JP2024089925A - Liquid dishwashing detergent composition - Google Patents

Abstract

The present invention provides a liquid detergent composition for dishes that can enhance the cleaning power against oily stains and suppress the formation of water spots.
[Solution] The composition comprises component (A): a nonionic cellulose having a weight average molecular weight of 100,000 or more, component (B): a nonionic surfactant, and component (C): at least one selected from a compound represented by the following formula (c1) and a compound represented by the following formula (c2).
R ³ -O-(C ₂ H ₄ O) _x -(C ₃ H ₆ O) _y -R ⁴ ... (c1), C ₆ H ₅ -(C ₂ H ₄ O) _l -(C ₃ H ₆ O) _m -(CH ₂ ) _n -R ⁵ ... (c2)
[Selection diagram] None

Description

The present invention relates to a liquid detergent composition for dishwashing.

When washing dishes, in addition to the "grease-removing power" required to thoroughly remove grease stains from the dishes being washed, "quick-drying" (the ability to dry so that no water droplets or stains remain on the dishes after washing) is also required in order to improve the image of cleanliness and hygiene.
The cause of water spots on washed dishes after drying is water droplets remaining on the surface. When water droplets that remain on the surface after washing dry, they form water spots on the surface. To address this problem, studies have been conducted to change the condition of the surface of the dishes after washing by adsorbing polymers, etc. to the surface of the dishes.

For example, Patent Document 1 proposes a liquid detergent composition for dishwashing, which contains an anionic surfactant, an amine oxide surfactant or an amphoteric surfactant, a cationic polymer, a chelating agent, and a propylene oxide adduct of a trihydric to hexahydric alcohol in a specific ratio. According to the invention of Patent Document 1, sliminess is reduced and drainage is improved.
Patent Document 2 proposes a liquid detergent composition for hard surfaces, which contains a cationic polysaccharide, an alkaline agent, an anionic surfactant, and water in a specific mass ratio. According to the invention of Patent Document 2, the cleaning power for oily stains and the antifouling properties are improved.

JP 2022-063462 A JP 2022-055708 A

However, while conventional techniques can suppress water spots on ceramic and polyvinyl chloride (PVC) dishes, they did not assume the use of polypropylene (PP) dishes. PP is hydrophobic, and oil stains attached to hydrophobic dishes are strong. For this reason, there is a demand for a cleaner that can suppress water spots while improving the cleaning power against oil stains.
Therefore, an object of the present invention is to provide a liquid detergent composition for dishes that can further enhance the cleaning power against oily stains and suppress the formation of water spots.

The present invention has the following aspects.
<1>
(A) component: nonionic cellulose having a weight average molecular weight of 100,000 or more;
(B) component: a nonionic surfactant;
Component (C): at least one selected from a compound represented by the following formula (c1) and a compound represented by the following formula (c2),
A liquid detergent composition for dishwashing, comprising:
R ³ —O—(C ₂ H ₄ O) _x /(C ₃ H ₆ O) _y —R ⁴ ... (c1)
In formula (c1), R ³ and R ⁴ are each independently H, OH, an alkenyl group having 1 to 6 carbon atoms, or a phenyl group, x is a number from 0 to 5 representing the average number of repetitions of (C ₂ H ₄ O), and y is a number from 0 to 5 representing the average number of repetitions of (C ₃ H ₆ O) (however, x and y cannot be 0 at the same time).
_C6H5- ( _{C2H4O ) l} /( _C3H6O ) _m- ( _CH2 ) _n ^- _{R5 ...} (c2)
(In formula ( _c2 ), ^R5 is H or OH, l is a number from 0 to 5 representing the average number of repetitions of ( _C2H4O ), m is a number from 0 to 5 representing the average number of repetitions of ( _C3H6O ), and n is a number from 0 to 3 representing _the average number of repetitions of ( _CH2 ).)
＜2＞
The liquid detergent composition for dishwashing according to <1>, wherein the mass ratio of the component (B) to the component (A) is 0.2 to 200.
＜3＞
The liquid detergent composition for tableware according to <1> or <2>, wherein the mass ratio of the component (C) to the component (A) is 0.05 to 200.
＜4＞
The liquid detergent composition for dishwashing according to <1> or <2>, which is for spray use.

The liquid detergent composition for dishes of the present invention can further enhance the cleaning power against oily stains and suppress water spots.

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

<Component (A)>
The component (A) is a nonionic cellulose having a weight average molecular weight of not less than 100,000. By containing the component (A), the liquid detergent composition can suppress the formation of water spots (water spot suppression effect).

Component (A) is a cellulose derivative having hydroxyl groups that do not ionize when dissolved in water, and in which some of the hydroxyl groups have been substituted with alkoxy groups or hydroxyalkoxy groups.
Examples of the alkoxy group as a substituent include alkoxy groups having 1 to 3 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, etc. Examples of the hydroxyalkoxy group as a substituent include hydroxyalkoxy groups having 1 to 3 carbon atoms, such as a hydroxymethoxy group, a hydroxyethoxy group, a hydroxypropoxy group, etc. Hereinafter, alkoxy groups and hydroxyalkoxy groups are collectively referred to as (hydroxy)alkoxy groups.
The degree of substitution with (hydroxy)alkoxy groups in component (A) is preferably 4 to 70 mol%, and more preferably 4 to 30 mol%. When the degree of substitution is equal to or greater than the lower limit, the cleaning power and the effect of suppressing water spots can be further improved. When the degree of substitution is equal to or less than the upper limit, the cleaning power and the effect of suppressing water spots can be further improved.

Component (A) may be hydroxypropylmethylcellulose (HPMC), methylcellulose (MC), hydroxyethylcellulose (HEC), etc. Among these, component (A) is preferably HPMC. These components (A) can further increase the cleaning power and further enhance the effect of suppressing water spots.

The weight average molecular weight of component (A) is 100,000 or more, preferably 200,000 to 1,000,000, and more preferably 200,000 to 300,000. When the weight average molecular weight is equal to or greater than the lower limit, the effect of suppressing water spots can be further improved. When the weight average molecular weight is equal to or less than the upper limit, the cleaning power can be further improved.

The viscosity of a 2% by mass aqueous solution of component (A) is preferably 40 to 20,000 mPa·s, more preferably 3,000 to 14,000 mPa·s, and even more preferably 3,000 to 5,600 mPa·s. When the viscosity is equal to or greater than the lower limit, the effect of suppressing water spots can be further improved. When the viscosity is equal to or less than the upper limit, the cleaning power can be further improved.
The viscosity is a value measured using a Brookfield viscometer for a 2% by mass aqueous solution of component (C) at 25° C. The viscosity measurement conditions are as follows:

Measurement condition:
[rotor]
The rotor numbers and rotor rotation speeds corresponding to the viscosities to be measured are as follows:
Viscosity less than 500 mPa·s: rotor number 2, rotation speed 60 rpm.
Viscosity of 500 mPa·s or more and less than 2000 mPa·s: rotor number 3, rotation speed 60 rpm.
Viscosity of 2000 mPa·s or more and less than 10000 mPa·s: rotor number 4, rotation speed 60 rpm.
Viscosity of 10,000 mPa·s or more and less than 50,000 mPa·s: rotor number 4, rotation speed 12 rpm.

The content of component (A) is preferably 0.1 to 2 mass%, more preferably 0.5 to 1.5 mass%, and even more preferably 0.5 to 1 mass%, based on the total mass of the liquid detergent composition. When the content of component (A) is equal to or greater than the lower limit, the effect of suppressing water spots can be further improved. When the content of component (A) is equal to or less than the upper limit, the cleaning power can be further improved.

<Component (B)>
The component (B) is a nonionic surfactant. The liquid detergent composition contains the component (B), which enhances the cleaning power against oily stains. In addition, the liquid detergent composition contains the component (B), which allows the composition to be sprayed uniformly over a wide area when discharged from a spray container (excellent sprayability).

Component (B) includes polyoxyalkylene-type nonionic surfactants, alkyl polyglycosides having an alkyl group with 8 to 18 carbon atoms, sucrose fatty acid esters having a fatty acid group with 8 to 18 carbon atoms, and alkyl polyglyceryl ethers having an alkyl group with 8 to 18 carbon atoms. Among these, polyoxyalkylene-type nonionic surfactants are preferred from the viewpoint of improving sprayability.

An example of a polyoxyalkylene-type nonionic surfactant is a surfactant represented by the following formula (b1).

R ¹ -O-(R ² O) _j -H... (b1)

In formula (b1), R ¹ is a linear or branched hydrocarbon group having 10 to 18 carbon atoms, R ² is preferably an alkylene group or an alkenylene group having 1 to 3 carbon atoms, more preferably an alkylene group, and even more preferably an ethylene group, and j represents the average number of repetitions of (R ² O) and is a number from 1 to 20.

R ¹ preferably has 8 to 10 carbon atoms.
R ¹ may be a saturated or unsaturated hydrocarbon group.
When R ¹ is linear, --O-- may be bonded to a primary carbon of R ¹ or to a secondary carbon of R ¹ .
^R1 is preferably a branched or secondary hydrocarbon.
^R2 preferably has 2 to 3 carbon atoms, and more preferably has 2 carbon atoms.

j represents the average number of repetitions of (R ² O) (that is, oxyalkylene group) (that is, the average number of moles of alkylene oxide added).

The content of component (B) is preferably 0.5 to 20 mass %, more preferably 5 to 15 mass %, and even more preferably 10 to 15 mass %, based on the total mass of the liquid detergent composition. When the content of component (B) is equal to or greater than the lower limit, the cleaning power can be further improved. When the content of component (B) is equal to or less than the upper limit, the water spot suppression effect can be further improved.

The mass ratio of component (B) to component (A), expressed as component (B)/component (A) (B/A ratio) is preferably 0.2 to 200, more preferably 3.33 to 30, and even more preferably 10 to 20. When the B/A ratio is equal to or greater than the lower limit, the cleaning power can be further improved. When the B/A ratio is equal to or less than the upper limit, the effect of suppressing water spots can be further improved.

<Component (C)>
Component (C) is at least one selected from a compound represented by the following formula (c1) (component (c1)) and a compound represented by the following formula (c2) (component (c2)). By containing component (C), the liquid detergent composition enhances the detergency against oily stains.

R ³ —O—(C ₂ H ₄ O) _x /(C ₃ H ₆ O) _y —R ⁴ ... (c1)

In formula (c1), R ³ and R ⁴ are each independently H, OH, an alkenyl group having 1 to 6 carbon atoms, or a phenyl group, x is a number from 0 to 5 representing the average number of repetitions of (C ₂ H ₄ O), and y is a number from 0 to 5 representing the average number of repetitions of (C ₃ H ₆ O) (however, x and y cannot be 0 at the same time).

In formula (c1), (C ₂ H ₄ O) _x /(C ₃ H ₆ O) _y indicates that the oxyethylene groups and the oxypropylene groups may be block polymerized or random polymerized.

As the (c1) component, a compound in which ^R3 is a phenyl group or an alkenyl group having 1 to 3 carbon atoms, ^R4 is H or OH, x is 0 to 4, and y is 0 is preferred, and a compound in which ^R3 is a phenyl group, ^R4 is H, x is 1 to 3, and y is 0 is preferred. Preferred examples of the (c1) component include phenyl glycol, phenyl carbitol, butyl carbitol, and phenyl triglycol.

_C6H5- ( _{C2H4O ) l} /( _C3H6O ) _m- ( _CH2 ) _n ^- _{R5 ...} (c2)
(In formula ( _c2 ), ^R5 is H or OH, l is a number from 0 to 5 representing the average number _of repetitions of ( _C2H4O ), m is a number from 0 to 5 representing the average number of repetitions of ( _C3H6O ), and n is a number from 0 to 3 representing the average number of repetitions of ( _CH2 ) (however, l, m, and n cannot be 0 at the same time).)

In formula (c2), (C ₂ H ₄ O) _l /(C ₃ H ₆ O) _m indicates that the oxyethylene groups and the oxypropylene groups may be block polymerized or random polymerized.

As the (c2) component, a compound in which ^R5 is OH, l is 0 to 3, m is 0 to 3, and n is 0 to 3 is preferred, and a compound in which l is 0, m is 0, and n is 1 to 3 is more preferred. Preferred examples of the (c2) component include benzyl alcohol and phenethyl alcohol.

As the component (C), phenyl glycol, phenyl carbitol, and benzyl alcohol are preferred.
The above component (C) may be used alone or in combination of two or more.

The content of component (C) is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 5 to 10% by mass, based on the total mass of the liquid detergent composition. When the content of component (C) is equal to or greater than the lower limit, the cleaning power can be further improved. When the content of component (C) is equal to or less than the upper limit, the water spot suppression effect can be further improved.

The mass ratio of component (C) to component (A), expressed as component (C)/component (A) (C/A ratio), is preferably 0.05 to 200, more preferably 0.67 to 30, and even more preferably 5 to 20. When the C/A ratio is equal to or greater than the lower limit, the cleaning power can be further improved. When the C/A ratio is equal to or less than the upper limit, the cleaning power can be further improved, and the water spot suppression effect can be further improved.

<Optional ingredients>
The liquid detergent composition may contain optional components other than the components (A) to (C) as long as the effects of the present invention are not impaired.
The total amount of components (A) to (C) and any optional components does not exceed 100% by mass.

Optional components may be any components that are used in liquid dishwashing detergent compositions. Optional components include water, surfactants other than component (B) (optional surfactants), hydrotropes, preservatives, pH adjusters, chelating agents, fragrances, colorants, thickeners, etc.

Water functions as a solvent for the liquid detergent composition. The water content is more preferably 40 to 85% by mass, and even more preferably 60 to 80% by mass, based on the total mass of the liquid detergent composition. If the water content is equal to or greater than the lower limit, gelation is suppressed and the uniformity of the liquid is increased. If the water content is equal to or less than the upper limit, the viscosity does not become too low, and usability is excellent.

Examples of the chelating agent include organic acids and their salts such as aminocarboxylic acid type chelating agents, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, gluconic acid, and salts thereof. Examples of the salts include sodium salts.
Examples of aminocarboxylic acid type chelating agents include ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), dihydroxyethylglycine (DHEG), hydroxyethyleneiminodiacetic acid (HIDA), diethylenetriaminepentaacetic acid (DTPA), methylglycine diacetic 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), iminodiacetic acid (IMDA), and β-alanine diacetic acid (ADAA). Examples of the salts of the aminocarboxylic acid type chelating agents include succinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), N-lauroylethylenediaminetriacetic acid, nitrilotriacetic acid (NTA), triethylenetetraaminehexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH), glycol ether diaminetetraacetic acid (GEDTA), dicarboxymethyl glutamic acid (CMGA), (S,S)-ethylenediaminedisuccinic acid (EDDS), and salts thereof. Examples of the salt forms of the aminocarboxylic acid type chelating agents include sodium salts and potassium salts.
As the aminocarboxylic acid type chelating agent, MGDA, GLDA, EDTA, HEDTA, DHEG, HIDA and DTPA are preferred, MGDA, GLDA and EDTA are more preferred, and MGDA is even more preferred.
These chelating agents may be used alone or in combination of two or more.

The content of the chelating agent is preferably 0.1 to 5 mass % relative to the total mass of the liquid detergent composition, more preferably 0.5 to 5 mass %, and even more preferably 1 to 3 mass %. If the content of the chelating agent is equal to or greater than the lower limit, water spots can be further reduced. If the content of the chelating agent is equal to or less than the upper limit, water spots can be further reduced and sliminess can be further suppressed.

The optional surfactant includes anionic surfactants, cationic surfactants, nonionic surfactants, and the like.
The content of the optional surfactant is preferably 0.1 to 5 mass % based on the total mass of the liquid detergent composition. However, it is preferable that the liquid detergent composition is substantially free of anionic surfactant. By not containing an anionic surfactant, the liquid detergent composition can further enhance the water spot suppression effect. Note that "substantially free" means an amount to the extent that the function of the liquid detergent composition is not affected by the anionic surfactant.

Examples of the hydrotropic agent include orthotoluenesulfonic acid, metatoluenesulfonic acid, paratoluenesulfonic acid, and salts thereof, cumenesulfonic acid, cumenesulfonate salts, ethanol, and butylcarbitol.
The preservatives include isothiazoline compounds, and specific examples thereof include benzisothiazolinone (1,2-benzisothiazolin-3-one), methylisothiazolinone (2-methyl-4-isothiazolin-3-one), butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, and dichlorooctylisothiazolinone.
Examples of the pH adjuster include inorganic alkaline agents, organic alkaline agents, and inorganic acids.
Examples of the inorganic alkaline agent include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
Examples of the organic alkaline agent include amine compounds such as monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N-(β-aminoethyl)ethanolamine, diethylenetriamine, morpholine, and N-ethylmorpholine.
Examples of the inorganic acid include hydrochloric acid and sulfuric acid.
The organic acid includes 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, the effect of suppressing water spots can be further improved.
The pH (25° C.) of the liquid detergent composition is a value measured by a method in accordance with JIS Z 8802:1984 "pH measurement method".

The viscosity of the liquid detergent composition of the present invention at 25°C is preferably 10 to 200 mPa·s, more preferably 50 to 150 mPa·s. If the viscosity is equal to or greater than the lower limit, dripping from the spout of the container can be effectively suppressed. If the viscosity is equal to or less than the upper limit, the liquid detergent composition can be more easily dispensed from the container.

The viscosity of the liquid detergent composition can be adjusted by the water content, the addition of a thickener, etc.
The viscosity of the liquid detergent composition is a value measured at 25° C. using a Brookfield viscometer with rotor number 1 at a rotor rotation speed of 60 rpm, 60 seconds after the rotor starts rotating.

(Production method)
The liquid detergent composition of the present invention is produced by a conventionally known production method.
Examples of methods for producing the liquid detergent composition include a method in which the components (A) to (C) and, if necessary, any optional components are added to a portion of water, mixed, the pH is adjusted, and then the remainder of the water is added.

Liquid Detergent Composition Articles
The liquid detergent composition may be contained in a container to form a liquid detergent composition article. The container may be a container used for washing dishes, such as a spray container or a pull-top container, or a refill pouch.

(how to use)
Examples of the method of using the liquid detergent composition include a method of applying the liquid detergent composition to a cleaning tool, foaming the liquid detergent composition on the cleaning tool, and scrubbing the dishware to be washed with the foamed cleaning tool. Another example of the method of applying the liquid detergent composition to the object to be washed and scrubbing it with the cleaning tool. In these cleaning methods, it is preferable to spray the liquid detergent composition from a spray container onto the cleaning tool or the object to be washed.
Alternatively, the liquid detergent composition may be dissolved in water to prepare a cleaning liquid, and the object to be cleaned may be immersed in the cleaning liquid and scrubbed with a cleaning tool. In either method, the object to be cleaned after scrubbing is rinsed with water, and then the water from the object to be cleaned is drained.

Cleaning tools include sponges, brushes, cloths, etc.
The objects to be washed include ceramics, metal utensils, etc. Examples of ceramics include tableware such as plates, bowls, rice bowls, etc. Examples of metal utensils include tableware such as forks and spoons, stainless steel sinks, etc.

The liquid detergent composition of the present invention contains components (A) to (C), and therefore has excellent detergency against oily stains and can suppress water spots on the washed items.
The liquid detergent composition of the present invention is particularly suitable for use as a spray when contained in a spray container.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

(Raw materials used)
<Component (A)>
A-1: HPMC-1, hydroxypropyl methylcellulose, degree of methoxy group substitution = 28 to 30 mol%, degree of hydroxypropoxy group substitution = 7 to 12 mol%, weight average molecular weight = 100,000, viscosity of 2 mass% aqueous solution 40 to 60 mPa s, product name "METLOSE 60SH-50", manufactured by Shin-Etsu Chemical Co., Ltd.
A-2: HPMC-2, hydroxypropyl methylcellulose, degree of methoxy group substitution = 28 to 30 mol%, degree of hydroxypropoxy group substitution = 7 to 12 mol%, weight average molecular weight = 300,000, viscosity of 2 mass% aqueous solution 3000 to 5600 mPa s, product name "METLOSE 60SH-4000", manufactured by Shin-Etsu Chemical Co., Ltd.
A-3: HPMC-3, hydroxypropyl methylcellulose, degree of methoxy group substitution = 28 to 30 mol%, degree of hydroxypropoxy group substitution = 7 to 12 mol%, weight average molecular weight = 500,000, viscosity of 2 mass% aqueous solution 7,500 to 14,000 mPa s, product name "METLOSE 60SH-10000", manufactured by Shin-Etsu Chemical Co., Ltd.
A-4: HPMC-4, hydroxypropyl methylcellulose, degree of methoxy group substitution = 19 to 24 mol%, degree of hydroxypropoxy group substitution = 4 to 12 mol%, weight average molecular weight = 120,000, viscosity of 2 mass% aqueous solution 80 to 120 mPa s, product name "METLOSE 90SH-100", manufactured by Shin-Etsu Chemical Co., Ltd.
A-5: HPMC-5, hydroxypropyl methylcellulose, degree of methoxy group substitution = 19 to 24 mol%, degree of hydroxypropoxy group substitution = 4 to 12 mol%, weight average molecular weight = 300,000, viscosity of 2 mass% aqueous solution 3500 to 5600 mPa s, product name "METLOSE 90SH-4000", manufactured by Shin-Etsu Chemical Co., Ltd.
A-6: MC, methyl cellulose, degree of methoxy group substitution = 26 to 33 mol%, weight average molecular weight = 360,000, viscosity of 2 mass% aqueous solution 3000 to 5600 mPa·s, product name "METLOSE SM-4000", manufactured by Shin-Etsu Chemical Co., Ltd.
A-7: HEC, hydroxyethyl cellulose, degree of hydroxyethoxy group substitution = 30 to 70 mol%, weight average molecular weight = 1 million, viscosity of 2 mass% aqueous solution 5,000 to 10,000 mPa·s, product name "HEC CF-V", manufactured by Sumitomo Seika Chemicals.

<Component (A')> Comparative products for component (A) A'-1: HPMC-6, hydroxypropyl methylcellulose, degree of methoxy group substitution = 28 to 30 mol%, degree of hydroxypropoxy group substitution = 7 to 12 mol%, weight average molecular weight = 70,000, viscosity of 2 mass% aqueous solution = 1.3 to 18 mPa·s, product name "METLOSE 60SH-15", manufactured by Shin-Etsu Chemical Co., Ltd.
A'-2: CMC, carboxymethyl cellulose, weight average molecular weight = 80,000, viscosity of 2% by mass aqueous solution 918 mPa·s, product name "CMC Daicel 1260", manufactured by Daicel FineChem Ltd.
A'-3: CC, cationized cellulose, weight average molecular weight = 200,000 to 800,000, viscosity of 2% by mass aqueous solution 75 to 175 mPa·s, product name "SUPRACARE 212", manufactured by Dow Chemical Japan.

<Component (B)>
B-1: C10-AE (EO10), alcohol ethoxylate, a compound of the formula (b1) in which R ¹ is a branched alkyl group having 10 carbon atoms, R ² O is an oxyethylene group, and j is 10. Trade name "Lutensol XP-100", manufactured by BASF.
B-2: C10-AE (EO5), alcohol ethoxylate, a compound of the formula (b1) in which R ¹ is a linear alkyl group having 10 carbon atoms, R ² O is an oxyethylene group, and j is 5. Product name "TO-5", manufactured by BASF.
B-3: C1214-AE (EO9), alcohol ethoxylate, a compound of the formula (b1) in which R ¹ is a mixture of a secondary alkyl group having 12 carbon atoms and a secondary alkyl group having 14 carbon atoms, R ² O is an oxyethylene group, and j is 9. Trade name "Leocol SC-90", manufactured by Lion Specialty Chemicals.
B-4: C1214-AE (EO6), alcohol ethoxylate, a compound of the formula (b1) in which R ¹ is a mixture of a primary linear alkyl group having 12 carbon atoms and a primary linear alkyl group having 14 carbon atoms, R ² O is an oxyethylene group, and j is 6.

<Component (B')> Optional surfactant B'-1: SAS, secondary alkanesulfonic acid, alkyl group carbon number = 12 to 14, trade name "HOSTAPUR SAS 30A", manufactured by Clariant Japan KK
B'-2: AES, polyoxyethylene alkyl ether sulfate (a compound obtained by adding 1 mole of EO to natural alcohol (trade name "CO-1270" manufactured by P&G)), trade name "BRES(1)", manufactured by Lion.
B'-3: LAS, linear or branched alkylbenzene sulfonate having an alkyl group having 10 to 14 carbon atoms, product name "Lipon (registered trademark) LH-200", manufactured by Lion Corporation.

<Component (C)>
C-1: Phenyl glycol, C ₆ H ₅ —O—(CH ₂ CH ₂ O)—H, trade name “Newpol EFP”, manufactured by Sanyo Chemical Industries, Ltd. Corresponding to the component (c1).
C-2: Benzyl alcohol, C ₆ H ₅ —(CH ₂ O)—H, trade name “Benzyl Alcohol”, manufactured by Junsei Chemical Co., Ltd. Corresponding to component (c2).
C-3: Phenyl carbitol (phenyl diglycol), C ₆ H ₅ —O—(CH ₂ CH ₂ O)—(CH ₂ CH ₂ O)—H, trade name “Phenyl Diglycol”, manufactured by Tokyo Chemical Industry Co., Ltd. Corresponding to the component (c1).
C-4: Butyl carbitol (diethylene glycol monobutyl ether), C ₄ H ₉ —O—C ₂ H ₄ —O—C ₂ H ₄ —OH, product name “Diethylene glycol monobutyl ether”, manufactured by Tokyo Chemical Industry Co., Ltd. This corresponds to the component (c1).

<Optional ingredients>
·Sodium hydroxide.
·ethanol.
·citric acid.
・Water: Ion-exchanged water.

(Evaluation method)
<Cleaning evaluation>
To improve visibility, Sudan IV was uniformly dissolved in extra virgin olive oil (manufactured by Ajinomoto Co., Inc.) to a concentration of 0.1% by weight, which was used as the soil for evaluation. The soil thus prepared was weighed on an electronic balance and 0.1 g was uniformly applied to a hydrophobic container (manufactured by Iwasaki Kogyo Co., Ltd., Lastro Neokeeper 870 mL) using a poly dropper to prepare hydrophobic surface soil.
8 mL of each of the Examples and Comparative Examples was sprayed onto the hydrophobic surface dirt using a Lion Corporation "Look Around the Range" trigger spray container and left to stand for 60 seconds. After the above, the surface was thoroughly rinsed with running water at 25°C and a flow rate of 5 L/min, and the remaining dirt was visually confirmed and evaluated into three stages according to the following evaluation criteria.

Evaluation Criteria
○: Almost no dirt remains.
△: A little bit of dirt remains.
×: A large amount of dirt remains.

<Water spot reduction effect>
A hydrophobic container (Iwasaki Kogyo Co., Ltd., Lastro Neokeeper 870mL) was sprayed 8 times from a position 15cm away using the trigger spray of "Look around the range", and the hydrophobic container and the spray tip were thoroughly rinsed evenly with running water at 25°C and a flow rate of 5L/min. Then, 20g of tap water at 25°C was placed on the hydrophobic container, and the hydrophobic container was tilted at 80°. Immediately after tilting, the time it took for a water film to flow down the surface of the hydrophobic tableware was measured, and the results were classified according to the following evaluation criteria.
When a water film is formed on the surface of a hydrophobic food container, the water flows down slowly in a film-like manner, and water droplets that cause water spots are less likely to remain on the surface. On the other hand, if a water film is not formed on the surface of a hydrophobic container, the water flows away in a short time, and water droplets that cause water spots remain on the surface.

Evaluation Criteria
◎: More than 8 seconds.
○: 5 seconds or more and less than 8 seconds.
△: 2 seconds or more but less than 5 seconds.
×: Less than 2 seconds.

(Examples 1 to 31, Comparative Examples 1 to 11)
According to the compositions shown in Tables 1 to 4, components (A) to (C) and optional components were added to water and mixed to prepare liquid detergent compositions of each example.
The amounts in the table are calculated as pure contents. Ingredients without a listed amount in the table are not included. The "appropriate amount" of sodium hydroxide in the table is the amount required to achieve the pH in the table. The "balance" of water in the table is the amount required to make the liquid detergent composition 100% by mass.
The liquid detergent of each example was evaluated for its effect of reducing water spots and its cleaning power, and the results are shown in the table.

As shown in Tables 1 to 4, in Examples 1 to 31 in which the present invention was applied, the cleaning power was rated as "△" or "◯", and the water spot reduction effect was rated as "△" to "◎".
Comparative Examples 1 to 4, which contained the component (A') instead of the component (A), and Comparative Example 9, which lacked the component (A), were rated "x" for the effect of reducing water spots.
In Comparative Examples 5 to 7, which contained the component (B') instead of the component (B), the effect of reducing water spots was rated "x".
The cleaning power of Comparative Example 8, in which the amount of ethanol was increased instead of component (C), Comparative Example 10 lacking component (B), and Comparative Example 11 lacking component (C) were rated as "x".
From the above results, it was confirmed that the application of the present invention can reduce water spots and improve cleaning power.

Claims (4)

(A) component: nonionic cellulose having a weight average molecular weight of 100,000 or more;
(B) component: a nonionic surfactant;
Component (C): at least one selected from a compound represented by the following formula (c1) and a compound represented by the following formula (c2),
A liquid detergent composition for dishwashing, comprising:
R ³ —O—(C ₂ H ₄ O) _x /(C ₃ H ₆ O) _y —R ⁴ ... (c1)
In formula (c1), R ³ and R ⁴ are each independently H, OH, an alkenyl group having 1 to 6 carbon atoms, or a phenyl group, x is a number from 0 to 5 representing the average number of repetitions of (C ₂ H ₄ O), and y is a number from 0 to 5 representing the average number of repetitions of (C ₃ H ₆ O) (however, x and y cannot be 0 at the same time).
_C6H5- ( _{C2H4O ) l} /( _C3H6O ) _m- ( _CH2 ) _n ^- _{R5 ...} (c2)
(In formula ( _c2 ), ^R5 is H or OH, l is a number from 0 to 5 representing the average number of repetitions of ( _C2H4O ), m is a number from 0 to 5 representing the average number of repetitions of ( _C3H6O ), and n is a number from 0 to 3 representing _the average number of repetitions of ( _CH2 ).) The liquid dishwashing detergent composition according to claim 1, wherein the mass ratio of component (B) to component (A) is 0.2 to 200. The liquid dishwashing detergent composition according to claim 1 or 2, wherein the mass ratio of component (C) to component (A) is 0.05 to 200. The liquid dishwashing detergent composition according to claim 1 or 2, which is for spraying.