WO2024014555A1

WO2024014555A1 - Liquid detergent composition for dishes

Info

Publication number: WO2024014555A1
Application number: PCT/JP2023/026151
Authority: WO
Inventors: 絵美神村
Original assignee: ライオン株式会社
Priority date: 2022-07-15
Filing date: 2023-07-14
Publication date: 2024-01-18

Abstract

A liquid detergent composition for dishes comprising a specific amount of (A) component, which is an anionic surfactant (which is not a soap (higher fatty acid salt)), (B) component, which is at least one surfactant selected from among semipolar surfactants and amphoteric surfactants, a specific amount of (C) component, which is cationized cellulose, and (D) component, which is an aminocarboxylic acid type chelating agent, the mass ratio indicated by (A) component/(D) component being 0.8-23.

Description

Liquid cleaning composition for tableware

FIELD OF THE INVENTION The present invention relates to liquid cleaning compositions for tableware.
This application claims priority to Japanese Patent Application No. 2022-113774 filed in Japan on July 15, 2022, the contents of which are incorporated herein.

Due to changes in consumer lifestyles, ``convenience'' and ``cleanliness'' are becoming more important in dishwashing behavior. Important factors that lead to ``simplicity'' include ``oil stain cleaning power'' that effectively removes oil stains, and ``fewer slimy stains'' during dishwashing. An important factor related to ``cleanliness'' is that ``no water marks or stains remain'' after the dishes are dry. It is desired that liquid detergent compositions for tableware satisfy these factors.

In response to these demands, Patent Document 1 discloses that an anionic surfactant, at least one kind selected from a semipolar surfactant and an amphoteric surfactant, a cationized cellulose, and a specific polyoxyalkylene alkyl ether. Liquid dishwashing detergent compositions containing specific mass ratios have been proposed.
Patent Document 2 describes a liquid detergent composition for tableware that contains a specific amount of an anionic surfactant, at least one selected from semipolar surfactants and amphoteric surfactants, and cationized cellulose. is proposed.
Patent Document 3 describes an anionic surfactant, at least one selected from semipolar surfactants and amphoteric surfactants, and at least one selected from fatty acid monoalkanolamide and polyoxyethylene fatty acid monoalkanolamide, A liquid detergent composition for tableware containing cationized cellulose in a specific mass ratio has been proposed.
According to the inventions of Patent Documents 1 to 3, it is intended to more quickly drain water from the surface of tableware after washing (improve water draining performance).

Japanese Patent Application Publication No. 2018-035251 Japanese Patent Application Publication No. 2003-155499 Japanese Patent Application Publication No. 2018-035252

Liquid dishwashing detergent compositions are sometimes used to clean stainless steel sinks. In order to keep the sink clean, it is desirable that the sink be dried cleanly without leaving any water droplets after washing.
However, when conventional liquid dishwashing detergent compositions are used to clean stainless steel sinks, water does not drain evenly and water droplets remain, forming water spots after drying. Put it away. There is a problem in that simply increasing the concentration of each component in a liquid detergent composition for tableware increases the sliminess of objects to be cleaned such as sinks and tableware.
Therefore, the present invention aims to provide a liquid detergent composition for tableware that can reduce water spots after drying and suppress sliminess, regardless of the material of the object to be cleaned.

The present invention has the following aspects.
<1>
Contains (A) component, (B) component, (C) component, and (D) component,
The component (A) is an anionic surfactant (excluding soap (higher fatty acid salt)),
The component (B) is at least one selected from semipolar surfactants and amphoteric surfactants,
The component (C) is cationized cellulose,
The component (D) is an aminocarboxylic acid type chelating agent,
For the total mass of the liquid cleaning composition,
The content of the component (A) is 4 to 12% by mass,
The content of the component (C) is 0.05 to 2.5% by mass,
A liquid detergent composition for tableware, wherein the mass ratio represented by the component (A)/component (D) is from 0.8 to 23.
<2>
The liquid detergent composition for tableware according to <1>, wherein the mass ratio represented by the component (A)/(component (C) + component (D)) is 0.5 to 12.5. thing.
<3>
The liquid detergent composition for tableware according to <1> or <2>, wherein the mass ratio represented by the component (A)/component (B) is 0.25 to 2.
<4>
The liquid detergent composition for tableware according to any one of <1> to <3>, wherein the component (D) is at least one selected from methylglycine diacetic acid and its salt.
<5>
The liquid detergent composition for tableware according to any one of <1> to <4>, wherein the component (B) is an alkylamine oxide type semipolar surfactant.
<6>
The liquid detergent composition for tableware according to <5>, wherein the component (B) is lauryl dimethylamine oxide.
<7>
The liquid detergent composition for tableware according to any one of <1> to <6>, wherein the degree of cationization of the component (C) is 0.5 to 3.5% by mass.
<8>
The mass ratio represented by the component (A)/component (D) is 4.0 to 10.0,
The mass ratio represented by the component (A)/(component (C) + component (D)) is 3.2 to 8.42,
The liquid detergent composition for tableware according to any one of <1> to <7>, wherein the mass ratio represented by the component (A)/component (B) is 0.8 to 1.7. .
<9>
The content of the component (A) is 6 to 10% by mass,
The content of the component (B) is 5.0 to 10% by mass,
The content of the component (C) is 0.1 to 1.0% by mass,
The liquid detergent composition for tableware according to any one of <1> to <8>, wherein the content of the component (D) is 0.8 to 1.5% by mass.

According to the liquid detergent composition for tableware of the present invention, water spots can be reduced and sliminess can be suppressed.

(Liquid detergent composition for tableware)
The liquid detergent composition for tableware of the present invention (hereinafter sometimes simply referred to as "liquid detergent composition") contains components (A) to (D).

<(A) component>
Component (A) is an anionic surfactant (excluding soap (higher fatty acid salt)). By containing component (A), the liquid cleaning composition can enhance cleaning power and reduce water spots.

Component (A) is preferably a polyoxyalkylene alkyl ether sulfate or a salt thereof, an alkyl group-containing alkanesulfonic acid or a salt thereof, a linear alkylbenzenesulfonic acid or a salt thereof, a sulfosuccinic acid dialkyl ester or a salt thereof, and a polyoxyalkylene alkyl ether sulfate or a salt thereof. More preferred are alkylene alkyl ether sulfates or salts thereof, alkanesulfonic acids having an alkyl group or salts thereof, and linear alkylbenzenesulfonic acids or salts thereof.

Examples of the polyoxyalkylene alkyl ether sulfate or its salt include a compound represented by the following formula (1).
R ¹ -O-(EO) _n -SO ₃ -M ⁺ ...(1)
[In formula (1), R ¹ is a straight chain alkyl group having 8 to 18 carbon atoms, and the carbon atom bonded to the oxygen atom is the first carbon atom. EO is an oxyethylene group, and n indicates the average number of added moles of EO, and 0<n≦4. M ⁺ is a cation other than a hydrogen ion. ]

Examples of M ⁺ include alkali metal ions, alkaline earth metal ions, ammonium ions, protonated ethanolamine, and the like. Examples of alkali metal ions include sodium ions and potassium ions. Examples of alkaline earth metal ions include calcium ions and magnesium ions. Examples of protonated ethanolamine include alkanolamine salts such as diethanolamine and triethanolamine. Note that when M ⁺ is a cation with a valence of two or more, the number of M ⁺ is the number multiplied by 1/the valence and is bonded to -SO ₃ . For example, if M ⁺ is a magnesium ion, the number of M ⁺ is 1/2. As M ⁺ , an alkali metal ion is preferable, and a sodium ion and a potassium ion are more preferable.

The number of carbon atoms in R ¹ is preferably 10 to 14, more preferably 12 to 14. Further, R ¹ is preferably an alkyl group derived from an oil or fat raw material.
A particularly preferred component (A) is polyoxyethylene (1) linear alkyl (C12/14=75/25; derived from natural fats and oils) sulfate sodium salt.
The number in parentheses following "polyoxyethylene" is the average number of repeating oxyethylene groups (ie, the average number of added moles of ethylene oxide). Further, the number after "C", such as "C12", is the number of carbon atoms.

Examples of alkanesulfonic acids or salts thereof having an alkyl group include alkanesulfonic acids having 10 to 20 carbon atoms or salts thereof, preferably alkanesulfonic acids having 14 to 17 carbon atoms or salts thereof, and alkanesulfonic acids having 14 to 17 carbon atoms or salts thereof. Particularly preferred are secondary alkanesulfonic acids (SAS) or salts thereof. Examples of SAS salts include sodium salts.

The linear alkylbenzene sulfonic acid (LAS) salt is preferably a linear alkylbenzene sulfonic acid or a salt thereof in which the linear alkyl group has 8 to 16 carbon atoms; Particularly preferred are sulfonic acids or their salts. Examples of LAS salts include sodium salts, potassium salts, and the like.

These (A) components may be used alone or in combination of two or more.

The content of component (A) is preferably 4 to 12% by mass, more preferably 6 to 10% by mass, based on the total mass of the liquid cleaning composition. When the content of component (A) is at least the above lower limit, water spots can be further reduced. When the content of the component (A) is below the above upper limit, water spots can be further reduced and nulling can be further suppressed. In addition, when the content of component (A) is below the above upper limit, gelation and separation of the liquid cleaning composition can be suppressed, and liquid stability can be improved.

<(B) component>
Component (B) is at least one selected from semipolar surfactants (component (b1)) and amphoteric surfactants (component (b2)). By containing the component (B), the liquid cleaning composition of the present invention can further reduce water spots and suppress sliminess.

Component (b1) is a surfactant having a semipolar bond (a bond with properties intermediate between a nonpolar bond and a polar bond). The component (b1) exhibits cationic or non-polar properties depending on the pH of the solution in which it is dissolved or the dispersion system in which it is dispersed.
Examples of the component (b1) include alkylamine oxide type semipolar surfactants and alkylamide amine oxide type semipolar surfactants.

Examples of the component (b1) include compounds represented by the following formula (b1).

Formula (b1) In the formula, R ²¹ is a linear or branched alkyl group having 8 to 18 carbon atoms, or a linear or branched alkenyl group having 8 to 18 carbon atoms, and R ²² and R ²³ are each They are independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ²⁴ is an alkylene group having 1 to 4 carbon atoms. A is -CONH-, -NHCO-, -COO-, -OCO- or -O-, and r is a number of 0 or 1.

As the alkylamine oxide type semipolar surfactant, an alkyldimethylamine oxide having an alkyl group having 8 to 18 carbon atoms is preferable, and an alkyldimethylamine oxide having an alkyl group having 12 to 14 carbon atoms is more preferable. Examples of the alkylamine oxide type semipolar surfactant include lauryl dimethylamine oxide, myristyl dimethylamine oxide, coconut oil dimethylamine oxide, and the like.
Among these components (b1), alkyl amine oxide type semipolar surfactants are preferred, lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and coconut oil dimethyl amine oxide are more preferred, and lauryl dimethyl amine oxide is even more preferred.

Component (b2) includes, for example, carbobetaine-based amphoteric surfactants, amidobetaine-based amphoteric surfactants, sulfobetaine-based (hydroxysulfobetaine-based, amidosulfobetaine-based) amphoteric surfactants, and imidazolinium betaine-based amphoteric surfactants. Examples include surfactants, phosphobetaine-based amphoteric surfactants, and aminopropionic acid-based amphoteric surfactants.

Examples of carbobetaine-based amphoteric surfactants include betaine laurate dimethylaminoacetate, betaine myristyldimethylaminoacetate, and betaine stearyldimethylaminoacetate.
Examples of amidobetaine-based amphoteric surfactants include coconut oil fatty acid amidopropyl betaine (cocamidopropyl betaine), amidopropyl laurate, and isostearamidopropyl betaine.
Examples of the sulfobetaine-based amphoteric surfactants include laurylhydroxysulfobetaine and lauryldimethylsulfobetaine.

Among these components (b2), carbobetaine-based amphoteric surfactants, amidobetaine-based amphoteric surfactants, and sulfobetaine-based amphoteric surfactants are preferred, and amidopropyl laurate, lauryl dimethylaminoacetic acid betaine, and lauryl hydroxysulfonate are preferred. Betaine is more preferred.

The above-mentioned component (B) may be used alone or in combination of two or more. As the component (B), it is preferable that the component (b1) is included, and the component (b1) is preferable.

The content of component (B) is preferably 1 to 20% by mass, more preferably 2.5 to 15% by mass, and even more preferably 5 to 10% by mass, based on the total mass of the liquid cleaning composition. When the content of the component (B) is equal to or higher than the above lower limit, water spots can be further reduced and nulling can be further suppressed. If the content of component (B) is below the above upper limit, liquid stability can be improved.

In the liquid cleaning composition, the mass ratio of component (A) to component (B), expressed as component (A)/component (B) (A/B ratio), is 0.25 to 2. is preferable, and 0.8 to 1.7 is more preferable. If the A/B ratio is equal to or higher than the above lower limit, water spots can be further reduced. If the A/B ratio is less than or equal to the above upper limit, nulling can be further suppressed.

<(C) component>
Component (C) is cationized cellulose. By containing component (C), the liquid cleaning composition can further reduce water spots.

As component (C), for example, a compound represented by the following formula (c1) ((c1) component), a compound represented by the following formula (c2) ((c2) component), a compound represented by the following formula (c3) (component (c3)), a compound represented by the following formula (c4) (component (c4)), and the like. Examples of the component (C) include cation-modified hydroxyethylcellulose such as hydroxytrimethylammoniumpropylhydroxyethylcellulose chloride and hydroxyethylcellulose dimethyldiallylammonium chloride polymer. Among these, as component (C), a compound represented by the following formula (c1) is preferable from the viewpoint of the balance between the effect of reducing water spots and the effect of suppressing sliminess.

In formula (c1), s, t, and u are numbers representing the number of repeats of the repeating unit in parentheses. (c2) In formula, q and r are numbers representing the number of repetitions of the repeating unit in [].
In formula (c4), w, x, v, and y are numbers representing the number of repetitions of the repeating unit in parentheses.
The mass average molecular weight of component (c1) is from 10,000 to several million (eg, 1 million).
The mass average molecular weight of component (c2) is from 10,000 to several hundred thousand (eg, 500,000).
The mass average molecular weight of component (c3) is from 10,000 to several hundred thousand (eg, 500,000).
The mass average molecular weight of component (c4) is from 10,000 to several million (eg, 1 million).

The degree of cationization of component (C) is preferably 0.5 to 3.5% by mass, more preferably 1.5 to 2.5% by mass. If the degree of cationization is within the above range, water spots can be further reduced.
Here, the "degree of cationization" refers to the content (mass%) of nitrogen atoms derived from the cationizing agent in the molecules of component (C), that is, the percentage of nitrogen atoms derived from the cationizing agent relative to the total mass of component (C). It means the content rate.

The degree of cationization of component (C) can be determined by calculation based on the specified chemical structure. When the chemical structure of component (C) is not specified, such as when the ratio of the structural units in component (C) is unknown, the degree of cationization of component (C) is calculated from the experimentally determined nitrogen content. Ru. As a method for measuring the nitrogen content of component (C), the Kjeldahl method can be used, but other methods may be used for convenience.

The viscosity of the 2% by mass aqueous solution of component (C) at 25° C. is preferably 50 to 35,000 mPa·s, more preferably 70 to 500 mPa·s, and even more preferably 70 to 200 mPa·s. When the viscosity of the 2% by mass aqueous solution of component (C) is within the above range, there is an excellent balance between the effect of reducing water spots and the stability of the liquid composition.
The viscosity is a value measured using a B-type viscometer for a 2% by mass aqueous solution of component (C) at 25°C. The conditions for measuring viscosity are as follows.

Measurement condition:
[rotor]
The rotor number and rotor rotation speed corresponding to the viscosity of the object to be measured are as follows.
・Viscosity is less than 500 mPa・s: Rotor number No. 2. Rotation speed 60 rpm.
・Viscosity is 500 mPa・s or more and less than 2000 mPa・s: Rotor number No. 3. Rotation speed 60 rpm.
・Viscosity is 2000 mPa・s or more and less than 10000 mPa・s: Rotor number No. 4. Rotation speed 60 rpm.
・Viscosity is 10,000 mPa・s or more and less than 50,000 mPa・s: Rotor number No. 4. Rotation speed 12 rpm.
[Reading numbers]
60 seconds after the rotor starts rotating.

As component (C), for example, the product name "Leogard GP (quaternary nitrogen content 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", the product name "Leogard MGP (quaternary nitrogen content 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", product name: "Leogard MLP (quaternary nitrogen content: 0.6% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", product name: "UCARE" JR125 (Quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Company)", product name "UCARE JR400 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Company)", product name Examples include "UCARE LR30M (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Company)". Among these, "UCARE JR125" and "UCARE JR400" are preferred, and "UCARE JR125" is more preferred, from the viewpoint of further enhancing the effect of reducing water spots.
Component (C) may be used alone or in combination of two or more.

The content of component (C) is preferably 0.05 to 2.5% by mass, more preferably 0.1 to 1% by mass, and 0.1 to 0.5% by mass based on the total mass of the liquid cleaning composition. Mass % is more preferred. If the content of component (C) is at least the above lower limit, water spots can be further reduced. If the content of component (C) is below the above upper limit, sliminess can be further suppressed and the liquid stability of the liquid cleaning composition can be further improved.

<(D) component>
Component (D) is an aminocarboxylic acid type chelating agent. By containing the component (D), the liquid cleaning composition can further reduce water spots and suppress sliminess.

Component (D) includes, for example, ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), dihydroxyethylglycine (DHEG), hydroxyethyleneiminodiacetic acid (HIDA), diethylenetriaminepentaacetic acid (DTPA), and methylglycine diacetic acid. Acetic acid (MGDA), aspartic acid diacetic acid (ASDA), isoserine diacetic acid (ISDA), β-alanine diacetic acid (ADAA), serine diacetic acid (SDA), glutamic acid diacetic acid (GLDA), iminodisuccinic acid (IDS), hydroxy Iminodisuccinic acid (HIDS), N-lauroylethylenediaminetriacetic acid, nitrilotriacetic acid (NTA), triethylenetetraaminehexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino- Examples include 2-hydroxypropanetetraacetic acid (DPTA-OH), glycol ether diamine tetraacetic acid (GEDTA), dicarboxymethylglutamic acid (CMGA), (S,S)-ethylenediaminedisuccinic acid (EDDS), and salts thereof. . Examples of the salt form of component (D) include sodium salt, potassium salt, and the like.
As the component (D), from the viewpoint of the balance between the water spot reduction effect and the nulliness suppression effect, MGDA, GLDA, EDTA, HEDTA, DHEG, HIDA, and DTPA are preferable, and MGDA, GLDA, and EDTA are more preferable, and MGDA, GLDA, and EDTA are more preferable. MGDA is preferred.
These (D) components may be used alone or in combination of two or more.

The content of component (D) is preferably 0.2 to 5% by mass, more preferably 0.5 to 2.5% by mass, based on the total mass of the liquid cleaning composition. When the content of component (D) is equal to or higher than the above lower limit, water spots can be further reduced and nulling can be further suppressed. If the content of the component (D) is below the above upper limit, water spots can be further reduced and nulliness can be further suppressed.

In the liquid cleaning composition, the mass ratio of component (A) to component (D), expressed as component (A)/component (D) (A/D ratio), is 0.8 to 23. is preferable, 2.5 to 16 is more preferable, and 5 to 10 is even more preferable. If the A/D ratio is equal to or higher than the above lower limit, water spots can be further reduced and nulls can be further suppressed. If the A/D ratio is below the above upper limit, water spots can be further reduced and nulls can be further suppressed.

In a liquid cleaning composition, it is the mass ratio of the (A) component to the total of the (C) component and (D) component, and is expressed as (A) component/((C) component + (D) component) The mass ratio (A/(C+D) ratio) is preferably 0.5 to 12.5, more preferably 3.5 to 8.5. If the A/(C+D) ratio is equal to or higher than the above lower limit, water spots can be further reduced and nulls can be further suppressed. When the A/(C+D) ratio is equal to or less than the above upper limit, water spots can be further reduced and nulling can be further suppressed.

<Optional ingredients>
The liquid cleaning composition may contain optional components other than components (A) to (D) within a range that does not impair the effects of the present invention.

Any component used in a liquid detergent composition for tableware may be used as an optional component. Optional ingredients include water, surfactants other than components (A) and (B) (optional surfactants), hydrotropes, preservatives, pH adjusters, chelating agents other than component (D) (optional chelating agents), fragrances, pigments, thickeners, etc.

Water functions as a solvent for the liquid cleaning composition. The water content is determined by considering the appropriate concentration of components other than water (component (A), component (B), component (C), component (D), etc.), and taking the remainder of these components as However, for example, the amount is more preferably 40 to 85% by weight, and even more preferably 60 to 80% by weight, based on the total weight of the liquid cleaning composition. If the water content is at least the above lower limit, gelation will be suppressed and the uniformity of the liquid will increase. If the water content is below the above upper limit, the viscosity will not become too low and the usability will be excellent.

Optional chelating agents include organic acids and salts thereof, such as glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, gluconic acid, and salts thereof. Examples of salts include sodium salts.
As the optional chelating agent, citric acid and its salts are more preferred.
The content of the chelating agent is preferably 0.1 to 5% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 3% by mass, based on the total mass of the liquid cleaning composition. If the content of the chelating agent is at least the above lower limit, water spots can be further reduced. If the content of the chelating agent is below the above upper limit, water spots can be further reduced and sliminess can be further suppressed.

Examples of the optional surfactant include cationic surfactants, nonionic surfactants, and the like.
Examples of the hydrotrope include orthotoluenesulfonic acid, metatoluenesulfonic acid, paratoluenesulfonic acid, or salts thereof, cumene sulfonic acid, cumene sulfonate, ethanol, butyl carbitol, and the like.
Examples of preservatives include isothiazoline compounds, specifically benzisothiazolinone (1,2-benzisothiazolin-3-one) and methylisothiazolinone (2-methyl-4-isothiazolin-3-one). ), butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, and the like.
Examples of the pH adjuster include inorganic alkaline agents, organic alkaline agents, and inorganic acids.
Examples of inorganic alkali agents include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.
Examples of organic alkali agents include monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N-(β-aminoethyl)ethanolamine, diethylenetriamine, morpholine, N- Examples include amine compounds such as ethylmorpholine.
Examples of inorganic acids include hydrochloric acid and sulfuric acid.
Examples of organic acids include acetic acid and the like.

<Physical properties>
The pH of the liquid detergent composition of the present invention at 25° C. is preferably 6 to 8. If the pH of the liquid detergent at 25° C. is within the above range, water spots can be further reduced and sliminess can be further suppressed.
The pH (25°C) of the liquid cleaning composition is a value measured by a method based on JIS Z 8802:1984 "pH measurement method".

The viscosity of the liquid cleaning composition of the present invention at 25° C. is preferably 10 to 200 mPa·s, more preferably 50 to 150 mPa·s. When the viscosity is equal to or higher than the above lower limit, dripping from the spout of the container can be satisfactorily suppressed. When the viscosity is below the above upper limit, the liquid cleaning composition can be more easily discharged from the container.

The viscosity of the liquid detergent composition can be adjusted by adjusting the water content, adding a thickener, etc.
The viscosity of the liquid cleaning composition was measured using a B-type viscometer with the object to be measured at 25°C, and the viscosity was measured using rotor No. 1. This value is measured 60 seconds after the rotor starts rotating at a rotor rotation speed of 60 rpm.

(Production method)
The liquid cleaning composition of the present invention is manufactured by a conventionally known manufacturing method.
Examples of the method for producing the liquid cleaning composition include a method in which components (A) to (D) are added to a portion of water, mixed, the pH is adjusted, and then the remainder of the water is added.

(how to use)
Examples of methods for using the liquid cleaning composition include applying the liquid cleaning composition to a cleaning tool, lathering the liquid cleaning composition onto the cleaning equipment, and scrubbing the item to be cleaned with the lathered cleaning equipment. It will be done. Alternatively, there is a method in which a liquid cleaning agent composition is dissolved in water to obtain a cleaning liquid, and the object to be cleaned is immersed in the cleaning liquid and rubbed with a cleaning tool. In either method, the scrubbed object is rinsed with water, and then the object is drained.

Examples of cleaning tools include sponges, brushes, cloths, and the like.
Examples of objects to be cleaned include ceramics, metal utensils, and the like. Examples of ceramics include tableware such as plates, bowls, and bowls. Examples of metal utensils include tableware such as forks and spoons, stainless steel sinks, and the like.

By containing the component (A), the liquid cleaning composition of the present invention can reduce water spots on objects to be cleaned. By containing the component (B), the liquid cleaning composition can suppress sliminess of the object to be cleaned. By containing component (C), the liquid cleaning composition can reduce water spots on ceramics.
In addition, by containing component (D), the liquid cleaning composition can reduce water spots on metals. This is considered to be because the presence of the component (D) on the metal surface makes it easier for the component (C) to adsorb onto the metal surface. Moreover, the liquid cleaning composition can suppress sliminess by containing the component (D). This is considered to be because component (D) forms a complex with components (A) to (C) to reduce charge repulsion.

In addition, in one preferred embodiment of the present invention,
The mass ratio represented by the component (A)/component (D) is 4.0 to 10.0,
The mass ratio represented by the component (A)/(component (C) + component (D)) is 3.2 to 8.42,
The mass ratio represented by the component (A)/component (B) is 0.8 to 1.7.
In yet another preferred embodiment of the present invention,
The content of the component (A) is 6 to 10% by mass,
The content of the component (B) is 5.0 to 10% by mass,
The content of the component (C) is 0.1 to 1.0% by mass,
The content of the component (D) is 0.8 to 1.5% by mass.
In these preferred embodiments, the effects of the present invention can be further enhanced.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following description.

(Raw materials used)
<(A) component>
- A-1 (AES (1)): polyoxyethylene (1) linear alkyl (C12/14 = 75/25; derived from natural fats and oils) sulfate ester sodium salt, prepared in Production Example 1 below.

<Production Example 1> Preparation method of AES (1) In a 4L autoclave, 400 g of Procter &Gamble's brand name "CO1270 alcohol (C12/C14 = 75%/25%, mass ratio)" as raw alcohol and and 0.8 g of potassium hydroxide as a reaction catalyst, and after purging the inside of the autoclave with nitrogen, the temperature was raised while stirring. Subsequently, 91 g of ethylene oxide was introduced and reacted while maintaining the temperature at 180° C. and the pressure at 0.3 MPa or less. The average number of moles of ethylene oxide added to the obtained polyoxyalkylene ether was 1.
Next, 237 g of the obtained polyoxyalkylene ether ethylene oxide was placed in a 500 mL flask equipped with a stirrer, and the flask was purged with nitrogen, and then 96 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40°C. After completion of the dropwise addition, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid.
Next, the obtained polyoxyethylene alkyl ether sulfuric acid was neutralized with an aqueous sodium hydroxide solution to obtain A-1.

- A-2 (LAS): Sodium linear alkylbenzene sulfonate having 10 to 14 carbon atoms, "Tayka Power (registered trademark) L121" manufactured by Teika, neutralized with sodium hydroxide.
- A-3 (SAS): Sodium secondary alkanesulfonate having 14 to 17 carbon atoms, "HOSTAPUR (registered trademark) SAS30A" manufactured by Clariant Japan.

<(B) component>
- B-1 (AX): lauryl dimethylamine oxide, "Cadenax (registered trademark) DM12D-W" manufactured by Lion Specialty Chemicals.
- B-2 (APAX): Lauric acid amidopropyl dimethylamine oxide, manufactured by Clariant Japan Co., Ltd., trade name "GENAMINOX (registered trademark) AP").
- B-3 (LHB): lauryl hydroxysulfobetaine, manufactured by Kao Corporation, trade name "Amhitol (registered trademark) 20HD".

<(C) component>
- C-1 (CC1): Cationized cellulose (manufactured by Dow Chemical Company, trade name "UCAREJR125", quaternary nitrogen content 1.9% by mass, viscosity of 2% by mass aqueous solution at 25°C 130 mPa·s).
・C-2 (CC2): Cationized cellulose (manufactured by Dow Chemical Company, product name "UCAREJR 400", quaternary nitrogen content 1.9% by mass, viscosity of 2% by mass aqueous solution at 25°C 400 mPa・s) .
・C-3 (CC3): Cationized cellulose (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Leoguard GP", quaternary nitrogen content 1.8% by mass, viscosity of 2% by mass aqueous solution at 25 ° C. 300 mPa・s).
- C-4 (CC4): Cationized cellulose (manufactured by Dow Chemical Company, trade name "UCARELR30M", quaternary nitrogen content 1.0% by mass, viscosity of 2% by mass aqueous solution at 25°C 30000 mPa·s).
Note that the viscosity of the 2% by mass aqueous solution at 25°C was measured based on the above measurement conditions.

<(C') component>
- C'-1 (CMC): Sodium carboxymethylcellulose, manufactured by Daicel Chemical Industries, Ltd., trade name "CMC1260".
- C'-2 (HPMC): Hydroxypropyl methylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd., trade name "Metrose".

<(D) component>
- D-1 (MGDA-Na): trisodium methylglycine diacetate, manufactured by BASF, trade name "Trilon M Max BioBased L).
- D-2 (GLDA-Na): Tetrasodium L-glutamic acid diacetate, manufactured by Akzo Nobel, trade name "Dissolvine (registered trademark) GL-47-S".
- D-3 (EDTA-Na): Tetrasodium ethylenediaminetetraacetate, manufactured by BASF, trade name "Trilon BX Liquid".

<Optional ingredients>
・CA (citric acid): (manufactured by Fuso Chemical Industry Co., Ltd.).
- EtOH: Ethanol (manufactured by Nippon Alcohol Sales Co., Ltd.).
-pTS-H: para-toluenesulfonic acid (manufactured by Kanto Chemical Industry Co., Ltd.).
- Benzoic acid: Sodium benzoate (manufactured by Fushimi Pharmaceutical Co., Ltd.).
- BDG: Butyl diglycol (butyl carbitol, manufactured by Nippon Nyukazai Co., Ltd., trade name "Butyl diglycol").
- Nonionic surfactant (XP-100): 2-propylheptyl alcohol ethoxylate (alkyl group: branched chain with 10 carbon atoms, average repeating number of oxyethylene group is 10 (manufactured by BASF, Lutensol XP-100).
≪Preservative≫
- BIT: 1,2-benzisothiazolin-3-one (manufactured by Arch Chemicals, trade name "PROXELXL2").
- MIT: 2-methyl-4-isothiazolin-3-one (manufactured by Rohm & Haas Japan Co., Ltd., trade name "Neolon M-10").
≪Fragrance≫
- Perfume: A 1:1 (mass ratio) mixture of perfume composition A and perfume composition B listed in Tables 1 to 6 of Japanese Patent Application No. 2017-085282 (Japanese Patent Application Publication No. 2018-184494).
≪Dye≫
・Green No. 3: Manufactured by Kinmi Kasei Co., Ltd.
≪pH adjuster≫
・NaOH: Sodium hydroxide, manufactured by Kanto Chemical Industry Co., Ltd.
・Sulfuric acid: Manufactured by Kanto Chemical Industry Co., Ltd.
≪Solvent≫
・Water: Ion exchange water.

(Evaluation method)
<Water spot reduction effect>
The object to be cleaned was a stainless steel plate (SUS304) measuring 5 cm x 2.5 cm. Add 38 g of tap water and 2 g of the liquid cleaning composition to a dishwashing sponge measuring 11.5 cm x 7.5 cm x 3 cm, rub it by hand 10 times, and then rub the surface of one stainless steel plate of the object to be cleaned 10 times. I scrubbed it. Thereafter, the operation of rinsing with tap water for 10 seconds was repeated three times. This stainless steel plate was stood upright so as to be almost vertical, and a water film formed on the surface of the stainless steel plate was visually observed. The observation results were classified according to the following evaluation criteria, and if it was 0 or higher, it was judged that the water spot reduction effect was excellent. Note that when a water film is formed on the surface of the stainless steel plate, the water flows down in a film form, making it difficult for water droplets to remain when the stainless steel plate dries. For this reason, the larger the area of the water film on the surface of the stainless steel plate, the fewer the number of water droplets and the less likely it is that water spots will form.

≪Evaluation criteria≫
◎◎: 80% or more of the area of the stainless steel plate is covered with a water film.
◎: 50% or more and less than 80% of the area of the stainless steel plate is covered with a water film.
○: 20% or more and less than 50% of the area of the stainless steel plate is covered with a water film.
×: Less than 20% of the area of the stainless steel plate is covered with a water film.

<Null suppression effect>
The object to be cleaned was a 21 cm diameter ceramic plate with no dirt attached. 45 g of tap water and 5 g of the liquid cleaning composition were placed in a 100 mL beaker and stirred to prepare a cleaning liquid. 40 g of the cleaning liquid was dropped onto the ceramic dish of the object to be cleaned. This plate was rubbed with fingers 10 times, and the degree of sliminess was evaluated using the following evaluation criteria. In this evaluation method, five professional evaluators performed the evaluation, and the evaluation scores of each evaluator were totaled. A total score of 〇 or higher (4 points or higher) was considered a pass.

(Evaluation criteria)
3 points: Nullness is greatly reduced.
2 points: Nullness is considerably reduced.
1 point: Slightly reduced nulliness.
0 point: Nullness is not reduced at all.

◎◎: Total score of 5 professional evaluators is 15-12 points.
◎: Total score of 5 expert evaluators is 11-8 points.
○: Total score of 5 expert evaluators is 7 to 4 points.
×: Total score of 5 expert evaluators is 3 to 0 points.

(Examples 1 to 42, Comparative Examples 1 to 12)
According to the compositions shown in Tables 1 to 5, components (A) to (D) and optional components were added to water and mixed to prepare liquid cleaning compositions for each example.
The blending amounts in the table are pure equivalent values. Components whose blending amounts are not listed in the table are not blended. In the table, the "appropriate amount" of the pH adjuster content is the amount required to achieve the pH shown in the table. In the table, the water content "balance" is the amount required to make the liquid cleaning composition 100% by mass.
The liquid cleaning agent of each example was evaluated for water spot reduction effect and slimy suppression effect, and the results are shown in the table.

As shown in Tables 1 to 5, in Examples 1 to 42 to which the present invention is applied, the water spot reduction effect is “〇” to “◎◎”, and the nulling suppression effect is “〇” to “◎◎”. ◎◎”.
Comparative Example 1, in which the content of component (A) was 3% by mass, was rated "poor" in terms of water spot reduction effect and nulling suppression effect.
Comparative Example 2, in which the content of the component (A) was 13% by mass, and Comparative Example 4, in which the content of the component (C) was 3% by mass, was rated "x" in the nulling suppression effect.
In Comparative Example 3 in which the content of component (C) was 0.01% by mass, the water spot reduction effect was rated "x".
Comparative Examples 5 and 6 containing component (C') in place of component (C) were rated "x" in terms of water spot reduction effect and nulling suppression effect.
In Comparative Example 7 where the A/D ratio was 0.5 and Comparative Example 8 where the A/D ratio was 30, the water spot reducing effect and nulling suppressing effect were rated "x".
Comparative Examples 9 to 12, which lacked any of the components (A) to (D), were rated "x" in the water spot reduction effect and the nulling suppression effect.
From the above results, it was confirmed that by applying the present invention, water spots on stainless steel can be reduced and nulling can be suppressed.

Claims

Contains (A) component, (B) component, (C) component, and (D) component,
The component (A) is an anionic surfactant (excluding soap (higher fatty acid salt)),
The component (B) is at least one selected from semipolar surfactants and amphoteric surfactants,
The component (C) is cationized cellulose,
The component (D) is an aminocarboxylic acid type chelating agent,
For the total mass of the liquid cleaning composition,
The content of the component (A) is 4 to 12% by mass,
The content of the component (C) is 0.05 to 2.5% by mass,
A liquid detergent composition for tableware, wherein the mass ratio represented by the component (A)/component (D) is from 0.8 to 23.
The liquid detergent composition for tableware according to claim 1, wherein the mass ratio represented by the component (A)/(component (C) + component (D)) is 0.5 to 12.5. thing.
The liquid detergent composition for tableware according to claim 1 or 2, wherein the mass ratio represented by the component (A)/component (B) is 0.25 to 2.
The liquid detergent composition for tableware according to claim 1 or 2, wherein the component (D) is at least one selected from methylglycine diacetic acid and a salt thereof.