JP6849408B2 - 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.
Patent Document 2 states that lipids and proteins are compounded to exhibit excellent cleaning performance against stains that are dried and firmly adhered to the surface of dishes, and that foaming caused by a surfactant is suppressed. An issue is a detergent composition for an automatic dishwasher containing polypropylene glycol (A) having a number average molecular weight of 4,500 or more and 50,000 or less, and a fatty acid ester-type nonionic surfactant (B). The content of the component (A) is 0.5% by mass or more and 10% by mass or less, and the mass ratio of the component (A) to the component (B) [(A) / (B)] is 0.2 or more. , 5.0 or less, is disclosed as a detergent composition for an automatic dishwasher.

Japanese Unexamined Patent Publication No. 2014-065812 Japanese Unexamined Patent Publication No. 2014-129493

In Patent Document 1, it cannot be said that the foam-suppressing property is sufficient, and in Patent Document 2, further improvement in detergency against complex stains of proteins and lipids 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 foam-suppressing property and storage stability.

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 used in an amount of 1.5% by mass or more, and (b) (meth) acrylic acid. A liquid cleaning agent for dishes, which comprises a copolymer with (meth) acrylic acid ester [hereinafter referred to as component (b)] and water, and the liquid is a dispersion liquid. Regarding the composition.

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 foam-suppressing property and storage stability.

The liquid cleaning agent composition for tableware of the present invention is excellent in detergency against complex stains of proteins and lipids. This is not always clear, but 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 complex of the protein and the lipid is formed. It is presumed that the detergency is increased.

<(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>
The liquid cleaning agent composition for tableware of the present invention means (meth) acrylic acid [methacrylic acid and / or acrylic acid as the component (b). ] And (meth) acrylic acid ester are contained from the viewpoint of storage stability.

(B) The hydrocarbon group constituting the ester of the (meth) acrylic acid ester, which is a constituent unit of the component, is preferably an alkyl group, and the number of carbon atoms thereof is preferably 8 or more, more preferably 10 or more, and It is preferably 30 or less, more preferably 22 or less. Further, the copolymer of the component (b) 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).

The ratio of the monomer constituent units from the (meth) acrylic acid ester in the copolymer of the component (b) is, in terms of mass ratio, (meth) acrylic acid ester to 100 (meth) acrylic acid ester, preferably 0.2. The above is more preferably 0.5 or more, preferably 10 or less, and more preferably 5 or less.
The component (b) may include a (meth) acrylic acid polymer that is later esterified.

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, it is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, 0.08 with respect to 100 parts by mass of the total of (meth) acrylic acid and (meth) acrylic acid ester. It is more than parts by mass, 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.

The ratio of the total content of the (meth) acrylic acid, the (meth) acrylic acid ester, and the cross-linking agent when used in the total polymer of the component (b) is preferably 95% by mass or more, more preferably 99. It is 5% by mass or more, preferably 100% by mass or less, and may be 100% by mass.

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

As the component (b), for example, commercially available products such as Carbo-Mer ETD2020 manufactured by Noveon Inc., Akpek HV501ER manufactured by Sumitomo Seika Chemical Co., Ltd., and Akpek HV701EDR can be used. These can be used in combination of two or more.

<Ingredient (c)>
It is preferable that the liquid cleaning agent composition for tableware of the present invention contains a defoaming agent [hereinafter referred to as the component (c)] as the component (c) from the viewpoint of foam-suppressing property.
As the component (c), one or more selected from polyalkylene glycol having 3 or 4 carbon atoms, 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 proper blending, and carbon is preferable. More preferably, one or more selected from the polyalkylene glycol of the number 3 or 4 and the silicone compound. These can also be used in combination.

Examples of the polyalkylene glycol having 3 or 4 carbon atoms as the component (c) include polypropylene glycol and polybutylene glycol, and polypropylene glycol is preferable.
The number average molecular weight of the polyalkylene glycol having 3 or 4 carbon atoms is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, from the viewpoint of suppressing foaming during use. Then, it is preferably 20,000 or less, more preferably 10,000 or less, still more preferably 6,000 or less, and even 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.

(C) 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 (c) 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 (c) can be 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 composition for tableware of the present invention, the component (b) is preferably 0.15% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5 by mass, from the viewpoint of storage stability. Mass% or more, more preferably 0.75% 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. It is preferably contained in an amount of 4% by mass or less, more preferably 2% by mass or less. The content (% by mass) of the component (b) is calculated based on the acid conversion.

In the present invention, a crosslinked (meth) acrylic acid polymer may be contained as the component (b') from the viewpoint of detergency. The crosslinked (meth) acrylic acid polymer is a polymer in which the main constituent monomer is (meth) acrylic acid, and the crosslinked (meth) acrylic acid polymer has a molar ratio of less than 0.1 (meth) with respect to 100 (meth) acrylic acid, for example. Those using an ester of acrylic acid and a polyol are preferable. Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, glycerin, pentaerythritol, polyethylene glycol, polypropylene glycol, polyglycerin, and various other sugars. The viscosity of the component (b') is the same as the range described in the above-mentioned component (b).

The ratio of the total content of the (meth) acrylic acid and the cross-linking agent in the total polymer of the component (b') is preferably 98% by mass or more, more preferably 99% by mass or more, and preferably 100% by mass. It may be less than or equal to 100% by mass.

As the component (b'), 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.

In the liquid cleaning agent composition for tableware of the present invention, the component (b') is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 0. It is contained in an amount of 5% by mass or less, more preferably 0.3% by mass or less. The content (% by mass) of the component (b') is calculated based on the acid conversion.

In the liquid cleaning composition for tableware of the present invention, the component (c) is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and stored from the viewpoint of defoaming or defoaming property. From the viewpoint of stability, it is preferably contained in an amount of 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 (c) in the liquid cleaning agent composition for tableware is more preferably as follows depending on the compound of the component (c).
When the component (c) is a polyalkylene glycol having 3 or 4 carbon atoms, the liquid cleaning agent composition for dishes of the present invention preferably contains the component (c) from the viewpoint of defoaming or defoaming property. 1% by mass or more, more preferably 0.15% by mass or more, still 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, from the viewpoint of storage stability. Therefore, it is preferably contained in an amount of 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less.
When the component (c) 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 makes the component (c) 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 (c) is a silicone compound, the tableware liquid cleaning composition of the present invention contains the component (c) 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 (b) / (a) of the content of the component (b) to the content of the component (a) is preferably 0 from the viewpoint of storage stability. 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, 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.} Further, the content (mass%) of the component (b) is calculated based on the acid conversion.

In the liquid cleaning agent 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 determined from the viewpoint of defoaming property or defoaming property. It is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, still more preferably 0.04 or more, still more preferably 0.1 or more, still more preferably 0.3 or more. From the viewpoint of detergency, it is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, still 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 agent composition for tableware of the present invention is a polymer other than the component (b), and as a component (d), an acrylic acid-maleic acid copolymer or a salt thereof, or a methacrylic acid-malein, from the viewpoint of detergency. It is preferable to contain an acid copolymer or a salt thereof, and one or more polymers selected from a diisobutylene-maleic acid copolymer or a salt thereof.

The weight average molecular weight of the component (d) is preferably 10,000 or more, more preferably 15,000 or more from the viewpoint of detergency, and preferably 100,000 or less, more preferably from the viewpoint of low temperature stability. It is less than 50,000. The weight average molecular weight can be determined by gel permeation chromatography using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent and polyethylene glycol as a standard substance.

In the liquid cleaning agent composition for tableware of the present invention, the component (d) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, still more preferably, from the viewpoint of detergency. Is 4% by mass or more, more preferably 6% by mass or more, and from the viewpoint of storage stability, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, still more preferable. Contains 11% by mass or less.

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 preferably 100 mPa · s or more, more preferably 300 mPa · s or more, still more preferably 500 mPa · s or more, still more preferably, from the viewpoint of storage stability. Is 700 mPa · 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, more preferably 10,000 mPa · s. Below, it is more preferably 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 composition for tableware of the present invention is a dispersion at 20 ° C., and may be an emulsion 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.
The liquid cleaning agent composition for tableware of the present invention is in the state of a dispersion, even if an anionic surfactant having an alkyl group or an alkenyl group having 10 carbon atoms, which is a component (a), is used. In addition, since the cleaning agent composition is excellent in foam suppressing property, it is preferable as a liquid cleaning agent composition for automatic tableware. 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 which is a component (c).
Further, even in the state of such a dispersion liquid, the liquid cleaning agent composition for tableware of the present invention is excellent in storage stability by using the component (b).

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.

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, even more preferably 0.19% by mass or more, and from the viewpoint of economic efficiency, preferably 0.5% by mass or less, more preferably 0. It is .31% by mass or less, more preferably 0.25% by mass or less, still more preferably 0.22% by mass or less, still more preferably 0.21% by 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 (b) to an appropriate amount of ion-exchanged water, dispersing it at 3500 rpm using a disper (Homodisper manufactured by PRIMIX), and then at room temperature (25 ° C.). A) component, (c) component, (d) component and citric acid (manufactured by Fuso Chemical Co., Ltd.) were added, and the mixture was 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) Storage stability 30 g of the liquid cleaning agent composition for tableware shown in Table 1 was added to PS-No. The mixture was placed in a 6-standard glass bottle, allowed to stand at room temperature (20 ° C.), and followed up for 20 days.
In Examples 1, 2 and 4, the number of days until the dispersion liquid (emulsion liquid or suspension) was visually recorded was recorded and shown in Table 1. In Comparative Example 3, the number of days until the transparent solution became turbid or changed in separation was recorded and shown in Table 1.
20 days or more in the table means that the appearance was unchanged and stable during the storage stability test period.

(3) Foam-suppressing property After putting 6 g of the liquid dishwashing liquid cleaning composition shown in Table 1 into a table-top dishwasher (NP-TR3 manufactured by Panasonic Corporation), washing was started using tap water in a standard course. , The height of the foam after 20 minutes was measured. The height of the foam was measured by measuring the height of the foam generated with reference to the drain port inside the washing machine.
In this evaluation, the height of the bubbles is preferably 7 cm or less, more preferably 6 cm or less, further preferably 5 cm or less, still more preferably 4 cm or less.
[Evaluation criteria]
A: Bubble height is 4 cm or less B: Bubble height is more than 4 cm, 7 cm or less C: Bubble height is more than 7 cm

(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) Component b-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, Viscosity of 1 mass% aqueous solution 37500 mPa · s
Component (b') (Comparison component of component (b))
B'-1: 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 (b) or the component (b') in Table 1 is an effective amount.
Further, the viscosity of the component (b) or the component (b') was adjusted to pH 7.0 with sodium hydroxide, and a 1% by mass aqueous solution of the component (b) or the component (b') was added to the Brookfield type at 20 ° C. It is a value measured by a viscometer (rotor No. 3, rotation speed 30 r / m).

(C) Ingredients-Polypropylene glycol: 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.
-Silicone compound: Mixture of silica fine particles and silicone, manufactured by Toray Dow Corning Co., Ltd., XIAMETER ACP-1500 ANTIFOAM COMPOUND

(D) Ingredients-Salt of maleic acid copolymer: Na acrylate / Na maleate = 2.3 (molar ratio), weight average molecular weight 21000, manufactured by Kao Co., Ltd., Poise 520

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, and (b) (meth) acrylic acid and (meth) acrylic acid. Copolymer with ester [hereinafter referred to as component (b)], (c) one or more antifoaming agents selected from polypropylene glycol, polybutylene glycol, and silicone compounds [hereinafter referred to as component (c)] and water. A liquid cleaning agent composition for dishes containing
The ester of the (meth) acrylic acid ester of the component (b) is composed of an alkyl group having 8 or more carbon atoms and 30 or less carbon atoms.
The ratio of the monomer constituent units from the (meth) acrylic acid ester in the copolymer of the component (b) is 0.2 or more for the (meth) acrylic acid ester to 100 (meth) acrylic acid in terms of mass ratio. 10 or less,
A liquid cleaning agent composition for tableware, wherein the composition is a dispersion liquid.
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 composition for tableware according to claim 1, wherein the component (b) is contained in an amount of 0.15% by mass or more. The liquid cleaning composition for tableware according to claim 1 or 2, wherein the mass ratio (b) / (a) of the content of the component (b) to the content of the component (a) is 0.1 or more. The tableware according to any one of claims 1 to 3, wherein the mass ratio (c) / (a) of the content of the component (c) to the content of the component (a) is 0.01 or more and 5 or less. Liquid cleaning agent composition for. The liquid cleaning agent composition for tableware according to any one of claims 1 to 4 , which has a viscosity of 100 mPa · s or more at 20 ° C. 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.