JP6849407B2 - Liquid cleaning agent composition for tableware - Google Patents

Description

The present invention relates to a liquid cleaning composition for tableware.

Examples of stains adhering to tableware include oil stains, starch stains such as rice grains, protein stains such as eggs, and pigment stains such as tea. Among these, dirt that is dried by combining lipids and proteins represented by soft-boiled eggs is difficult to remove because it adheres firmly to the dishes, and it is difficult to remove by washing with an automatic dishwasher. Become. In addition, oil stains are difficult to clean and have the problem of reattaching to tableware.
It is difficult to wipe off such dry stains and oil stains with a cloth or kitchen paper before cleaning with an automatic dishwasher, and the stains remain even after cleaning with an automatic dishwasher, so wash your hands again. Need to do.

Patent Document 1 discloses a cleaning agent containing decyl sulfate and condensed phosphate in a predetermined mass ratio as a cleaning agent having excellent foam-suppressing property and detergency.
In Patent Document 2, a liquid cleaning agent composition for an automatic dishwashing machine having good enzyme stability and cleaning performance is selected from (a) enzyme, (b) glycerin, ethylene glycol, and propylene glycol 1). A liquid cleaning composition containing more than one kind of water-soluble solvent, (c) water-soluble calcium salt, (d) alkanolamine compound, and water is disclosed.

Japanese Unexamined Patent Publication No. 2014-065812 Japanese Unexamined Patent Publication No. 2008-133340

When an enzyme is added to the cleaning agent described in Patent Document 1, it is difficult to keep the enzyme activity stable, and the liquid cleaning agent composition described in Patent Document 2 further treats complex stains of proteins and lipids. Improvement of detergency is desired.

The present invention provides a liquid cleaning agent composition for tableware, which is excellent in detergency against complex stains of proteins and lipids and is also excellent in storage stability of enzyme activity.

In the present invention, (a) an anionic surfactant having an alkyl group or an alkenyl group having 10 carbon atoms [hereinafter referred to as (a) component] is 1.5% by mass or more, and (b) an enzyme [hereinafter, (b). ) Ingredients], and a liquid cleaning agent composition for tableware containing water and having a viscosity at 20 ° C. of 100 mPa · s or more.

According to the present invention, it is possible to provide a liquid cleaning agent composition for tableware, which is excellent in detergency against complex stains of proteins and lipids and is also excellent in storage stability of enzyme activity.

The anionic surfactant having an alkyl group or an alkenyl group having 10 carbon atoms of the component (a) used in the liquid cleaning agent composition for tableware of the present invention is excellent in complex stains of proteins and lipids. Although this is not always clear, the chain length of the hydrocarbon group portion of the alkyl group or alkenyl group having 10 carbon atoms in the component (a) changes the secondary structure of the protein, so that the lipid stain in the complex is affected. It is presumed that the cleanability is improved. However, when the component (a) and the enzyme are added to the composition, the stability of the enzyme, which is a protein coexisting in the composition, decreases. The present inventors have found that by setting the viscosity of the liquid cleaning agent composition to a certain level or higher, the cleaning power against complex stains of proteins and lipids is excellent, and the storage stability of enzyme activity is excellent. This is not always clear, but it is presumed that the enzyme of the component (b) is less likely to be attacked by the surfactant of the component (a) by making the viscosity above a certain level.

<(A) component>
The component (a) of the present invention is an anionic surfactant having an alkyl group or an alkenyl group having 10 carbon atoms.
Examples of the component (a) include carboxylic acid-based, sulfonic acid-based, and sulfuric acid-based, and specifically, alkylbenzene sulfonic acid or its salt, fatty acid or its salt, alkane sulfonic acid or its salt, alkyl sulfate ester or its salt. Salt, polyoxyethylene alkyl ether sulfate ester or salt thereof, α-olefin sulfonic acid or salt thereof, α-sulfo fatty acid methyl ester salt, polyoxyethylene alkyl (or alkenyl) ether carboxylic acid or salt thereof, and polyoxyethylene amide. Included is one or more selected from alkyl (or alkenyl) ether carboxylic acids or salts thereof. Examples of the salt include sodium salt, potassium salt, ammonium salt, quaternary ammonium salt and the like, and one or more of these can be used.

More specific component (a) includes decanoic acid or a salt thereof which is a fatty acid having 10 carbon atoms, a sulfonic acid having an alkyl group or an alkenyl group having 10 carbon atoms (alkane sulfonic acid, alkene sulfonic acid) or a salt thereof. And one or more selected from sulfates having an alkyl group or an alkenyl group having 10 carbon atoms (alkyl sulfate, alkenyl sulfate, alkyl ether sulfuric acid, alkenyl ether sulfate) or salts thereof, preferably an alkyl sulfate having 10 carbon atoms. , And one or more selected from alkyl ether sulfates having 10 carbon atoms, more preferably alkyl sulfates having 10 carbon atoms.
The alkyl group or alkenyl group may be a straight chain or a branched chain, and a linear alkyl group or alkenyl group is preferable from the viewpoint of excellent detergency (hereinafter, also simply referred to as detergency) for composite stains. , Straight chain alkyl groups are more preferred.

As the component (a) of the present invention, an anionic surfactant represented by the following general formula (a1) is preferable from the viewpoint of excellent foam-suppressing property and detergency of complex stains.
R ^1- O- (PO) _m1- SO _3- M ¹ (a1)
[In the formula, R ¹ represents an alkyl group or an alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, and m1 represents the average number of moles of PO added, which is 0 or more and 1.5 or less. M ¹ represents a hydrogen atom or a cation. ]

In the above general formula (a1), R ¹ is an alkyl group or an alkenyl group having 10 carbon atoms from the viewpoint of detergency, and may be a straight chain or a branched chain. R ¹ is preferably a linear alkyl group having 10 carbon atoms.
m1 indicates the average number of moles added of PO, which is 0 or more, and is 1.5 or less, preferably 1.0 or less, more preferably 0.7 or less, still more preferably 0, from the viewpoint of detergency and foam-suppressing property. It is 5.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less. It is also preferable that m1 is 0.

M ¹ is a hydrogen atom or a cation, and examples of the cation forming a salt include alkali metal ion, alkanolammonium ion, and ammonium ion. Examples of the alkali metal ion include sodium ion, potassium ion, and lithium ion, and examples of the alkanolammonium ion include monoethanolammonium ion, diethanolammonium ion, and triethanolammonium ion. Of these, sodium ion or potassium ion is preferable.

As the component (a), two or more different compounds may be used as the compound represented by the general formula (a1).

The compound represented by the general formula (a1) ^{can be obtained by sulfating the raw material alcohol represented by R 1} O- (PO) _m1 H, but as long as the present invention is not impaired, R ¹ O. A raw material alcohol in which ethylene oxide is slightly added to − (PO) _{m1 H may be used.}

<(B) component>
Examples of the component enzyme (b) include one or more selected from cellulase, protease, lipase, amylase, esterase, pectinase, lactase and peroxidase, and are particularly selected from protease and amylase from the viewpoint of starch stain cleaning performance1. Species and above are preferred, with amylase being more preferred.

Examples of commercially available enzymes that can be used as proteases include alcalase, sabinase, evarase, cannase, esperase, ovozyme (Novozymes Japan Co., Ltd.), Plafect, Properase, and Plafect OX (Genencore International).

Commercially available enzymes that can be used as amylase include Rapidase (Gist-Brockers), Termamil, Duramil, Stainzyme (Novo Nordisk Bioindustry Co., Ltd.), Plaster ST, and Plaster OxAm (Genencore International). it can.

The liquid cleaning agent composition for tableware of the present invention preferably contains amylase as the component (b), and a protease and amylase may be used in combination.

<Ingredient (c)>
It is preferable that the liquid cleaning agent composition for tableware of the present invention contains a thickener [hereinafter referred to as the component (c)] as the component (c) from the viewpoint of stably blending the enzyme and improving the viscosity.

Examples of the component (c) include (1) nonionic polysaccharides such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, guar gum and locust bean gum, and (2) xanthan gum, carrageenan and gellan gum. Examples thereof include one or more selected from natural polymers such as anionic polysaccharides and synthetic polymers such as (3) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol and polyacrylic acid-based polymers, and (a) components. From the viewpoint of compoundability and low temperature stability, one or more selected from synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, and polyacrylic acid-based polymers are preferable, and one selected from polyacrylic acid-based polymers 1 More than seeds are more preferred.

The viscosity of the thickener was adjusted to pH 7.0 with sodium hydroxide in a 1% by mass aqueous solution of the thickener at 20 ° C. with a Brookfield type viscometer (rotor No. 3 or rotor No. 3 depending on the measured viscosity. 4. The viscosity measured at a rotation speed of 30 r / m) is preferably 1,000 mPa · s or more, more preferably 3,000 mPa · s or more, further preferably 5,000 mPa · s or more, still more preferably 10,000 mPa. · S or more, preferably 200,000 mPa · s or less, more preferably 100,000 mPa · s or less, still more preferably 70,000 mPa · s or less, still more preferably 50,000 mPa · s or less.

The polyacrylic acid-based polymer means (meth) acrylic acid [methacrylic acid and / or acrylic acid. ] Is a polymer polymer mainly composed of the derived monomer constituent units.

Examples of the polyacrylic acid-based polymer include a crosslinked (meth) acrylic acid-based polymer [hereinafter referred to as (c1)] and a copolymer of (meth) acrylic acid and (meth) acrylic acid ester [hereinafter referred to as (c2)). ] Is preferably used, and may be used in combination. In addition, (c1) is one kind of carboxyvinyl polymer.

(C1) is preferably an acidic polymer compound having a carboxyl group, and is a polymer in which the main constituent monomer is (meth) acrylic acid, and the molar ratio as a cross-linking agent is less than 0.1 with respect to 100 (meth) acrylic acid. Those containing an ester of (meth) acrylic acid and a polyol are preferable, and those usually used in cosmetics and external preparations for pharmaceuticals can be used without limitation. Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, glycerin, pentaerythritol, polyethylene glycol, polypropylene glycol, polyglycerin, and various other sugars. Of these, (c1) is preferably a crosslinked acrylic acid homopolymer.

As (c1), for example, commercially available products such as Carbo-Mer 980 manufactured by Noveon Inc., Carbo-Mer 981 and Akpek 501E manufactured by Sumitomo Seika Chemical Co., Ltd. can be used. These can be used in combination of two or more.

The hydrocarbon group constituting the ester of the (meth) acrylic acid ester [meaning acrylic acid ester and / or methacrylic acid ester], which is the constituent unit of (c2), is preferably an alkyl group, and the number of carbon atoms thereof is determined to be an alkyl group. It is preferably 8 or more, more preferably 10 or more, and preferably 30 or less, more preferably 22 or less. Further, the copolymer of (c2) may contain a structural unit derived from an alkylene oxide having 2 or more and 4 or less carbon atoms (hereinafter referred to as AO).
Further, the ratio of the monomer constituent units from the (meth) acrylic acid ester in the copolymer of (c2) is such that the (meth) acrylic acid ester is preferably 0. It is 2 or more, more preferably 0.5 or more, and preferably 10 or less, more preferably 5 or less.
Further, the copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferably crosslinked. Examples of the cross-linking agent include compounds having two or more ethylenically unsaturated groups such as pentaerythritol allyl ether, diethylene glycol diallyl ether, and polyethylene glycol diallyl ether.
When a cross-linking agent is used, the ratio of the cross-linking agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass, based on 100 parts by mass of the total of (meth) acrylic acid and (meth) acrylic acid ester. More than parts, more preferably 0.08 parts by mass or more, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, still more preferably 0.3 parts by mass or less.
It should be noted that (c2) includes a (meth) acrylic acid polymer that is later esterified.

As (c2), for example, commercially available products such as Carbo-Mer ETD2020 manufactured by Noveon Inc., Akpek HV501ER manufactured by Sumitomo Seika Chemical Co., Ltd., and 701EDR can be used. These can be used in combination of two or more.

<Ingredient (d)>
The liquid cleaning agent composition for tableware of the present invention preferably contains an antifoaming agent [hereinafter referred to as component (d)] as component (d).
As the component (d), one or more selected from polypropylene glycol, a fatty acid ester having a hydrocarbon group having 16 or more and 18 or less carbon atoms, and a silicone compound are preferable from the viewpoint of foam-suppressing property, and polypropylene glycol is more preferable.

When polypropylene glycol is used as the component (d), the number average molecular weight of polypropylene glycol is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2, from the viewpoint of suppressing foaming during use. It is 000 or more, and preferably 20,000 or less, more preferably 10,000 or less, still more preferably 6,000 or less, still more preferably 4,000 or less.
The number average molecular weight can be obtained from the hydroxyl value. Further, the hydroxyl value can be measured by a method according to JIS K-1557-1.

(D) As the fatty acid ester having a hydrocarbon group having 16 or more and 18 or less carbon atoms, one or more selected from sorbitan fatty acid ester, sucrose fatty acid ester, fatty acid monoglyceride, and polyglycerin fatty acid ester are used. Among these, one or more selected from sorbitan fatty acid ester and fatty acid monoglyceride are preferable. Specifically, glyceryl monopalmitate, glyceryl monomalgalate, glyceryl monostearate, glyceryl monooleate, palm kernel oil composition fatty acid monoglyceride, sorbitan monopalmitate, sorbitan monomalgarate, sorbitan monostearate, sorbitan monoole One or more selected from ate, sucrose monopalmitate, sucrose monomalgarate, sucrose monostearate, and sucrose monooleate can be mentioned.

The silicone compound of the component (d) is not particularly limited to oil type, solution type, powder type, emulsion type and the like, but for example, a dispersion liquid or emulsion of polyorganosiloxane oil or resin such as polydimethylsiloxane, And the combination of polyorganosiloxane and silica particles in which polyorganosiloxane is chemically adsorbed or melted on silica can be mentioned. Among them, the component (d) is preferably polydimethylsiloxane.

<Water>
The liquid cleaning composition for tableware of the present invention contains water. Water is used in an amount that is the balance of the composition. As the water, ion-exchanged water or distilled water can be used. Further, a small amount of chlorine may be contained for the purpose of sterilizing or sterilizing water.

<Composition of liquid cleaning agent composition for tableware>
The liquid cleaning agent composition for tableware of the present invention contains the component (a) in an amount of 1.5% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4 from the viewpoint of detergency. From the viewpoint of mass% or more and foam-suppressing property, it is preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 6. Contains less than% by mass. The content (% by mass) of the component (a) is calculated based on the sodium salt conversion, that is, the compound conversion amount in which ^{M 1 in the general formula (a1) is sodium ion.}

In the liquid cleaning agent composition for tableware of the present invention, the component (b) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, more preferably 0.01% by mass or more, in terms of the amount of enzyme protein, from the viewpoint of detergency. Is 0.05% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less from the viewpoint of reducing the manufacturing cost.

In the tableware liquid cleaning composition of the present invention, the component (c) is preferably 0.15% by mass or more, more preferably 0.3% by mass or more, and further preferably 0. 5% by mass or more, and from the viewpoint of improving handleability, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less, still more preferably 4% by mass or less, still more preferable. Is contained in an amount of 2% by mass or less. When the component (c) is a polyacrylic acid-based polymer, the content (mass%) of the component (c) is calculated based on the acid conversion.

In the liquid cleaning agent composition for tableware of the present invention, the component (d) is preferably 0.1% by mass or more, more preferably 0.15% by mass or more from the viewpoint of enzyme stability, defoaming or defoaming property. From the viewpoint of storage stability, the content is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less.
Further, the content of the component (d) in the liquid cleaning agent composition for tableware is more preferably as follows depending on the compound of the component (d).
When the component (d) is polypropylene glycol, the liquid cleaning agent composition for dishes of the present invention contains the component (d) in an amount of preferably 0.1% by mass or more, more preferably from the viewpoint of defoaming or defoaming property. Is 0.15% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and preferably 5% by mass from the viewpoint of storage stability. Hereinafter, the content is more preferably 4% by mass or less, still more preferably 3% by mass or less.
When the component (d) is a fatty acid ester having a hydrocarbon group having 16 or more and 18 or less carbon atoms, the liquid cleaning agent composition for dishes of the present invention uses the component (d) from the viewpoint of defoaming or defoaming property. Therefore, preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and from the viewpoint of storage stability, preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass. % Or less, more preferably 2% by mass or less, still more preferably 1% by mass or less.
When the component (d) is a silicone compound, the tableware liquid cleaning composition of the present invention contains the component (d) in an amount of preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and From the viewpoint of storage stability, the content is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, still more preferably 1% by mass or less.

In the liquid cleaning composition for tableware of the present invention, the mass ratio (c) / (a) of the content of the component (c) to the content of the component (a) is preferably 0 from the viewpoint of storage stability. 01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, even more preferably 0.04 or more, and from the viewpoint of detergency, preferably 5 or less, more preferably 4 or less, still more preferably. It is 3 or less, more preferably 2 or less, and even more preferably 1 or less. The content (% by mass) of the component (a) is calculated based on the sodium salt conversion, that is, the compound conversion amount in which ^{M 1 in the general formula (a1) is sodium ion.} When the component (c) is a polyacrylic acid-based polymer, the content (% by mass) of the component (c) is calculated based on the acid conversion.

In the liquid cleaning agent composition for tableware of the present invention, the mass ratio (d) / (a) of the content of the component (d) to the content of the component (a) is determined from the viewpoint of defoaming property and enzyme stability. It is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, still more preferably 0.25 or more, and from the viewpoint of detergency, preferably 5 or less, more preferably 4 or less. , More preferably 3 or less, even more preferably 2 or less, still more preferably 1 or less. The content (% by mass) of the component (a) is calculated based on the sodium salt conversion, that is, the compound conversion amount in which ^{M 1 in the general formula (a1) is sodium ion.}

The liquid cleaning composition for tableware of the present invention contains water, preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 98% by mass or less, more preferably 98% by mass or less. It is contained in an amount of 95% by mass or less, more preferably 93% by mass or less.

The pH of the liquid cleaning agent composition for tableware of the present invention at 20 ° C. is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and from the same viewpoint, from the viewpoint of detergency and mildness. It is preferably 10 or less, more preferably 9.5 or less, still more preferably 9 or less, even more preferably 8.5 or less, and even more preferably 8 or less.

The viscosity of the liquid cleaning agent composition for tableware of the present invention at 20 ° C. is 100 mPa · s or more, preferably 300 mPa · s or more, more preferably 500 mPa · s or more, still more preferably 700 mPa · s. s or more, more preferably 900 mPa · s or more, and from the viewpoint of handleability, preferably 100,000 mPa · s or less, more preferably 50,000 mPa · s or less, still more preferably 10,000 mPa · s or less, and more. More preferably, it is 5,000 mPa · s or less. The viscosity can be measured according to the description of JIS Z 8803: 2011, and specifically, a Brookfield type viscometer (rotor No. 3 or rotor No. 4, rotation speed 30r / depending on the measured viscosity). It can be measured using m).

The liquid cleaning agent composition for tableware of the present invention is liquid at 20 ° C., and is preferably a dispersion liquid from the viewpoint of enzyme stability, and may be an emulsion liquid or a suspension.
To be a dispersion, the liquid cleaning agent composition for tableware of the present invention is put in a quartz cell having an optical path length of 1 cm as it is, and an absorptiometer (for example, U-3300 manufactured by Hitachi, Ltd.) is used to measure 800 nm. When the permeability is measured (20 ° C.) and the permeability is 70% or less, it can be determined that the cleaning agent composition is a dispersion liquid.
When the liquid cleaning agent composition for tableware of the present invention is in the state of a dispersion, the storage stability of the enzyme is more excellent. It is presumed that this is because the enzyme of the component (b) is less likely to be attacked by the surfactant of the component (a).
The liquid cleaning composition for tableware of the present invention can be made into a dispersion, for example, by adding an oil agent or a defoaming agent as a component (d) to the cleaning agent composition.

The liquid cleaning composition for dishes of the present invention contains a solvent, a hydrotrope, a dispersant, a pH adjuster, a thickener, a viscosity adjuster, a fragrance, a colorant, and an oxidation, as long as the object of the present invention is not impaired. Other components such as an inhibitor, a preservative, a foam suppressant, a bleaching agent, and a bleaching activator (however, those which do not correspond to the components (a) to (d)) can be blended.
As other preferable components, from the viewpoint of detergency, preferably, an acrylic acid-maleic acid copolymer or a salt thereof, a methacrylic acid-maleic acid copolymer or a salt thereof, and a diisobutylene-maleic acid copolymer or a salt thereof. It is preferable to contain one or more polymers selected from the above.

The liquid dishwasher composition of the present invention can be used for both dishwashers, automatic dishwashers, and hand washing, and can be used for both dishwashers, liquid dishwashers, and automatic dishwashers. Suitable as a liquid cleaning agent composition for use. Further, it is suitably used for washing with a commercial dishwasher. The tableware includes cooking utensils, washing utensils, and the like.
When cleaning with a dishwasher and further with a commercial dishwasher, the liquid dishwasher composition of the present invention is used as a cleaning solution mixed with water. At that time, a certain amount of the composition is arbitrarily transferred to the inside of the dishwasher by the supply device, and an appropriate concentration of the washing liquid is maintained. The liquid liquid cleaning agent composition for tableware of the present invention in liquid form is supplied by, for example, directly inserting a tube dedicated to a commercial dishwasher into a container such as plastic filled with the composition and sucking it up. After that, the cleaning liquid is supplied to the inside of the commercial dishwasher.

From the viewpoint of economy, it is preferable that the cleaning liquid prepared from the liquid cleaning agent composition for tableware of the present invention is usually maintained at a constant concentration in a storage tank provided in an automatic washing machine.

According to the present invention, a cleaning liquid for an automatic washing machine obtained by diluting the liquid cleaning agent composition for tableware of the present invention with water 320 times (mass ratio, the same applies hereinafter) or more and 770 times or less, and automatic cleaning using the cleaning liquid. A washing method for washing dishes is provided by the machine. In this washing method, a step of diluting the liquid washing agent composition for tableware of the present invention with water to 320 times or more and 770 times or less to prepare a washing liquid for an automatic washing machine, and a dishwasher using the washing liquid, and further. It may include the step of washing the dishes with an automatic dishwasher. The dilution ratio at the time of using the liquid cleaning agent composition for tableware of the present invention is preferably 770 times (mass ratio, the same applies hereinafter) or less, more preferably 700 times or less, still more preferably 600 times or less, still more preferably 550 times. Below, it is more preferably 530 times or less, and preferably 320 times or more, more preferably 400 times or more, still more preferably 450 times or more, still more preferably 470 times or more.

From the viewpoint of detergency, the concentration of the liquid cleaning agent composition for tableware of the present invention in the cleaning liquid is preferably 0.1% by mass or more, more preferably 0.14% by mass or more, still more preferably 0. It is 17% by mass or more, more preferably 0.18% by mass or more, further preferably 0.19% by mass or more, and from the viewpoint of economic efficiency, preferably 0.5% by mass or less, more preferably 0.31. It is mass% or less, more preferably 0.25 mass% or less, still more preferably 0.22 mass% or less, still more preferably 0.21 mass% or less.

The cleaning time is preferably 10 seconds or longer, more preferably 20 seconds or longer, still more preferably 30 seconds or longer from the viewpoint of cleanability, and preferably 3 minutes or less from the viewpoint of productivity and economy. , More preferably 2 minutes or less, still more preferably 1 minute or less.

The cleaning temperature of the cleaning liquid is preferably 40 ° C. or higher, more preferably 50 ° C. or higher from the viewpoint of productivity and cleanability, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower from the viewpoint of cleanability. Is.
After the dishes are washed, usually immediately in the same dishwasher and then in an automatic dishwasher, water, hot or hot water, eg, preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and preferably. Rinsing is performed with hot water at 80 ° C. or lower for 5 minutes or more and 40 minutes or less.

The liquid cleaning agent composition for tableware shown in Table 1 was prepared, and the following items were evaluated. The results are shown in Table 1. The liquid cleaning agent composition for tableware shown in Table 1 is prepared by adding the component (c) to an appropriate amount of ion-exchanged water and dispersing it at 3500 rpm using a disper (Homodisper manufactured by PRIMIX) at room temperature (25 ° C.) (a). ), (B) and (d) were added and stirred at 9500 rpm using a homomixer (same as above). Further, monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.) was added to adjust the pH (20 ° C.).

<Evaluation method>
(1) Detergency of protein / lipid complex stains 0.1 g (dry mass) of semi-ripe egg yolk heated to 70 ° C. was applied to a 5 cm × 2.5 cm slide glass and dried for 1 day to allow protein / lipid composite stains to adhere. A slide glass was prepared. A plurality of slide glasses to which the stains were attached were prepared. The liquid cleaning agent composition for tableware shown in Table 1 was diluted with ion-exchanged water so as to be a 0.2% by mass aqueous solution to prepare a cleaning liquid. A cleaning test was conducted by the leanut test method using this cleaning solution and three slide glasses to which the above stains were attached. The washing time was 7 minutes and the washing temperature was 40 ° C. After cleaning, the cleaning rate is calculated for each slide glass by the following formula, and the average value is shown in Table 1.
Cleaning rate (%) = [(mass of slide glass before cleaning-mass of slide glass after cleaning) /0.1] × 100
The higher the cleaning rate (%), the better the cleaning power. In this evaluation, 50% or more is preferable, 70% or more is more preferable, and 80% or more is further preferable.

(2) Detergency of starch stains 0.55 g of cooked white rice was thinly applied to a pottery bowl (15 cm in diameter) and then dried at room temperature for 24 hours.
After installing two bowls coated with the white rice in a built-in dishwasher (manufactured by Panasonic Corporation, NP-45VS6), add 6 g of the liquid cleaning agent composition for tableware shown in Table 1, and then use tap water. Then, the standard course was used for cleaning.
After the cleaning was completed, a 0.05 M iodine aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was sprayed to evaluate the detergency of starch stains according to the following evaluation criteria. The results are shown in Table 1.
[Evaluation criteria]
A: Not stained at all after spraying iodine aqueous solution B: Partially stained after spraying iodine aqueous solution C: The entire surface is stained after spraying iodine aqueous solution

(3) Storage stability of enzyme (residual activity of amylase)
The liquid cleaning agent composition for tableware shown in Table 1 is placed in a transparent glass container (standard bottle No. 11) and stored in a constant temperature room at 25 ° C. for 1 week. Enzymatic activity of the composition before storage and the composition after storage. Was measured by the following methods, and the residual activity rate of the enzyme (amylase) was determined.
0.5 g of the liquid cleaning agent composition for tableware before and after storage was weighed, 4.5 mL of pre-ice-cooled ion-exchanged water was added, and the mixture was stirred. This was used as the diluent (1).
Dissolve 0.5 mL of the diluent (1), 4.5 mL of ice-cooled ion-exchanged water, and 0.0348 g of PMSF ethanol diluent (PMSF (PhenylMethylSulfonyl Fluoride)) in another test tube with 2 mL of primary ethanol. 50 μL was added and stirred. This was used as the diluent (2).
4 mL of 50 μM Britton-Robinson Buffer (prepared with reference to Basic Biochemical Experimental Method 6 (written by Koichi Anan et al., P277. Maruzen Co., Ltd.)) was prepared in a test tube (50 ° C.). This was used as a diluent (3).
One tablet of Fadevas amylase test (manufactured by Shinotest Co., Ltd.) was added to a test tube containing the diluted solution (3), and the mixture was stirred and then held at 50 ° C. for 10 minutes.
Then, 200 μL of the diluted solution (2) was added to the solution of the diluted solution (3), and the mixture was held at 50 ° C. for 15 minutes.
1 μL of 1N NaOH was added and stirred to stop the reaction. After centrifugation at 400 G for 5 minutes, the absorbance of the obtained centrifugal supernatant at 620 nm was measured, and the residual activity rate of amylase was calculated by the following formula. The larger the residual activity rate of amylase, the more excellent the storage stability of the enzyme, which is preferable.
Residual activity rate of amylase (%) = 100 × Absorbance after storage / Absorbance before storage

(4) Judgment of the state of the liquid of the cleaning agent composition Put the liquid cleaning agent composition for tableware shown in Table 1 as it is in a quartz cell with an optical path length of 1 cm, and put it in an absorptiometer (Hitachi, Ltd., U-3300). Then, the transmittance at 800 nm was measured (20 ° C.). When the permeability is 70% or less, the cleaning agent composition is determined to be a dispersion, and when the permeability exceeds 70%, it is determined to be a transparent solution. Further, the dispersion liquid is determined to be an emulsion when only the liquid oil content is dispersed from the blended raw material composition, and is a suspension when the solid oil content or the solid oil content and the liquid oil content are dispersed. I decided. The results are shown in Table 1.

(5) Viscosity measurement The viscosity of the liquid cleaning agent composition for table 1 in Table 1 was measured at 20 ° C. with a Brookfield type viscometer (rotor No. 3 (rotor No. 4 if the viscosity is high) depending on the measured viscosity. ), The rotation speed was 30 r / m, 1 minute). The results are shown in Table 1.

The components in the table are as follows.
Component (a), sodium decyl sulfate: Fluorochem Ltd. made, in the general formula (a1), a straight-chain alkyl group of ^{R 1} is 10 carbon atoms, m1 is 0, the anionic surfactant ^{M 1} is a sodium ion C10 (PO) 0.6AS: An anionic surfactant produced in the same manner as in Example 3 of JP-A-2009-035714 except that the raw material alcohol was changed to 10 carbon atoms [general formula (a1). ) in a linear alkyl group of 10 carbon atoms, m1 is 0.6, the anionic surfactant ^{M 1} is sodium]. That is, an average of 0.6 mol of a propyleneoxy group is added to 1 mol of a natural alcohol having an alkyl chain having 10 carbon atoms, the mixture is sulfated with sulfur trioxide, neutralized with an aqueous sodium hydroxide solution, and the anionic surfactant is used. An activator was obtained.

Component (a') (Comparative component of component (a))
- sodium dodecyl sulfate: manufactured by Wako Pure Chemical Industries, Ltd., in the general formula (a1), a straight-chain alkyl group of R ¹ is 12 carbon atoms, m1 is 0, the anionic surfactant M ¹ is a sodium ion

(B) Ingredients-Amylase preparation: Novozymes, Termamil Ultra 300L (enzyme protein amount is 11% by mass)
The content of the component (b) in Table 1 is a tangible amount.

(C) Ingredients / Viscosity Agent 1: Crosslinked acrylic acid / alkyl methacrylate (10 to 30 carbon atoms) copolymer (mass ratio of acrylic acid / alkyl methacrylate 100/1), manufactured by Sumitomo Seika Co., Ltd., Akpek HV701EDR , 1 mass% aqueous solution viscosity 37500 mPa · s
Thickener 2: Crosslinked polyacrylic acid, manufactured by Sumitomo Seika Chemical Co., Ltd., Acpec HV501E, 1% by mass aqueous solution viscosity 12500 mPa · s
The content of the component (c) in Table 1 is an effective amount.
The viscosity of each component (c) was adjusted to pH 7.0 with sodium hydroxide, and a 1% by mass aqueous solution of each component (c) was mixed with a Brookfield viscometer (rotor No. 3, rotation speed) at 20 ° C. It is a value measured at 30 r / m).

(D) Ingredients-Polypropylene glycol: manufactured by Asahi Glass Co., Ltd., Excelol 3030, number average molecular weight 3000
The number average molecular weight of polypropylene glycol was a value obtained from the hydroxyl value, and the hydroxyl value was measured according to JIS K-1557-1.

Claims (7)

(A) Anionic surfactant [hereinafter referred to as (a) component] represented by the following general formula (a1) is 1.5% by mass or more, (b) amylase [hereinafter referred to as (b) component], (C) A liquid cleaning agent composition for tableware containing one or more thickeners selected from polyacrylic acid-based polymers and water and having a viscosity at 20 ° C. of 100 mPa · s or more.
R ^1- O- (PO) _m1- SO _3- M ¹ (a1)
[In the formula, R ¹ represents an alkyl group or an alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, and m1 represents the average number of moles of PO added, which is 0 or more and 1.5 or less. M ¹ represents a hydrogen atom or a cation. ] The liquid cleaning agent composition for tableware according to claim 1 , wherein the mass ratio (c) / (a) is 0.01 or more and 5 or less. The liquid cleaning agent composition for tableware according to claim 1 or 2 , wherein the liquid cleaning agent composition for tableware is a dispersion liquid. The liquid cleaning agent composition for tableware according to any one of claims 1 to 3 , further comprising (d) an antifoaming agent. The liquid cleaning agent composition for tableware according to claim 4 , wherein the mass ratio (d) / (a) is 0.1 or more and 5 or less. The liquid cleaning agent composition for tableware according to any one of claims 1 to 5 , wherein the pH is 5 or more and 9 or less at 20 ° C. The liquid dishwashing composition for dishes according to any one of claims 1 to 6 , which is for an automatic dishwasher.