JP2016145306A - Liquid tableware detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid tableware detergent composition excellent in storage stability while exhibiting excellent washing performance to strains strongly adhered to a tableware surface by compositing and drying lipid and protein, and a washing method of dishes using the same.SOLUTION: There is provided a liquid tableware detergent composition containing alkanesulfonate (a) and a thickener (b) and having viscosity at 20°C of 60 mPa s to 5,000 mPa s and pH at 25°C of 6 to 11.SELECTED DRAWING: None

Description

  The present invention relates to a liquid dishwashing composition and a dishwashing method using the same.

Dirt that is a combination of lipid and protein, such as semi-boiled egg yolk, is firmly fixed to the tableware when dried. Therefore, pre-treatment such as pre-soaking in water is required before washing, which takes time and effort. ing.
Therefore, it is desired to develop a liquid dishwashing composition that can remove dirt without performing such a laborious pretreatment.

Conventionally, various cleaning compositions using an anionic surfactant or the like have been studied in order to improve the cleaning performance against dirt adhering to a hard surface. Patent Document 1 discloses a liquid detergent for hard surfaces having a pH of 3 or less, which contains an anionic surfactant such as acid, sodium alkanesulfonate, a nonionic surfactant, a thickening polysaccharide, and the like. According to Patent Document 1, it is disclosed that the liquid cleaning agent is excellent in spreadability to a slope portion of a toilet bowl, has high cleaning power for yellowing stains on ceramic tiles, and prevents adhesion of scale due to residual water droplets. .
Patent Document 2 discloses a method for producing a cleaning agent such as a thickening polysaccharide, a water-soluble solvent, an anionic surfactant, and a liquid cleaning agent for toilets containing water, and a liquid cleaning agent such as a shampoo, rinse, and cosmetics. Is described.
Patent Document 3 describes a composition for reducing microorganisms containing water, an antibacterial agent containing an anionic surfactant, an antifoaming agent, a sour agent, a stabilizer, and a thickener, and a method for cleaning agricultural products. ing.
Further, Patent Document 4 describes a liquid cleaning composition containing an alkyl sulfate surfactant and having good grease cleaning and foaming.

JP 2012-229381 A JP2013-249354A Special table 2013-533215 gazette Special table 2010-532813 gazette

However, although the invention of Patent Document 1 has been studied to prevent the adhesion of scale due to the remaining water droplets, it has not been studied on the detergency of dirt in which lipid and protein firmly bonded to tableware are combined. Moreover, although patent document 2 is described about examination of a manufacturing method, it is not examined about detergency. Furthermore, Patent Documents 3 and 4 do not discuss the detergency of dirt in which lipid and protein firmly bonded to tableware are combined.
According to the present invention, a liquid dishwashing composition that is excellent in storage stability as well as having excellent cleaning performance against dirt that is a complex of lipid and protein, dried and firmly fixed to the tableware surface, And a method for cleaning dishes using the same.

That is, the gist of the present invention is as follows.
[1] Contains an alkane sulfonate (a) and a thickener (b), has a viscosity at 20 ° C. of 60 mPa · s or more and 5,000 mPa · s or less, and a pH at 25 ° C. of 6 or more, 11 A liquid dishwashing composition which is:
[2] A method for washing dishes, wherein washing water obtained by diluting the liquid dishwashing composition according to [1] to 150 times or more and 3000 times or less is brought into contact with an object to be washed attached to the dishes.

  According to the present invention, a liquid dishwashing composition that is excellent in storage stability as well as having excellent cleaning performance against dirt that is a complex of lipid and protein, dried and firmly fixed to the tableware surface, And the washing | cleaning method of the tableware using the same can be provided.

It is a perspective view of the container main body of a fixed discharge squeeze container. It is sectional drawing of the cap member for fixed amount discharge squeeze containers. It is a cross-sectional perspective view of the cap member for fixed amount discharge squeeze containers.

[Liquid dishwashing composition]
The liquid dishwashing composition of the present invention contains an alkanesulfonate (a) and a thickener (b), has a viscosity at 20 ° C. of 60 mPa · s to 5,000 mPa · s, and 25 A liquid dishwashing composition having a pH of 6 or more and 11 or less at 0 ° C., in which lipids and proteins are complexed and show excellent washing performance with respect to dirt that has been dried and firmly adhered to the tableware, It has excellent storage stability.

<Alkanesulfonate (a)>
In the present invention, alkane sulfonate is used for the purpose of obtaining a detergency against dirt which is a complex of lipid and protein, dried and firmly fixed to tableware.
The alkane sulfonate is preferably an alkane sulfonate having an alkyl group having preferably 10 or more carbon atoms, more preferably 12 or more carbon atoms, and preferably 20 or less, more preferably 18 or less. The secondary alkane sulfonates are more preferred. These alkane sulfonates may be used alone or in combination of two or more.
Examples of salts of alkane sulfonate include salts of group 1 or group 2 elements such as sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, etc. Among them, tea astringent stains, lipids and proteins are included. From the viewpoint of improving detergency against complex dirt and the like, a sodium salt is preferable.
Specific examples of the alkane sulfonate include sodium tetradecane sulfonate, sodium hexadecane sulfonate, and sodium octadecane sulfonate.
Among these, from the viewpoint of obtaining superior detergency, a mixture of secondary alkane sulfonates having 14 to 17 carbon atoms is preferable.
Commercially available products include Clariant, HOSTAPUR SAS60, Bayer MERSOLATE H-95, Kao Corporation, Ramtel PS, and the like.

  The content of the alkane sulfonate (a) in the liquid dishwashing composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and still more preferably. Is 1.2% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 4% by mass or less, and still more preferably 3% by mass. % Or less, more preferably 2% by mass or less.

<Thickener (b)>
In the present invention, the thickener (b) is used for the purpose of adjusting the viscosity of the liquid dishwashing composition.
Examples of the thickener (b) include pectin, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, tragacanth gum, carrageenan, locust bean gum, dextrin, dextrin fatty acid ester, Examples thereof include water-soluble polymers such as (meth) acrylic acid polymers or salts thereof, xanthan gum, guar gum, gelatin, sodium alginate, gum arabic, and starch, and water-swellable clay minerals such as smectite. As the water-soluble polymer having a sugar chain in the main chain, one that has been hydrophobized by introducing an alkyl group may be used.
Among these, from the viewpoint of thickening and storage stability, water-soluble polymers are preferable, hydroxyethyl cellulose, (meth) acrylic acid polymer salts and xanthan gum are more preferable, and (meth) acrylic acid polymer salts and Xanthan gum is even more preferred.

(Meth) acrylic acid polymers or salts thereof include (meth) acrylic acid homopolymers or salts thereof (hereinafter also referred to as “(b-1) component”), and (meth) acrylic acid and (meth) acrylic. 1 or more types chosen from the copolymer with an acid ester or its salt (henceforth "(b-2) component") are mentioned.
In the present specification, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”.
Examples of the “salt” in the component (b-1) and the component (b-2) include one or more selected from sodium salts, potassium salts, alkanolamine salts, and ammonium salts.
The component (b-1) and the component (b-2) may be a polymer using a salt-type compound as a monomer or a polymer neutralized after copolymerization, and both are used in combination. May be.

[(B-1) component]
The component (b-1) is a homopolymer of (meth) acrylic acid or a salt thereof, and specifically, a polymer or a salt thereof whose main constituent monomer is acrylic acid is preferable.

The amount of the structural unit derived from acrylic acid in the polymer constituting the component (b-1) is preferably 99.9 mol% or more, and preferably substantially 100 mol%.
The homopolymer of (meth) acrylic acid or a salt thereof is more preferably a crosslinked polyacrylic acid or a salt thereof obtained by using a compound having at least two ethylenically unsaturated groups as a crosslinking agent.

Examples of the compound having at least two ethylenically unsaturated groups include one or more selected from pentaerythritol tetraallyl ether, tetraallyloxyethane, triallyl phosphate, and polyallyl saccharose.
The amount of the crosslinking agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 3 parts by mass or less with respect to 100 parts by mass of acrylic acid.
Examples of the commercially available component (b-1) include Carbopol 980 and Carbopol 981, manufactured by Noveon Inc., and ACPEC HV501E and HV505E manufactured by Sumitomo Seika Co., Ltd.
These components (b-1) may be used alone or in combination of two or more.

[(B-2) component]
The component (b-2) is a copolymer of (meth) acrylic acid and (meth) acrylic acid ester or a salt thereof.
In the (meth) acrylic acid ester constituting the component (b-2), the hydrocarbon group constituting the ester is preferably an alkyl group, and the carbon number thereof is preferably 8 or more and 30 or less, more preferably 10 or more and 30 or less. It is.
Moreover, (b-2) component adds C2-C4 alkylene oxide (henceforth "AO") to 1 or more types chosen from (meth) acrylic acid and (meth) acrylic acid ester. A monomer unit, that is, a structural unit derived from one or more monomers selected from (meth) acrylic acid AO adducts and (meth) acrylic acid ester AO adducts may be included. Examples of AO include ethylene oxide, propylene oxide, and butylene oxide. Among these, ethylene oxide is preferable. (B-2) When the component contains a structural unit derived from one or more monomers selected from (Meth) acrylic acid AO adducts and (meth) acrylic acid ester AO adducts, the average addition mole of AO The number is preferably 5 or more and 20 or less.

In the component (b-2), the ratio of the (meth) acrylic acid ester monomer is preferably 0.2 mol or more and 10 mol or less, more preferably 100 mol of (meth) acrylic acid. It is 0.5 mol or more and 5 mol or less.
In addition, when a structural unit derived from AO is introduced, the ratio of one or more monomers selected from (meth) acrylic acid AO adducts and (meth) acrylic acid ester AO adducts is (meth) acrylic acid 100 Preferably it is 0.2 mol or more and 10 mol or less with respect to mol.

The component (b-2) preferably contains substantially only acrylic acid and methacrylic acid alkyl ester as constituent monomers, and further, a compound having at least two ethylenically unsaturated groups as a crosslinking agent, A cross-linked acrylic acid / alkyl acrylate copolymer or a salt thereof obtained by using 0.01 to 3 parts by mass with respect to 100 parts by mass of acrylic acid is more preferable.
Examples of commercially available (b-2) components include Carbopol ETD2020 manufactured by Noveon Inc., ACCEC HV501ER, ACCEC HV701EDR manufactured by Sumitomo Seika Co., Ltd., and the like.
These components (b-2) may be used alone or in combination of two or more.

Component (b-1) or component (b-2) has a viscosity of an aqueous solution of preferably 500 mPa · s or more, more preferably 1,000 mPa · s or more, still more preferably 3,000 mPa · s or more, and still more preferably. Is 5,000 mPa · s or more, more preferably 10,000 mPa · s or more, and preferably 100,000 mPa · s or less, more preferably 70,000 mPa · s or less, still more preferably 50,000 mPa · s or less. More preferably, it is 40,000 mPa · s or less.
In addition, the viscosity of the aqueous solution of the component (b-1) or the component (b-2) is such that the concentration of the component (b-1) or the component (b-2) is 1.0% by mass, It means the viscosity of an aqueous solution adjusted to pH 7.0 with sodium, measured at 20 ° C. using a Brookfield viscometer (rotor No. 4, rotation speed 12 r / m).

  It is preferable that 1 or more types of components chosen from (b-1) component and (b-2) component exist in a liquid dishwashing agent composition as a salt with the below-mentioned pH adjuster.

[Smectite]
In the present invention, smectite can be used as the thickener (b).
The smectite may be natural or synthetic, but those having a glassy content, feldspar, quartz, mica, calcium sulfate, calcium carbonate, manganese carbonate and the like are preferably 5% by mass or less.
Specific examples of the smectite include natural or synthetic colloidal silicates such as dioctahedral group montmorillonite, beidellite, nontroit, or trioctahedral group saponite, hectorite, stevensite.
Among these, hectorite is preferable, and commercially available products include Laponite series manufactured by Rockwood Additives, Kunipia manufactured by Kunimine Industries, and Smecton.

  The content of the thickener (b) in the liquid dishwashing composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. And preferably it is 7 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 4 mass% or less.

  The mass ratio [(a) / (b)] of the alkanesulfonic acid salt (a) to the thickener (b) is preferably 0.1 or more, more preferably from the viewpoint of the balance between detergency and viscosity. 0.2 or more, more preferably 0.3 or more, still more preferably 0.4 or more, and preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less, Still more preferably, it is 10 or less, More preferably, it is 8.0 or less, More preferably, it is 7.0 or less, More preferably, it is 6.0 or less.

<Silicone compound (c)>
In the present invention, it is preferable to use the silicone compound (c) for the purpose of suppressing foaming.
The silicone compound (c) is preferably a water-insoluble silicone compound from the viewpoint of suppressing foaming. In the present specification, “water-insoluble” means a property in which the amount dissolved in 1 L of ion-exchanged water at 20 ° C. is 1 g or less.

Specific examples of the silicone compound (c) include straight silicone compounds such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and modified silicones. In the present specification, “modified silicone” refers to polysiloxane having an organic group introduced at the side chain or terminal.
Modified silicones include long chain alkyl modified silicone, alkyl aralkyl modified silicone, alkyl polyether modified silicone, polyether modified silicone, higher alcohol ester modified silicone, higher fatty acid ester modified silicone, fluoroalkyl modified silicone, amino modified silicone, amide modified. One selected from silicone, amino polyether modified silicone, epoxy modified silicone, carboxyl modified silicone, carbinol modified silicone, phenol modified silicone, methacryl modified silicone, oxazoline modified silicone, polyester modified silicone, hydroxy modified silicone, and alkoxy modified silicone The above can be used.
Among these, at least one selected from dimethylpolysiloxane, methylphenylpolysiloxane, and polyether-modified silicone represented by the following formulas (c-1) to (c-3c) is preferable.

(C-1) Dimethylpolysiloxane As dimethylpolysiloxane, what is represented, for example by a following formula (c-1) is preferable.

(In Formula (c-1), a represents a number of 3 or more and 20,000 or less, preferably 10 or more and 10,000 or less, more preferably 100 or more and 5,000 or less, and still more preferably. Is 500 or more and 1,000 or less.)

(C-2) Methylphenyl polysiloxane As methylphenyl polysiloxane, what is represented, for example by a following formula (c-2a) or (c-2b) is preferable.

(In formula (c-2a), b represents a number of 1 or more and 20,000 or less, preferably 10 or more and 10,000 or less, more preferably 100 or more and 5,000 or less, and still more preferably. Is not less than 500 and not more than 2,000 In formula (c-2b), c and d are each a number of 1 or more and represent a number of 2 or more and 500 or less in total, preferably 5 or more, 300 Or less, more preferably 10 or more and 100 or less, and still more preferably 30 or more and 80 or less.

(C-3) Polyether-modified silicone As the polyether-modified silicone, for example, those represented by the formula (c-3a), (c-3b) or (c-3c) are preferable.

(In formulas (c-3a), (c-3b) and (c-3c), R ⁵¹ represents a group — (CH ₂ ) ₃ —O— (C ₂ H ₄ O) _g — (C ₃ H ₆ O). _h- A [A is a hydrogen atom or an alkyl group having 1 or more and 12 or less carbon atoms, and g and h each represent an integer of 0 or more and 50 or less in total, preferably 5 or more and 30 or less. E is an integer of 1 or more and 2,000 or less, preferably 10 or more and 1,000 or less, more preferably 50 or more and 500 or less. F represents an integer of 1 or more and 1,000 or less, preferably 10 or more and 500 or less, and more preferably 50 or more and 300 or less.

In the present invention, among these silicone compounds, a silicone compound represented by the formula (c-1) or (c-3a) is more preferable from the viewpoint of suppressing foaming.
The silicone compound (c) in the present invention may be in any form such as an oil type, an emulsion type, and a compound type, and among these, it is a compound type that is a mixture with an inorganic compound such as silica. Is preferred.

The weight average molecular weight of the silicone compound (c) is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and preferably 1,000,000 or less, more preferably 800,000 or less. More preferably, it is 600,000 or less.
The viscosity of the silicone compound (c) at 25 ° C. is preferably 100 mPa · s or more, more preferably 200 mPa · s or more, still more preferably 500 mPa · s or more, and preferably 10,000 mPa · s or less. More preferably, it is 5,000 mPa * s or less, More preferably, it is 1,500 mPa * s or less.

  When the liquid dishwashing composition contains the silicone compound (c), the content of the silicone compound (c) is preferably 0.005% by mass or more, more preferably 0.01% from the viewpoint of suppressing foaming. % Or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, and from the viewpoint of production cost and storage stability, preferably 3% by mass or less, more preferably 1% by mass or less. More preferably, it is 0.5 mass% or less, More preferably, it is 0.3 mass% or less, More preferably, it is 0.2 mass% or less.

<Anionic surfactant (d)>
In the present invention, together with the alkanesulfonic acid salt (a), an anionic surfactant represented by the following formula (d-1) (hereinafter referred to as component (d-1)) and the following formula (d- It is preferable to use one or more anionic surfactants selected from the anionic surfactants represented by 2) (hereinafter also referred to as component (d-2)). By using the alkane sulfonate (a) and the anionic surfactant (d) in combination, the cleaning performance is improved. In addition, by using the alkane sulfonate (a) and the anionic surfactant (d) in combination, after preparing a liquid dishwashing composition, the appearance does not occur for a long time without separation. An excellent liquid dishwashing composition can be obtained. Hereinafter, this property may be referred to as “storage stability of appearance”.

[(D-1) component]
The component (d-1) in the present invention is an anionic surfactant represented by the following formula (d-1).
R ^1a -O - _{[(PO) m / (EO)} n ] ^{_{-SO 3 - M (d-1}} )
(In formula (d-1), R ^1a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, and m and n are averages of PO or EO. The number of moles added is a number that is 0 or more and 1.5 or less, M is an inorganic or organic cation, the order of addition of PO and EO is not limited, and “/” is PO and (This means that the addition form of EO may be block or random.)

M in the formula (d-1) is 0 or more, preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.4 or more, from the viewpoint of improving the storage stability and cleaning performance of the appearance. And 1.5 or less, preferably 1 or less, more preferably 0.8 or less.
Further, n in the formula (d-1) is 1.5 or less, preferably 1 or less, more preferably 0.1 or less, and further preferably 0, from the viewpoint of improving the storage stability and washing performance of the appearance. It is.
As the component (d-1) in the present invention, m is preferably 0.2 or more and 1 or less, more preferably 0.4 or more and 0.8 or less, from the viewpoint of improving the storage stability and washing performance of the appearance. And a compound in which n is 0 is preferable.

  M in the formula (d-1) is selected from an inorganic cation selected from sodium ion, potassium ion, lithium ion, magnesium ion, and ammonium ion, monoethanolammonium ion, diethanolammonium ion, and triethanolammonium ion acid salt. The organic cation is preferably sodium ion, potassium ion, magnesium ion or ammonium ion.

The method for preparing the compound of formula (d-1) is not particularly limited. For example, a predetermined amount of ethylene oxide and / or propylene oxide was added to the fatty alcohol represented by R ^1a —OH depending on the purpose. Thereafter, it is sulfated with a sulfating agent selected from sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid and chlorosulfonic acid, and neutralized with a predetermined alkali agent. The addition reaction of ethylene oxide and / or propylene oxide requires a catalyst, and an alkali hydroxide such as NaOH or KOH can be used. Moreover, the catalyst which has a magnesium oxide as a main component as described in Unexamined-Japanese-Patent No. 8-323200 can be used, The former can obtain polyoxyethylene alkyl ether with a comparatively wide average addition mole number distribution, The latter is A compound having a relatively narrow average added mole number distribution can be obtained. Further, as disclosed in JP-A-10-158384, the average addition mole number distribution can be controlled by using an alkali catalyst and a metal oxide catalyst in combination.

[(D-2) component]
The component (d-2) in the present invention is an anionic surfactant represented by the following formula (d-2).

(In the formula (d-2), R ^2a and R ^3a each independently have 5 or more carbon atoms, preferably 6 or more, more preferably 7 or more, and 18 or less, preferably 15 or less, more Preferably, it is an alkyl group having 13 or less or a hydrogen atom, and at least one of R ^2a and R ^3a is an alkyl group having 5 to 18 carbon atoms, and A ¹ and A ² each independently have 2 or more carbon atoms. And an alkylene group of 4 or less, preferably 3 or less, x and y are the average number of added moles and are 0 or more and 6 or less, and M is an inorganic or organic cation.)

A ¹ and A ² are each independently an alkylene group having 2 or more and 4 or less carbon atoms, preferably 2 or more and 3 or less carbon atoms, from the viewpoint of improving the storage stability and washing performance of the appearance.
x and y are average added mole numbers, and from the viewpoint of improving the storage stability and washing performance of the appearance, each is 0 or more and 6 or less, preferably 0 or more and 2 or less, more preferably 0 or more, 1 or less, particularly preferably 0.

When the component (d-2) is a sulfosuccinic acid dialkyl ester or a salt thereof, R ^2a and R ^3a in the formula (d-2) may be the same or different, and the storage stability and washing performance of the appearance From the viewpoint of improving the alkyl group, it is an alkyl group having 5 to 18 carbon atoms, more preferably 5 to 14 carbon atoms, more preferably 5 to 12 carbon atoms.
In addition, when the component (d-2) is a sulfosuccinic acid monoalkyl ester or a salt thereof, one of R ^2a and R ^{3a in} the formula (d-2) is a viewpoint that improves storage stability and washing performance of the appearance. Is an alkyl group having 5 to 18 carbon atoms, preferably 5 to 14 carbon atoms, more preferably 5 to 12 carbon atoms, and the other is a hydrogen atom.
R ^2a and R ^3a are each an alkyl group having 5 or more and 18 or less carbon atoms, preferably 5 or more and 14 or less, more preferably 5 or more and 12 or less, from the viewpoint of improving the storage stability and cleaning performance of the appearance. In other words, the component (d-2) is preferably a sulfosuccinic acid dialkyl ester or a salt thereof.

In formula (d-2), R ^2a and R ^3a are specifically hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, 2-ethylhexyl, n-octyl, sec -Octyl group, isopentyl group, isononyl group, isodecyl group, cyclohexyl group, particularly preferably a group selected from n-octyl group, sec-octyl group, decyl group, isodecyl group, and 2-ethylhexyl group. Among them, 2-ethylhexyl group is most preferable.
Examples of M include inorganic cations selected from hydrogen ions, sodium ions, potassium ions, magnesium ions, and ammonium ions, and organic cations selected from monoethanolammonium ions, diethanolammonium ions, and triethanolammonium ions. Is a cation selected from sodium ion, potassium ion, magnesium ion, and ammonium ion.

When the component (d-2) is a sulfosuccinic acid dialkyl ester or a salt thereof, the preparation method of the compound in which R ^2a and R ^3a are the same is not particularly limited. For example, US Pat. , 028,091 can be produced by referring to the method described in JP-A No. 58-24555, and an asymmetric compound having different R ^2a and R ^3a can be produced by referring to, for example, JP-A-58-24555. Can do. When a commercially available compound is used, Perex OT-P (a compound in which R ^2a and R ^3a are both 2-ethylhexyl groups) manufactured by Kao Corporation, a compound in which the same Plex TR (R ^2a and R ^3a are both tridecyl groups) ), LusitA-BO (a compound in which R ^2a and R ^3a are both 2-ethylhexyl groups) manufactured by BASF, and aerosol AY-100 (R ^2a and R ^3a are both amyl groups) available from Mitsui Cytec Co., Ltd. A certain compound), the same aerosol A-196 (a compound in which R ^2a and R ^3a are both cyclohexyl groups), and the like.

  Specific examples of the component (d-2) include, for example, sodium salt of sulfosuccinic acid di (2-ethylhexyl) ester, sodium salt of sulfosuccinic acid di (1,3-dimethylbutyl) ester, sodium salt of sulfosuccinic acid dicyclohexyl ester Is mentioned. Among these, a sodium salt of sulfosuccinic acid di (2-ethylhexyl) ester is preferable.

  When an anionic surfactant (d) is used, the amount of the anionic surfactant (d) in the liquid dishwashing composition improves the storage stability of the appearance and the cleaning performance of the cleaning composition. From the viewpoint of making it preferable, it is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.7% by mass or more. Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less.

<Solvent>
In the present invention, a solvent other than water may be used. Solvents include ethanol, polyethylene glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, phenoxyethanol, phenyl glycol , Phenoxyisopropanol, butyl diglycol (diethylene glycol monobutyl ether), dibutylene glycol, and benzyl alcohol can be used.
Among these, propylene glycol and butyl diglycol are preferable, and propylene glycol is particularly preferable.
In the case of using a solvent, the amount of the solvent in the liquid dishwashing composition is preferably 2% by mass or more, more preferably 3% by mass or more from the viewpoint of improving the stability of the composition, and the production is inexpensive. From the viewpoint, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less.

<Metal ion sequestering agent>
In the present invention, it is preferable to use a sequestering agent for the purpose of capturing hardness components in the wash water and improving the washability.
As sequestering agent, citric acid, malic acid, tartaric acid, succinic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, 1,3-propanediamine triacetic acid, 1,3-diamino-2-hydroxy Polycarboxylic acids such as propanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, methylglycinediacetic acid, and hydroxyethylethylenediaminedicarboxymethylglutamic acid or salts thereof Can be used.
Among these, citric acid, succinic acid, ethylenediaminetetraacetic acid, dihydroxyethylglycine, methylglycine diacetic acid, hydroxyethylethylenediaminedicarboxymethylglutamic acid, and alkali metal salts thereof are preferable.
In the case of containing a sequestering agent, the content of the sequestering agent in the liquid dishwashing composition is preferably 1% by mass or more, more preferably 5% by mass or more, from the viewpoint of improving detergency. Preferably it is 10 mass% or more, More preferably, it is 12 mass% or more, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

<PH>
The pH at 25 ° C. of the liquid dishwashing composition is 6 or more and 11 or less. The storage stability of a liquid dishwashing composition improves that pH in 25 degreeC is in the said range.
The pH at 25 ° C. of the liquid dishwashing composition is 6 or more, preferably 7 or more, more preferably 7.2 or more, and 11 or less, preferably 9 or less, from the viewpoint of improving storage stability. More preferably 8.5 or less, and still more preferably 8 or less.

<PH adjuster>
In the present invention, a pH adjuster can be used to adjust the pH value to the above range.
As the pH adjuster, one or more selected from inorganic acids such as hydrochloric acid and sulfuric acid, sodium hydroxide, potassium hydroxide, and monoethanolamine can be used.
Among these, hydrochloric acid and sodium hydroxide are preferable.

<Other ingredients>
In the present invention, as other cleaning components, surfactants other than the above-mentioned surfactants, polymer components such as polypropylene glycol, and water-soluble such as sulfates, sulfites, hydrogen sulfates, hydrochlorides, phosphates, etc. Inorganic salts can be used.
Moreover, the other component which can be used for a normal liquid dishwashing agent composition can be mix | blended. Examples include bleaching agents, bleach activators, enzyme stabilizers such as calcium salts and formic acid, fragrances, fungicides, antifungal agents, and dyes.

<Viscosity>
The viscosity at 20 ° C. of the liquid dishwashing composition is 60 mPa · s or more and 5,000 mPa · s or less. When the viscosity at 20 ° C. is within the above range, liquid leakage or clogging from a specific container containing the liquid dishwashing composition can be prevented.
The viscosity at 20 ° C. of the liquid dishwashing composition is 60 mPa · s or more, preferably 100 mPa · s or more, more preferably 150 mPa · s or more, from the viewpoint of preventing liquid leakage or clogging of the liquid dishwashing composition. More preferably 200 mPa · s or more, still more preferably 250 mPa · s or more, and 5,000 mPa · s or less, preferably 2,000 mPa · s or less, more preferably 1,000 mPa · s or less, still more preferably Is 800 mPa · s or less, more preferably 600 mPa · s or less.
In addition, the viscosity at 20 ° C. of the liquid dishwashing composition in the present specification means a viscosity measured at 20 ° C. using a Brookfield viscometer (B-type viscometer). The rotor and the number of rotations when performing measurement are appropriately set so as to be close to full scale.

<The container suitable for the liquid dishwashing agent composition of this invention>
As a container for storing the liquid dishwashing composition of the present invention, for example, a fixed amount discharge that discharges a predetermined amount of the liquid dishwashing composition as a content liquid from the discharge port of the container by deforming the container body It is preferable to use a squeeze container.
Hereinafter, the fixed discharge squeeze container will be described with reference to FIG. A quantitative discharge squeeze container 10 shown in FIG. 1 is a hollow bottle-shaped container made of a synthetic resin, including a container body 11, a mouth part 12, a body part 13, a squeeze operation part 14, and a bottom part 15.
A detachable cap member (not shown), which will be described later, is attached to the mouth part 12 of the container body 11. And the squeeze container 10 can be filled with the said liquid tableware cleaning composition as a content liquid.

The squeeze container 10 deforms the container body 11 by squeezing (squeezing) the squeeze operation part 14 in the squeeze direction X in a state where the body part 13 of the container body 11 is gripped and tilted or inverted, for example, a cap member It is possible to discharge a predetermined amount of the liquid dishwashing composition from the discharge port provided to the discharge location.
In this embodiment, the container main body 11 can be manufactured with well-known synthetic resins, such as a polyethylene terephthalate, a polypropylene, a high density polyethylene, a vinyl chloride, for example, and can be formed by blow molding, for example.

  Next, a cap member that can be attached to and detached from the mouth 12 of the container body 11 will be described with reference to FIGS. The cap member 20 in FIGS. 2 and 3 is used by being attached to the mouth-neck portion 12 of the container body 11, and the liquid dishwashing agent composition from the discharge port 24 by squeeze deformation (squeezing deformation) of the squeeze operation unit 14. A liquid flow path for discharging an object is provided. In addition, the mouth part 12 and the cap member 20 are detachably mounted via various known screwing means and fitting means.

The cap member 20 has a spiral channel 25 that constitutes at least a part of a liquid channel from the neck 12 of the container body 11 to the discharge port 24. The spiral flow path 25 is formed by a spiral blade 21 provided in a cylindrical lead-out path 26 facing the discharge port 24 of the cap member 20. The spiral blade 21 is a plastic molded product integrally formed with the central shaft member 22.
In this embodiment, the spiral blade 21 is disposed by joining a support rod 23 provided integrally with the lower end portion of the central shaft member 22 to the peripheral edge portion of the lower end opening of the cylindrical lead-out path 26. In addition, it is preferable that the peripheral end surface of the spiral blade 21 is in contact with the inner peripheral surface of the cylindrical lead-out path 26.

The bottom surface portion 25 a of the spiral flow path 25 provided by the spiral blade 21 is a descending slope that continuously inclines from the upper end portion of the spiral blade 21 toward the trunk portion 13 of the container body 11 in the upright state of the squeeze container 10. Form a gradient. Here, the downward gradient is not limited as long as the bottom surface portion 25a of the spiral channel 25 has a downward gradient as a whole, and there may be a horizontal portion in the middle.
In the present embodiment, a form in which the spiral blade 21 makes one round around the central shaft member 22 is adopted, but the spiral blade 21 may have a form of less than one round around the central shaft member 22. It may be in the form of a circumference or more.
According to the cap member 20 of the present embodiment, the bottom surface portion 25a of the spiral flow path 25 has a downward slope in the upright state of the squeeze container 10 as described above, and therefore in a state before the squeeze container 10 is squeezed. , Leakage of liquid contents and dripping can be effectively avoided.

  The present invention is not limited to the above embodiment, and various modifications can be made. For example, the member for forming the spiral flow path provided in at least a part of the liquid flow path from the neck portion of the container body to the discharge port is not limited to the above-described spiral blade, and other various members Can be used.

<Performance and application>
Since the liquid dishwashing composition of the present invention has higher cleaning performance than conventional liquid dishwashing compositions, the amount used can be reduced. Further, since the amount of use can be reduced, the container can be made compact, and the amount of packaging material used can be reduced.
Moreover, the liquid dishwashing composition of this invention is suitable as a cleaning composition for automatic dishwashers.

[How to wash dishes]
The tableware cleaning method of the present invention is to bring cleaning water obtained by diluting the liquid dishwashing composition from 150 times to 3000 times into contact with an object to be cleaned attached to the tableware. When cleaning is performed using cleaning water obtained by diluting the liquid dishwashing composition within the above range, cleaning can be performed at low cost while maintaining the cleaning power.
In the dishwashing method of the present invention, the dilution rate of the liquid dishwashing composition is 150 times or more, preferably 180 times or more, more preferably 200 times or more, and still more preferably, from the viewpoint of the balance between cleaning power and washing cost. Is 300 times or more and 3000 times or less, preferably 1500 times or less, more preferably 1200 times or less, and still more preferably 1000 times or less.

The reagents used in the examples and comparative examples are shown below.
<(A) component>
Alkanesulfonate (a1): HOSTAPUR SAS60, manufactured by Clariant (secondary sodium alkanesulfonate having 14 to 17 carbon atoms)
<(B) component>
Thickener (b1): Cross-linked sodium polyacrylate, ACPEC HV-501E, manufactured by Sumitomo Seika Co., Ltd. Thickener (b2): Echo gum T (xanthan gum), manufactured by DSP Gokyo Food & Chemical Co., Ltd.

<(C) component>
Silicone compound (c1): XIAMETER ACP-1500 ANTIFOAM COMPOUND, manufactured by Toray Dow Corning (component (d))
Anionic surfactant (d1): an anionic surfactant represented by the formula (d-1), wherein R ^1a is an alkyl group having 12 carbon atoms, m = 0.6, n = An anionic surfactant which is 0 and M is a sodium ion.
Anionic surfactant (d2): sodium di (2-ethylhexyl) sulfosuccinate, reagent, manufactured by Tokyo Chemical Industry Co., Ltd.

<Solvent>
Propylene glycol, manufactured by Wako Pure Chemical Industries, Ltd. <Metal sequestering agent>
Citric acid, manufactured by Wako Pure Chemical Industries, Ltd.

<PH adjuster>
Hydrochloric acid or sodium hydroxide <water>
Ion exchange water

<Examples 1 to 5, Comparative Examples 1 and 2>
Each component was mixed so that it might become the ratio of Table 1, and 100g of liquid dishwashing agent compositions of Examples 1-5 and Comparative Examples 1 and 2 were prepared, respectively. In addition, about pH of a composition, pH of all the Examples and the comparative examples was adjusted to 7.5 using sodium hydroxide or hydrochloric acid (concentration 1M).

<PH measurement>
The pH value at 25 ° C. was measured according to JIS Z-8802: 2011 using a pH meter (manufactured by Horiba, Ltd., “F-52”, pH electrode 6367-10D). In addition, as a measurement solution, the liquid dishwashing agent composition prepared by the said Example and comparative example was used as it was, without diluting. The results are shown in Table 1.

<Measurement method of viscosity>
The liquid dishwashing composition prepared in the examples and comparative examples was measured for viscosity at 20 ° C. using a B-type rotational viscometer. In the case of Examples 1 to 3, Example 5, and Comparative Example 1, No. No. 2 rotor, in the case of Example 4, no. No. 3 rotor and Comparative Example 2 1 was used, the rotation number was 60 rpm, and the value after 2 minutes of rotation was taken as the measured value.

The liquid dishwashing composition prepared in Examples and Comparative Examples was subjected to the following evaluation.
<Evaluation of detergency of dried soft-boiled egg yolk stains>
-Preparation of test dish (1) The chicken eggs (5 pieces) were broken and the egg yolks were separated using an egg yolk separator.
(2) Five yolks were put into the screw tube (No. 8) and heated in a water bath (73 to 75 ° C.) for 10 minutes.
(3) The screw tube was taken out of the water bath and allowed to stand at 25 ° C. for 1 hour, and the semi-ripe egg yolk was scraped into a tea strainer and strained.
(4) 1 g after the well-stirred material was mixed well, and uniformly applied to a ceramic dish (9 cm rim meat dish (diameter 233 mm × 24 mm), manufactured by Kamada Shoten Co., Ltd.) with a paintbrush.
(5) The soft-boiled egg yolk applied to the ceramic dish was dried at 25 ° C. for a whole day and night to prepare a test dish.

・ Cleaning test The liquid dishwashing composition prepared in the above examples and comparative examples was put into a detergent container of a dishwasher (Panasonic Corporation, model number “NP-45VS5S” (built-in type)) and washed in a speed course. Went. One soiled ceramic dish was placed in the rightmost dish tray in the lower right part of the dishwasher. The washing water was a diluted solution obtained by diluting the liquid dishwashing composition of Examples and Comparative Examples 500 times.

-Evaluation method By 5 evaluators, the egg yolk remaining on the surface of the ceramic dish was visually observed and evaluated according to the following evaluation criteria. The average value of five people is shown in Table 1 as a result.
Evaluation criteria 5: Completely cleaned.
4: Slight dirt remains, but it is almost cleaned (within the allowable range).
3: Mostly cleaned, but dirt remains. Or it remains thin overall (outside the acceptable range).
2: Although it was able to wash | clean a little, most dirt remains.
1: Almost no washing.
0: Not washed at all.

<Appearance after 1 day from blending>
The liquid dishwashing composition prepared in the Examples and Comparative Examples was No. 11 (diameter 50 mm, height 95 mm) 100 g was put in a standard bottle, capped, and allowed to stand for 1 day, and the change in appearance was observed.
-Evaluation criteria 4: Although it is slightly cloudy as a whole, it is in a uniform state.
Although it looks whiter than 3: 4, it is in a uniform state (within tolerance).
2: It is in a non-uniform state as a whole, or some droplets are floating.
1: Clearly two-phase separation.

  As is apparent from Table 1, the liquid dishwashing composition of the present invention exhibits excellent cleaning performance against soils in which lipids and proteins are complexed and dried and firmly adhered to the tableware surface.

Table 2 shows formulation examples of the liquid dishwashing composition of the present invention.

The reagents used in the formulation examples are as follows.
・ Dimethylaminopropylamide stearate Nikko Chemicals Co., Ltd., NIKKOL Amidoamine MPS
・ Stearic acid diethylaminoethylamide Nikko Chemicals, NIKKOL Amidoamine SV
・ Polyoxyethylene lauric acid monoethanolamide (EO = 2mol)
Kawaken Fine Chemical Co., Ltd., Amidette 2L-Y
・ Polyoxyethylene coconut oil fatty acid monoethanolamide (EO = 3mol)
Kawaken Fine Chemical Co., Ltd., Amidette 2C
・ Ethanol (Wako Pure Chemical Industries, Ltd.)
・ Citric acid (Wako Pure Chemical Industries, Ltd.)
・ P-cumene sulfonic acid Takeka Co., Ltd., Takeka Tox 500
・ Benzoic acid (Wako Pure Chemical Industries, Ltd.)

Claims (7)

  Contains an alkanesulfonate (a) and a thickener (b), has a viscosity at 20 ° C. of 60 mPa · s or more and 5,000 mPa · s or less, and a pH at 25 ° C. of 6 or more and 11 or less. Liquid dishwashing composition.   The content of the alkanesulfonate (a) is 0.1% by mass or more and 20% by mass or less, and the content of the thickener (b) is 0.1% by mass or more and 7% by mass or less. The liquid dishwashing composition according to claim 1, wherein a mass ratio [(a) / (b)] of the alkanesulfonate to the thickener (b) is 0.1 or more and 50 or less. .   The liquid dishwashing composition according to claim 1 or 2, further comprising a silicone compound (c).   The liquid dishwashing composition of Claim 3 whose content of the said silicone compound (c) is 0.005 mass% or more and 3 mass% or less. Furthermore, one or more anionic surfactants selected from an anionic surfactant represented by the following formula (d-1) and an anionic surfactant represented by the following formula (d-2) The liquid dishwashing agent composition in any one of Claims 1-4 containing an agent.
R ^1a -O - _{[(PO) m / (EO)} n ] ^{_{-SO 3 - M (d-1}} )
(In formula (d-1), R ^1a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, and m and n are averages of PO or EO. The number of moles added is a number that is 0 or more and 1.5 or less, M is an inorganic or organic cation, the order of addition of PO and EO is not limited, and “/” is PO and (This means that the addition form of EO may be block or random.)

(In formula (d-2), R ^2a and R ^3a are each independently an alkyl group having 5 or more and 18 or less carbon atoms or a hydrogen atom, and at least one of R ^2a and R ^3a has 5 or more carbon atoms. A ¹ and A ² are each independently an alkylene group having 2 or more and 4 or less carbon atoms, x and y are average added mole numbers, and are 0 or more and 6 or less. Inorganic or organic cation.)   The liquid dishwashing composition in any one of Claims 1-5 which is an object for automatic dishwashers.   A method for cleaning tableware, wherein cleaning water obtained by diluting the liquid dishwashing composition according to any one of claims 1 to 6 to 150 times or more and 3000 times or less is brought into contact with an object to be cleaned attached to the tableware.

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