass of the liquid detergent composition. 2.0% by mass is more preferable. (C) It is easy to structure a liquid detergent composition as content of a component is in the said numerical range. It is particularly preferable to use the acrylic acid-based polymer whose component (B) is the component (B-1) together with the component (C), because the liquid detergent composition can be more easily structured.

(solvent)
The liquid detergent composition of the present invention preferably contains water as a solvent from the viewpoints of ease of handling during production, solubility in water during use, and the like.
The content of the solvent is preferably 10-80% by mass with respect to the total mass of the liquid detergent composition.

(Organic solvent)
Examples of organic solvents include monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and R ¹⁸ —(OR ¹⁹ ) _u OH [wherein R ¹⁸ is alkyl having 1 to 6 carbon atoms, or a phenyl group, R ¹⁹ is an alkylene group having 2 to 4 carbon atoms, and u is 1 to 5 representing the average number of added moles. CH ₃ OCR ²⁰ (CH ₃ )CHR ²¹ CHR ²² OR ²³ [wherein R ²⁰ to R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ²³ is a hydrogen atom or an acetyl group].

Examples of monohydric alcohols having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol and 1-butanol.
Examples of polyhydric alcohols having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol and glycerin.
Glycol ether solvents represented by the formula R ¹⁸ -(OR ¹⁹ ) _u OH include, for example, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, and diethylene glycol monomethyl ether. , diethylene glycol monobutyl ether and the like.
Examples of the solvent represented by the formula CH ₃ OCR ²⁰ (CH ₃ )CHR ²¹ CHR ²² OR ²³ include 3-methoxymethanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-ethyl butanol, 3-methoxy-3-propylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy -1-ethylbutanol, 3-methoxy-1-propylbutanol, 3-methoxybutylacetate, 3-methoxy-3-methylbutylacetate, 3-methoxy-3-ethylbutylacetate, 3-methoxy-3-propylbutylacetate , 3-methoxy-2-methylbutyl acetate, 3-methoxy-2-ethylbutyl acetate, 3-methoxy-2-propylbutyl acetate, 3-methoxy-1-methylbutyl acetate, 3-methoxy-1-ethylbutyl acetate , 3-methoxy-1-propylbutyl acetate and the like.

As the organic solvent, ethanol, propylene glycol, glycerin, diethylene glycol monobutyl ether, 3-methoxy-3-methyl-1 can be used in view of fluidity as a liquid detergent composition, mild odor, and availability of raw materials. -butanol is preferred.
The content of the organic solvent is preferably 3 to 25% by mass with respect to the total mass of the liquid detergent composition.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.

(Viscosity reducer (solubilizer))
Viscosity reducing agents include glycols 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, polyethylene glycol having an average molecular weight of about 1000, dipropylene glycol, and paratoluenesulfonic acid. , cumenesulfonate, benzoate, and urea.
When the liquid detergent composition contains a viscosity reducer, the content of the viscosity reducer is preferably 0.01 to 15% by mass relative to the total weight of the liquid detergent composition.

(Chelating agent (metal ion scavenger))
Chelating agents include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like.
When the liquid detergent composition contains a chelating agent, the content of the chelating agent is preferably 0.1 to 20 mass % with respect to the total mass of the liquid detergent composition.

(Antioxidant)
Antioxidants include butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogensulfite and the like.
When the liquid detergent composition contains an antioxidant, the content of the antioxidant is preferably 0.01 to 2% by mass relative to the total weight of the liquid detergent composition.

(Preservative)
Examples of antiseptics include "Cason CG" (trade name) manufactured by Dow Chemical Co., Ltd., "Acticide MBS" (trade name) manufactured by Thor Japan, and "NIPACIDE BIT 20" (trade name) manufactured by Clariant. .
When the liquid detergent composition contains an antiseptic, the content of the antiseptic is preferably more than 0 and 1% by mass or less relative to the total mass of the liquid detergent composition.

(detergency improver/stability improver)
Detergency improvers/stability improvers include, for example, enzymes (protease, lipase, cellulase, etc.), texture improvers, alkali builders such as alkanolamine, hydrotropic agents, fluorescent agents, dye transfer inhibitors, and anti-staining agents. agents, pearl agents, soil release agents, and the like. These cleaning performance improvers and stability improvers may be used singly or in combination of two or more.

(coloring agent)
Colorants include, for example, Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Red No. 106, Yellow No. 203, Turquoise P-GR (all trade name) and general-purpose dyes and pigments.
When the liquid detergent composition contains a coloring agent, the content of the coloring agent is preferably 0.00005 to 0.005% by mass relative to the total weight of the liquid detergent composition.

(perfume)
Perfumes include, for example, perfume ingredients described in JP-A-2002-146399. These fragrances may be used alone or in combination of two or more.
When the liquid detergent composition contains a perfume, the content of the perfume is preferably 0.01 to 2% by mass with respect to the total mass of the liquid detergent composition.

(Insoluble particles (functionality-imparting particles))
The liquid detergent composition of the present invention may contain insoluble particles. The insoluble particles are particles that are difficult to dissolve in the components that constitute the liquid detergent composition.
Examples of insoluble particles include capsule particles, beads and pearlescent agents for imparting unique product aesthetics, bentonite, carboxymethylcellulose (CMC), and the like.
These insoluble particles may be used singly or in combination of two or more.

Capsule particles enclose an active ingredient in a capsule wall made of a polymer compound.
Capsule particles can be produced by known methods such as interfacial polymerization and in-situ polymerization.
Examples of the polymer compound forming the capsule wall include synthetic polymers such as polyacrylic acid-based, polyvinyl-based, polymethacrylic acid-based, melamine-based, and urethane-based polymers. These may be used individually by 1 type, and may use 2 or more types together.
Examples of active ingredients include perfume ingredients and sunscreen ingredients (ultraviolet absorbers, ultraviolet scattering agents, etc.).
Hereinafter, capsule particles in which a perfume component is encapsulated by a capsule wall made of a polymer compound are also referred to as "capsule perfume".
Specific examples of the capsule flavor include capsule flavor A, capsule flavor B, and capsule flavor C shown below.

・ Capsule fragrance A
Capsule perfume A contains the following perfume ingredients.
Limonene (0.10% by mass), ethyl 2-methylbutyrate (3.50% by mass), tripral (5.00% by mass), galvascon (0.20% by mass), spirogalvanone (0.60% by mass) ), cyclaset (9.00% by mass), cyclabate (0.10% by mass), tricyclodecenyl acetate (19.00% by mass), verdox (18.00% by mass), nectaryl (15.00% by mass) %), tetrahydrolinalool (14.00% by mass), α-ionone (0.50% by mass), β-ionone (14.00% by mass), dipropylene glycol (1.00% by mass).

・ Capsule fragrance B
Capsule perfume B contains the following perfume ingredients.
Tripral (2.40% by mass), cyclacet (10.00% by mass), tricyclodecenyl propionate (10.00% by mass), isopropylmethyl-2-butyrate (1.70% by mass), manzanate (2.00% by mass), Verdox (14.00% by mass), allyl amyl glycolate (2.00% by mass), allylcyclohexylpropionate (5.00% by mass), γ-decalactone (0.50% by mass) % by mass), γ-undecalactone (7.50% by mass), α-damascone (0.25% by mass), nerol (0.20% by mass), hedione (5.00% by mass), lyrial (12.0% by mass). 00% by mass), linalool (23.00% by mass), pt-butylcyclohexyl acetate (0.20% by mass), vanillin (0.10% by mass), lime oxide (2.40% by mass), dipropylene Glycol (1.75% by weight).

・ Capsule fragrance C
Capsule perfume C contains the following perfume ingredients.
Hexyl salicylate (3.71% by mass), ethyl 2-methylbutyrate (3.30% by mass), dihydroeugenol (8.49% by mass), camphor (1.46% by mass), 1,4-cineole (1.28% by mass), Verdox (9.04% by mass), γ-nonalactone (0.84% by mass), γ-decalactone (2.58% by mass), γ-undecalactone (3.70% by mass) %), allyl caproate (7.47% by mass), hexyl acetate (1.27% by mass), geranyl propionate (6.38% by mass), prenyl acetate (1.52% by mass), allylphenoxy acetate (0.60% by mass), dimethylbenzylcarbyl butyrate (0.95% by mass), nectaryl (8.54% by mass), geranyl acetate (11.13% by mass), lyrial (11.51% by mass), cyclamen Aldehyde (3.05% by mass), amyl salicylate (1.39% by mass), isoEsuper (1.08% by mass), γ-methylionone (1.34% by mass), ambroxane (0.13% by mass) %), habanolide (0.37% by weight), anisaldehyde (8.46% by weight), lime oxide (0.41% by weight).

When the liquid detergent composition contains insoluble particles, the content of the insoluble particles is preferably 0.01 to 20% by mass with respect to the total mass of the liquid detergent composition.

(Extracts of natural products, etc.)
Extracts of natural products such as dog pagoda, Arctic urchin, Echinacea, Scutellaria baicalensis, yellowfin, Japanese coptis, allspice, oregano, pagoda, chamomile, honeysuckle, clara, key mussel, kay, bay bay, magnolia, burdock, comfrey, jassho, burnet, Peony, ginger, goldenrod, sambucus nigra, sage, mistletoe, hosoba okera, thyme, hollyhock, clove, unshu mandarin, tea tree, barberry, houttuynia cordata, nanten, nymph, yellow rush, shirogaya, boletus, hollanda gourd, hops, honshitan, mountain grape , Murasaki sanguinea, Phyllanthus japonicum, Lily leopard, Mountain perilla, Eucalyptus, Lavender, Rose, Rosemary, Balan, Japanese cedar, Gilead balsam, Hakusen, Broom, Michiyanagi, Jingyo lily, Liquid lily, Vortex ginseng, Yamabishi, Yabugarashi, Glycyrrhiza, St. John's wort, etc. plants.
When the liquid detergent composition contains an extract such as a natural product, the content of the extract such as a natural product is preferably more than 0 and 0.5% by mass or less relative to the total mass of the liquid detergent composition.

(Antifoaming agent)
Antifoaming agents include, for example, 2-ethylhexyl 2-ethylhexanoate (2-ethylhexyl isooctate), 2-ethylbutyl 2-ethylhexanoate, and 2-ethyloctyl 2-ethylhexanoate described in JP-A-2017-8139. etc.
As for content of an antifoaming agent, when liquid cleaning composition contains an antifoaming agent, 0 more than 2.0 mass % or less is preferable with respect to the gross mass of a liquid cleaning composition.

(pH adjuster)
Examples of pH adjusters include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polycarboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide, alkanolamine, ammonia and the like. Among these, sulfuric acid, sodium hydroxide, potassium hydroxide and alkanolamine are preferred, and sulfuric acid and sodium hydroxide are preferred from the viewpoint of the stability of the liquid detergent composition over time.
One of the pH adjusters may be used alone, or two or more of them may be used in combination. For example, when the pH is controlled by adding a certain amount of sulfuric acid, sodium hydroxide, etc., an inorganic acid (preferably hydrochloric acid, sulfuric acid) or potassium hydroxide can be added for fine adjustment of the pH.

Each component mentioned above may be used individually by 1 type, and may use 2 or more types together.
The total amount of components that make up the liquid detergent composition does not exceed 100% by mass.

<Physical properties>
(pH)
The liquid detergent composition of the present invention preferably has a pH of 5-9, more preferably 5-8 at 25°C. When the pH at 25° C. is 5 to 9, good stability over time (storage stability) can be maintained even when the liquid detergent composition is stored for a long period of time.
The pH of the liquid detergent composition can be adjusted by adding a pH adjuster, if necessary.
In the present specification, pH means a value measured with a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) at 25°C.

(viscosity)
The viscosity of the liquid detergent composition is preferably 100 to 500 mPa·s, more preferably 200 to 400 mPa·s, even more preferably 250 to 350 mPa·s.
When the viscosity of the liquid detergent composition is at least the above lower limit, storage stability is likely to be improved. When the viscosity of the liquid cleaning composition is equal to or less than the above upper limit, the usability of the liquid cleaning composition is likely to be improved. When the viscosity is high, air bubbles tend to be difficult to escape when air is mixed in the liquid detergent composition during manufacture of the liquid detergent composition, refilling from the refillable container to the main container, use, or the like. When air bubbles are mixed in, not only does the specific gravity of the liquid detergent composition decrease, but foam adheres to the mouth of the container when filling the container during manufacturing or when refilling from a refillable container, which may impair manufacturing efficiency and usability. There is
The viscosity of the liquid detergent composition was measured by adjusting the object to be measured to 25° C. and measuring the rotor No. with a Brookfield viscometer. 2, measured after 1 minute at a rotation speed of 60 rpm.

(air content)
The air content of the liquid detergent composition is preferably less than 2% by mass, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, relative to the total mass. When the air content of the liquid detergent composition is equal to or less than the upper limit, the specific gravity of the liquid detergent composition can be easily increased. Although the lower limit of the air content of the liquid detergent composition is preferably as small as possible, it is substantially 0.1% by mass or more.
The air content of the liquid detergent composition can be obtained by measuring the specific gravity of the liquid detergent composition before and after the degassing step described below.

[Method for producing liquid detergent composition]
The method for producing a liquid detergent composition of the present invention has a degassing step of subjecting a dispersion liquid containing components (A) and (B) to a degassing treatment.

The liquid detergent composition of the present invention can be produced, for example, by the following method.
First, component (A), component (B), and optionally optional components are mixed in a solvent and stirred to obtain a dispersion adjusted to a predetermined pH (dispersion step).
Next, the liquid detergent composition is obtained by degassing the dispersion (degassing step).

In the degassing step, methods for degassing treatment include a vacuum decompression method, a centrifugal separation method, an ultrasonic method, a heat boiling method, and the like. From the viewpoint of performing degassing and easily improving the TI value, a vacuum depressurization method is preferable as the degassing treatment method.
As a method for vacuum degassing treatment, for example, a defoaming pump (DP-0300S, manufactured by Yokota Seisakusho Co., Ltd.) is used to instantaneously and continuously separate the liquid and the gas, and the vacuum pump is used. A method of removing gas is mentioned.

The number of times the dispersion is circulated by the defoaming pump (hereinafter also referred to as "the number of defoaming pump passes") is preferably 0.25 to 10 times, more preferably 0.5 to 7 times, and further 1 to 5 times. preferable. When the number of defoaming pump passes is at least the above lower limit, high shear can be applied to the dispersion, and the TI value can be easily improved. In addition, when the number of defoaming pump passes is at least the above lower limit, the dispersion stability of the functionality-imparting particles is likely to be improved. When the number of defoaming pump passes is equal to or less than the above upper limit, excessive shearing can be avoided, and storage stability can be easily improved.
The number of defoaming pump passes can be calculated based on the following formula.
Defoaming pump pass times (times) = flow rate per hour of dispersion passing through defoaming pump (m ³ /s) × treatment time (s) ÷ total volume of dispersion (m ³ )
In the above formula, the treatment time is the time for performing the degassing treatment on the dispersion liquid using the defoaming pump.

The frequency of the defoaming pump when circulating the dispersion liquid is preferably 30 to 100 Hz, more preferably 40 to 90 Hz, and even more preferably 50 to 80 Hz. When the frequency of the defoaming pump is equal to or higher than the above lower limit, high shear can be applied to the dispersion liquid, and the TI value can be easily improved. In addition, when the frequency of the defoaming pump is equal to or higher than the above lower limit, it is easy to improve the dispersion stability of the functionality-imparting particles. When the frequency of the defoaming pump is equal to or less than the above upper limit, excessive shearing can be avoided, and storage stability can be easily improved.

The shear rate of the defoaming pump is preferably 10,000 to 50,000/s, more preferably 20,000 to 40,000/s, even more preferably 25,000 to 30,000/s. When the shear rate of the defoaming pump is equal to or higher than the above lower limit, high shear can be applied to the dispersion and the TI value can be easily improved. When the shear rate of the defoaming pump is equal to or less than the above upper limit, excessive shearing can be avoided, and the storage stability can be easily improved.
The shear rate τ (1/s) of the defoaming pump is determined by the following formula.
Shear rate τ = π・n・d/d'
In the above formula, n is the rotation speed (1/s) of the impeller in the pump (hereinafter also simply referred to as "impeller"), d is the diameter of the impeller (mm), and d' is the clearance between the impeller and the casing. (mm).

The rotation speed of the impeller of the defoaming pump is preferably 10 to 50/s, more preferably 20 to 40/s, even more preferably 25 to 35/s. When the rotational speed of the impeller of the defoaming pump is equal to or higher than the above lower limit, high shear can be applied to the dispersion liquid, and the TI value can be easily improved. When the rotational speed of the impeller of the defoaming pump is equal to or less than the above upper limit, excessive shearing can be avoided, and the storage stability can be easily improved.

The diameter of the impeller of the defoaming pump is not particularly limited, and is preferably 100-400 mm.
The clearance between the impeller and the casing is preferably 0.1 to 3 mm, more preferably 0.25 to 2 mm, even more preferably 0.5 to 1.5 mm. When the clearance between the impeller and the casing is within the above numerical range, it is easy to adjust the shear rate to a desired value.

<Container>
Examples of containers for the liquid detergent composition of the present invention include plastic bottles, tube-shaped containers, pump-type containers, squeeze containers, and refillable bag-shaped containers.
Examples of plastic bottles include plastic bottles in which a container body is formed by blow molding. The container body has a bottom and has a circular or elliptical cross-section.
The mouth of the bottle is provided with a nozzle to be inserted inside the mouth, and further provided with a cap detachably attached to the mouth for tilting and pouring out the contents of the bottle.
As the nozzle attached to the plastic bottle, for example, known nozzles described in JP-A-2018-131240, JP-A-2018-131241, and JP-A-2018-131242 can be used.
As a plastic bottle, the plastic bottle 1 of FIG. 1 is mentioned.
A plastic bottle 1 has a container body 10 and a lid body 20 .
The container body 10 has a bottom portion 16 that is circular in plan view and a body portion 14 that rises from the periphery of the bottom portion 16 .
A shoulder portion 12 narrowing toward the upper end is formed near the upper end of the body portion 14 .
A lower ridge line 18 b extending in a direction parallel to the bottom portion 16 is formed near the bottom portion 16 of the body portion 14 when viewed from the front.
The lower ridgeline 18b curves upward toward both ends.
The trunk portion 14 is formed with two upper ridgelines 18a that extend downward from the shoulder portion 12 .
The two upper ridgelines 18a are separated from each other as they go downward from the shoulder portion 12 .
The lid 20 has a nozzle cap 22 and a metering cap 24 .
The nozzle cap 22 is attached to a cylindrical neck (not shown) formed around the opening of the container body 10 .
A metering cap 24 is screwed onto the nozzle cap 22 .

The tube-shaped container has a tube-shaped container body with one end closed and the other end open to serve as an extrusion port for the cleaning agent, and a cap such as a screw type or one-touch type cap attached to the extrusion port, By pushing the container body, the cleaning agent in the container body is pushed out from the extrusion port. As the tube-shaped container, a known tube-shaped container disclosed in, for example, JP-A-10-168500 can be used. In the liquid detergent composition having a specific TI value of the present invention, the diameter of the pouring opening of the nozzle is preferably 0.5 to 2.5 mm.

The pump-type container has a container body and a pump head attached to the upper end opening of the container body. By pressing the pump head downward, the cleaning agent in the container body is sucked up, and the nozzle of the pump head is pumped up. It is to be discharged from. Examples of pump-type containers include Japanese Utility Model Laid-Open Nos. 54-34641, 56-38783, 56-46572, 56-100378 and 56-121677. A known pump-type container such as those described in JP-A-59-28078, JP-A-2-105900 and the like can be used.

The squeeze container has a container body that is deformed by squeezing (squeezing) and a cap that is formed with a discharge port for discharging the cleaning agent in the container body and is attached to the mouth of the container body. While being inverted, the body of the container body is squeezed by hand to deform the container body and discharge the cleaning agent from the discharge port. In such a squeeze container, when the squeezed state is released, the deformation of the container body is released, and the cleaning agent remaining in the discharge port is returned to the container body by the bag suction mechanism (sucking mechanism) at that time. As the squeeze container, for example, a known squeeze container disclosed in Japanese Patent Application Laid-Open No. 2002-264958 can be used.

The bag-like container is made of a laminated material containing one or more layers made of plastic, the outermost layer (the layer on which light first enters) is made of nylon, the adhesive layer is made of polyethylene, and is vapor-deposited with aluminum. It is constituted at least in part by a layer that does not contain a plastic layer or an aluminum layer. For example, it may be a bag-like container described in [0019] to [0022] of JP-A-2001-098300. The bag-like container is made of a laminated material, and as a specific structure of the bag-like container, a base layer made of oriented nylon (ONy) is arranged as the outermost layer (the layer where light first enters). Then, an adhesive layer made of polyethylene such as linear low-density polyethylene (L-LDPE) or low-density polyethylene (LDPE) is arranged and laminated.

The thickness of the base material layer can be determined in consideration of bag-making processability, cost and strength, and is preferably 10-50 μm, more preferably 10-30 μm, and most preferably 10-20 μm. The thickness of the entire laminated material can also be determined in consideration of bag-making processability, cost, strength and rigidity, and is preferably 100 to 300 μm.
The bag-like container may additionally include, for example, an aluminum-deposited plastic layer, an aluminum layer, a PET (polyethylene terephthalate) layer, etc., in addition to the nylon layer and the polyethylene layer. Examples of the aluminum-deposited plastic layer or aluminum layer include layers described in JP-A-2010-222711. An aluminized plastic layer or an aluminum layer may be placed over the nylon and polyethylene layers.
The bag-like container can be suitably used as a container for refillable products. The bag-shaped container may have a spout portion having a pouring channel at a portion of the edge portion. The spout discharge port can be formed by manually opening the top edge of the bag. Furthermore, a spout may be attached to the tip of the spout.
Examples of the bag-like container include the bag-like container 100 of FIG.
The bag-like container 100 has a storage section 110 and a pouring section 120 .
The housing portion 110 is formed by bonding two sheets of film facing each other.
The accommodating portion 110 has a substantially rectangular shape extending in the vertical direction when viewed from the front, and one corner of the rectangular shape is cut off with a straight line.
A narrower region is formed near the upper end of the accommodating portion 110 than at the lower end.
The pouring part 120 is provided in a corner-cut portion of the accommodating part 110 .
The spout 120 has a spout 122 and a cap 124 .
The spout 122 is a cylindrical member that communicates the inside and outside of the housing portion 110 .
A cap 124 is screwed onto the spout 122 to close the opening of the spout 122 .

Moreover, for example, the bag-like container 200 of FIG. 3 is mentioned as a bag-like container.
The bag-like container 200 has a storage section 210 and a pouring section 120 .
The housing portion 210 is formed by bonding two films facing each other.
The accommodating portion 210 has a substantially rectangular shape extending in the vertical direction when viewed from the front, and one corner of the rectangular shape is cut off with a straight line.
The pouring portion 120 is provided in a corner-cut portion of the accommodating portion 210 .
The accommodating portion 210 has substantially the same width from the upper end to the lower end.

Alternatively, for example, the bag-like container may include the bag-like container 300 of FIGS.
The bag-like container 300 is a so-called standing pouch.
The bag-like container 300 is formed by bonding two sheets of film facing each other to integrally form a storage portion 310 and a pouring portion 320 .
The accommodating portion 310 has a substantially rectangular shape extending in the vertical direction when viewed from the front, and one corner of the rectangular shape is cut off with a straight line.
The spout portion 320 protrudes from the corner-cut portion of the housing portion 310 .
A planned cutting line 322 is formed in the spout portion 320 .
When extracting the contents 330 , the spouting part 320 is cut along the planned cutting line 322 and the contents 330 are extracted from the opening of the spouting part 320 .

The liquid detergent composition of the present invention has a TI value of 1.5 to 5 and is thixotropic. For this reason, when the refill container has a spout portion, shear is applied to the spout portion at the time of refilling, and the viscosity of the liquid detergent composition is lowered, which facilitates refilling, which is preferable. The diameter of the outlet of the bag-like container is preferably 1 to 15 mm, more preferably 5 to 10 mm.

<How to use>
As a method for using the liquid detergent composition according to the present invention (hereinafter also referred to as the product of the present invention), a normal method of use can be applied. For example, a method of putting the product of the present invention into water together with the laundry when washing, a method of directly applying the product of the present invention to mud stains or sebum stains, a method of preliminarily dissolving the product of the present invention in water and soaking the clothes, etc. is mentioned. It is also preferable to apply the product of the present invention to the laundry, leave it for a while, and then wash the laundry using an ordinary washing liquid.

<Effect>
In the liquid detergent composition of the present invention described above, the component (A) and the component (B) are contained in specific amounts, and the specific TI value and specific gravity are used to disperse the function-imparting particles. Improves stability and is excellent in storage stability and usability.
By the way, particles (insoluble particles), such as capsule particles, which are difficult to dissolve in the components constituting the liquid detergent composition are difficult to disperse uniformly in the liquid detergent composition, and even if they can be uniformly dispersed, the lapse of time Insoluble particles tend to settle or float, and it is difficult to maintain a uniformly dispersed state.
However, since the liquid detergent composition of the present invention is imparted with structural viscosity, when the liquid detergent composition contains insoluble particles, the insoluble particles can be uniformly dispersed in the liquid detergent composition. status can be maintained.
Moreover, since the liquid detergent composition of the present invention has a low viscosity, it is excellent in usability. In addition, since the liquid detergent composition of the present invention is also excellent in storage stability, the components contained in the liquid detergent composition are less likely to precipitate or separate even when a concentrated composition is formulated.
The liquid detergent composition of the present invention is suitable as a liquid detergent composition for clothes.

[EXAMPLES] Hereafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.
Raw materials and measurement/evaluation methods used in Examples and Comparative Examples are as follows.
The unit of the compounding amount of each component is "% by mass", which indicates the amount in terms of pure content.

[raw materials used]
<Composition (I)>
((A) component)
a mixture of _{C11H23CO ( OCH2CH2 ) mOCH3} and _{C13H27CO ( OCH2CH2} ) _mOCH3 in a mass ratio of _{8/2 (} MEE), _m = average 15, narrow 33% by weight, synthesized by the following synthesis method: 10% by weight.
· Polyoxyethylene alkyl ether (natural alcohol CO-1270 (trade name, manufactured by Procter & Gamble) added with an average of 15 moles of ethylene oxide): 10% by mass.
· Linear alkylbenzene sulfonic acid (trade name, Lipon LH-200, average molecular weight 322, manufactured by Lion Corporation): 15% by mass.
((B) component)
• A crosslinked copolymer (Carbopol Aqua 30, trade name, manufactured by Lubrizol) consisting of two or more monomers selected from among alkyl acrylate, alkyl methacrylate, acrylic acid, and methacrylic acid: 1.5% by mass.
((C) component)
- Dimethyldiallylammonium-acrylamide copolymer (trade name, Noverite 300, manufactured by Lubrizol): 0.3% by mass.
(First optional component)
· Polyethylene glycol (PEG#1000-60L, manufactured by Lion Corporation): 2% by mass.
Ethanol (trade name, specific alcohol 95 degree synthesis, Japan Alcohol Sales Co., Ltd.): 2% by mass.
- Coconut oil fatty acid (manufactured by NOF Corporation): 4% by mass.
- Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.): 3.6% by mass.
- Citric acid (manufactured by Ipposha Yushi Kogyo Co., Ltd., trade name, liquid citric acid): 0.1% by mass.
- Sodium benzoate (manufactured by Toagosei Co., Ltd., trade name, sodium benzoate): 0.5% by mass.
- 3-methoxy-3-methyl-1-butanol (manufactured by Kuraray Co., Ltd., trade name, Solfit). 5.5% by mass
(Second optional component)
・ TexCare SRN-170C ((trade name, Clariant Japan Co., Ltd., mass average molecular weight = 2000 to 3000, pH (5% by mass aqueous solution at 20 ° C.) = 4, viscosity (20 ° C.) = 300 mPa s), TexCare SRN- 100): 0.5% by weight.
2-Ethylhexyl isooctylate (trade name, 2-ethylhexyl isooctylate, manufactured by Lion Specialty Chemicals): 0.8% by mass.
- Glycerin (trade name, glycerin for cosmetics (85%), manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.): 0.56% by mass.
Perfume, Perfume component a described in JP-A-2009-108248: 0.8% by mass.
- Capsule fragrance, Capsule fragrance A described in the text: 0.1% by mass.
Yellow No. 203 (pigment), manufactured by Chuo Synthetic Chemical Co., Ltd., trade name “Yellow No. 203”: 0.0001% by mass.
Red No. 106 (pigment), manufactured by Kishi Kasei Co., Ltd., trade name “Red No. 106”: 0.00015% by mass.
- Isothiazolone liquid, trade name "Kayson CG", manufactured by Dow Chemical Company: 0.000077% by mass.
(water)
- Water (ion-exchanged water): Balanced so that the total amount is 20.000 kg.

<Composition (II)>
((A) component)
· Polyoxyethylene alkyl ether (natural alcohol CO-1270 (trade name, manufactured by Procter & Gamble) added with an average of 15 moles of ethylene oxide): 10% by mass.
· Linear alkylbenzene sulfonic acid (trade name, Lipon LH-200, average molecular weight 322, manufactured by Lion Corporation): 5% by mass.
((B) component)
• A crosslinked copolymer (Carbopol Aqua 30, trade name, manufactured by Lubrizol) consisting of two or more monomers selected from among alkyl acrylate, alkyl methacrylate, acrylic acid, and methacrylic acid: 1.5% by mass.
(First optional component)
· Polyethylene glycol (PEG#1000-60L, manufactured by Lion Corporation): 3% by mass.
Ethanol (trade name, specific alcohol 95 degree synthesis, Japan Alcohol Sales Co., Ltd.): 0.5% by mass.
- Coconut oil fatty acid (manufactured by NOF Corporation): 0.8% by mass.
- Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.): 0.3% by mass.
- Citric acid (trade name, liquid citric acid, manufactured by Ipposha Yushi Kogyo Co., Ltd.): 0.5% by mass.
- Sodium benzoate (manufactured by Toagosei Co., Ltd., trade name, sodium benzoate): 0.5% by mass.
(Second optional component)
- Glycerin (trade name, glycerin for cosmetics (85%), manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.): 0.56% by mass.
Perfume, Perfume component a described in JP-A-2009-108248: 0.8% by mass.
- Capsule fragrance, Capsule fragrance A described in the text: 0.1% by mass.
Yellow No. 203 (pigment), manufactured by Chuo Synthetic Chemical Co., Ltd., trade name “Yellow No. 203”: 0.0001% by mass.
Red No. 106 (pigment), manufactured by Kishi Kasei Co., Ltd., trade name “Red No. 106”: 0.00015% by mass.
- Isothiazolone liquid, trade name "Kayson CG", manufactured by Dow Chemical Company: 0.000077% by mass.
(water)
- Water (ion-exchanged water): Balanced so that the total amount is 20.000 kg.

<Composition (III)>
((A) component)
· Polyoxyethylene alkyl ether (natural alcohol CO-1270 (trade name, manufactured by Procter & Gamble) added with an average of 7 moles of ethylene oxide): 10% by mass.
· Linear alkylbenzene sulfonic acid (trade name, Lipon LH-200, average molecular weight 322, manufactured by Lion Corporation): 3% by mass.
· Polyoxyalkylene alkyl ether sulfate (AES, mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, average number of added moles of EO 1. Formula R ⁴⁰ —O—[(EO) _y / (PO) _z ]—SO ₃ ⁻ M ⁺ , R ⁴⁰ = linear alkyl groups of 12 and 14 carbon atoms, y=1, z=0, M=sodium, y=0 for the entire AES, Ratio of compounds with z = 0 = 43% by mass, synthesized by the following synthesis method): 7% by mass.
((B) component)
• A crosslinked copolymer (Carbopol Aqua 30, trade name, manufactured by Lubrizol) consisting of two or more monomers selected from among alkyl acrylate, alkyl methacrylate, acrylic acid, and methacrylic acid: 1.5% by mass.
(First optional component)
· Polyethylene glycol (PEG#1000-60L, manufactured by Lion Corporation): 3% by mass.
Ethanol (trade name, specific alcohol 95 degree synthesis, Japan Alcohol Sales Co., Ltd.): 1% by mass.
- Coconut oil fatty acid (manufactured by NOF Corporation): 3% by mass.
- Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.): 0.5% by mass.
- Citric acid (manufactured by Ipposha Yushi Kogyo Co., Ltd., trade name, liquid citric acid): 2% by mass.
(Second optional component)
- Glycerin (trade name, glycerin for cosmetics (85%), manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.): 0.56% by mass.
Perfume, Perfume component a described in JP-A-2009-108248: 0.8% by mass.
- Capsule fragrance, Capsule fragrance A described in the text: 0.1% by mass.
Yellow No. 203 (pigment), manufactured by Chuo Synthetic Chemical Co., Ltd., trade name “Yellow No. 203”: 0.0001% by mass.
Red No. 106 (pigment), manufactured by Kishi Kasei Co., Ltd., trade name “Red No. 106”: 0.00015% by mass.
- Isothiazolone liquid, trade name "Kayson CG", manufactured by Dow Chemical Company: 0.000077% by mass.
(water)
- Water (ion-exchanged water): Balanced so that the total amount is 20.000 kg.

(Method for synthesizing MEE)
It was synthesized according to the synthesis method described in JP-A-2000-144179.
Alumina-magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd., trade name “Kyoward 300”) having a composition of 2.5MgO.Al ₂ O ₃ .zH ₂ O is fired at 600 ° C. for 1 hour in a nitrogen atmosphere. A calcined alumina-magnesium hydroxide (unmodified) catalyst was obtained. 2.2 g of calcined alumina-magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester were charged in a 4 L autoclave, and the autoclave was The catalyst was reformed in-house. Then, after purging the inside of the autoclave with nitrogen, while maintaining the temperature at 180° C. and the pressure at 0.3 MPa, 1052 g of ethylene oxide was introduced and reacted with stirring.
The obtained reaction liquid was cooled to 80° C., and 159 g of water and 5 g each of activated clay and diatomaceous earth as filter aids were added and mixed, and then the catalyst was filtered off to obtain MEE.

(AES synthesis method)
Raw material alcohol (manufactured by Procter & Gamble, trade name “CO1270”, mixture of alcohol having 12 carbon atoms and alcohol having 14 carbon atoms at a mass ratio of 75/25) 400 g, and 0 potassium hydroxide catalyst as a reaction catalyst .8 g was placed in an autoclave having a capacity of 4 L, and after the inside of the autoclave was purged with nitrogen, the temperature was raised while stirring. Subsequently, while maintaining the temperature at 180° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain an alcohol ethoxylate.
Gas chromatograph mass spectrometer: GC-5890 manufactured by Hewlett-Packard, detector: flame ionization detector (FID), column: Ultra-1 (manufactured by HP, L25m × φ0.2mm × T0.11μm ), and the obtained alcohol ethoxylate had an average added mole number of ethylene oxide of 1.0. Moreover, the amount of the compound to which ethylene oxide was not added was 43% by mass with respect to the entire obtained alcohol ethoxylate.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer and purged with nitrogen. After completion of the dropwise addition, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Then, this was neutralized with an aqueous sodium hydroxide solution to obtain a polyoxyalkylene alkyl ether sulfate.

[Examples 1 to 13, Comparative Examples 1 to 4]
<Preparation of dispersion>
A dispersion liquid was prepared as follows so as to have the composition (I) described above.
A first optional component and water were placed in a 20 L blending tank, and stirred using a stirring blade with a three-one motor as a power source. Subsequently, component (C) was added and stirred well, and after confirming visually that there was no component (C) left undissolved, half of the prescribed amount of MEE among component (A) was added. Further, the component (B) and the remaining component (A) were added and thoroughly stirred and dissolved, after which the rest of the MEE was added and stirred. Then, the second optional component was added and further stirred to obtain a dispersion of composition (I) (pH 7.3 at 25°C).
The dispersions of compositions (II) and (III) described above were obtained in the same manner as the dispersion of composition (I), except that component (C) and MEE were not added. The pH at 25° C. of the dispersions of compositions (II) and (III) were both 7.3.
Examples 12 and 13 using dispersions of compositions (II) and (III) are reference examples.

<Preparation of liquid detergent composition>
The resulting dispersion was degassed using a defoaming pump (DP-0300S, manufactured by Yokota Manufacturing Co., Ltd., impeller rotation speed 30/s to 40/s) under the conditions shown in Tables 1 and 2. By applying, a liquid detergent composition of each example was obtained.
The obtained liquid detergent composition was sampled and evaluated for the following physical properties. The results are shown in Tables 1-2.
In addition, "(*)" in Table 2 indicates that degassing treatment was performed using an ultrasonic cleaner (SND Co., Ltd.) without using a defoaming pump.

<Measurement of TI value>
About the liquid detergent composition of each example, the viscosity after 24 hours of manufacture was measured as follows. 100 g of the liquid detergent composition was filled in a transparent glass bottle (standard wide mouth bottle PS-NO.11) and adjusted to 25° C. in a constant temperature bath. After that, using a Brookfield viscometer (rotor No. 2), the respective viscosities were measured after 5 minutes at a rotation speed of 6 rpm and after 1 minute at 60 rpm. A TI value was calculated from the obtained viscosity value, and the TI value was evaluated based on the following evaluation criteria. The results are shown in Tables 1-2.
"Evaluation criteria"
A: TI value of 1.8 or more.
○: TI value of 1.5 or more and less than 1.8.
x: TI value less than 1.5.

<Measurement of specific gravity>
Regarding the liquid detergent composition of each example, the specific gravity before and after the degassing step was measured as follows. A specific gravity cup was filled with 15 mL of the dispersion liquid before degassing, and the mass was measured with a precision balance. After that, the same specific gravity cup was filled with 15 mL of purified water, and the mass was measured with the same precision balance. Next, 15 mL of the degassed liquid detergent composition was filled in a specific gravity cup, and the mass was measured with a precision balance. The specific gravity of the liquid detergent composition was calculated according to the following formula.
Specific gravity = mass of 15 mL of liquid cleaning composition/mass of 15 mL of purified water

<Usability evaluation>
900 g of the liquid detergent composition of each example was filled into the bag-like container for refilling shown in FIG. 2, and the time required to refill 425 g of the plastic bottle shown in FIG. 1 was measured with a stopwatch. The refillability (usability) of the container was evaluated based on the following evaluation criteria. The results are shown in Tables 1-2.
"Evaluation criteria"
○: The time required for refilling the entire amount is within 30 seconds.
Δ: The time required for refilling the entire amount is more than 30 seconds and less than 45 seconds.
x: More than 45 seconds required for full refilling.

<Evaluation of storage stability>
Put 100 g of the liquid detergent composition of each example into a transparent glass bottle (wide-mouth standard bottle PS-NO.11), cover it, leave it in a constant temperature room at 50°C, and visually observe the appearance after a certain period of time. The storage stability was evaluated based on the following evaluation criteria. The results are shown in Tables 1-2.
"Evaluation criteria"
A: Phase separation is not observed even after 2 months.
◯: Separation into two layers (upper layer: transparent, lower layer: cloudy) after 1 month.
Δ: Separation into two very thin layers (upper layer: transparent, lower layer: cloudy) within one month.
x: Clearly separated into two layers (upper layer: transparent, lower layer: cloudy) within 1 month.

<Evaluation of dispersion stability of functionality-imparting particles>
Put 100 g of the liquid detergent composition of each example into a transparent glass bottle (wide-mouth standard bottle PS-NO.11), cover it, leave it in a constant temperature room at 50°C, and visually observe the appearance after one month. Then, the dispersion stability of the function-imparting particles was evaluated based on the following evaluation criteria. The results are shown in Tables 1-2.
"Evaluation criteria"
A: No floating or sedimentation of capsules was observed, and the liquid was transparent.
◯: No floating or sedimentation of capsules was observed, and the liquid was slightly cloudy.
x: Floating capsules are observed, and the air-liquid interface is cloudy.

As shown in Tables 1 and 2, in Examples 1 to 13 to which the present invention is applied, the evaluation of the TI value is "⊚" or "○", usability, storage stability, and dispersion stability of the function-imparting particles. was "⊚" or "○", and the usability, storage stability, and dispersion stability of the function-imparting particles were all excellent. On the other hand, in Comparative Examples 1 to 4 with a TI value of less than 1.5, the dispersion stability of the function-imparting particles was "poor".

It was found that the liquid detergent composition of the present invention improves the dispersion stability of the function-imparting particles, and is excellent in storage stability and usability.

1 Plastic bottle 10 Container main body 20 Lid 100, 200, 300 Bag-like container 110, 210, 310 Storage part 120, 220, 320 Extraction part 330 Contents

Claims (4)

(A) component: a surfactant;
(B) component: a structural viscosity-imparting agent;
(C) component: a repeating unit represented by the following general formula (c1) and the following general formula (c2)
With one or more repeating units selected from repeating units represented by the following general formula (c3)
containing a cationic polymer having a repeating unit represented by
The content of the component (A) is 15 to 60% by mass with respect to the total mass,
The content of the component (B) is 0.1 to 5.0% by mass with respect to the total mass,
The content of the component (C) is 0.1 to 5.0% by mass with respect to the total mass,
A liquid detergent composition having a thixotropic index of 1.5 to 5 and a specific gravity of 1.0 to 1.5.

In general formula (c1), R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X 1 ^- is a counter ion.
In general formula (c2), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X 1 ^- is a counter ion.

In general formula (c3), R ¹³ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or 1 -3 hydroxyalkyl groups. The component (B) is
(B-1) component: a repeating unit derived from a monomer represented by the following general formula (b1) and a repeating unit derived from a monomer represented by the following general formula (b2); molecule,
(B-2) component: polyurea resin, and
(B-3) component: triglyceride represented by the following general formula (b3)
The liquid detergent composition according to claim 1, which is one or more selected from

In general formula (b1), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom.
In general formula (b2), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 40 carbon atoms.

In general formula (b3), Z ¹ ～Z ³ each independently represents a hydrogen atom, a hydroxyl group or a carboxy group. In general formula (b3), a to f are numbers representing repeating methylene groups, and a+b=7 to 19, c+d=7 to 19, and e+f=7 to 19. The component (B) is
(B-1) component: a repeating unit derived from a monomer represented by the following general formula (b1) and a repeating unit derived from a monomer represented by the following general formula (b2); molecule
The liquid detergent composition according to claim 1.

In general formula (b1), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom.
In general formula (b2), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 40 carbon atoms. A method for producing the liquid detergent composition according to any one of claims 1 to 3,
a degassing step of subjecting the dispersion containing the component (A), the component (B), and the component (C) to a degassing treatment using a degassing pump ;
The number of times the dispersion is circulated by the defoaming pump in the degassing step is 0.25 to 10 times, the frequency of the defoaming pump is 30 to 100 Hz, and the shear rate of the defoaming pump is 10000 to 50000/s. , a method for producing a liquid detergent composition.

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