JP2017110057A - Solid detergent composition for tableware - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid detergent composition for tableware excellent in low temperature stability while satisfying detergency to composite soil of proteins and lipids even when using hard water.SOLUTION: There is provided a solid detergent composition for tableware containing (a) an anionic surfactant represented by the following general formula (a1), (b) a polymer containing a constitutional unit derived from carboxylic acid having a reactive unsaturated group with 3 to 6 carbon atoms or a salt thereof, (c) one or more kinds of aromatic sulfonic acid, aromatic carboxylic acid and a salt thereof and water. R-O-(PO)-SO-M(a1), where Rrepresents an alkyl group or an alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average addition molar number of PO and the number of 0 to 1.5 and Mrepresents a hydrogen atom or cation.SELECTED DRAWING: None

Description

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

  Examples of stains attached to tableware include oil stains, starch stains such as rice grains, protein stains such as eggs, and pigment stains such as tea. Among these, the dry stains that are formed by combining lipids and proteins typified by soft-boiled eggs are difficult to remove because they adhere firmly to the dishes and are 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.

Patent Document 1 discloses that a nonionic surfactant (A) having a hydrophilic / lipophilic balance (HLB) of 1 to 7.0 is 0.1 to 10% by mass, at least one compound of carbonate and silicate. A detergent composition for an automatic dishwasher containing 5 to 70% by mass of (B), 5 to 20% by mass of percarbonate (C), and having a pH of 9 to 13 in a 0.1% by mass aqueous solution at 25 ° C. Things are disclosed.
Patent Document 2 discloses a cleaning agent containing decyl sulfate and condensed phosphate at a predetermined mass ratio.
In addition, the liquid detergent composition has a problem of low temperature stability in which the solubility of the surfactant is reduced at a low temperature and solid matter is precipitated.

JP 2014-1111697 A1 JP 2014-0665812 A

The present invention provides a liquid detergent composition for tableware that is excellent in detergency against complex soil of protein and lipid even when hard water is used, and is excellent in low-temperature stability.
The hard water includes those having a German hardness of 4 ° DH or more, further 5 ° DH, 25 ° DH or less, and further 20 ° DH or less.

The present invention includes (a) an anionic surfactant represented by the following general formula (a1) [hereinafter referred to as component (a)], and (b) a reactive unsaturated group having 3 to 6 carbon atoms. Polymer containing a structural unit derived from carboxylic acid or a salt thereof [hereinafter referred to as component (b)], (c) one or more selected from aromatic sulfonic acid, aromatic carboxylic acid and salts thereof [hereinafter referred to as (c ) Component], and a liquid detergent composition for tableware containing water.
^{_{R 1 -O- (PO) m1 -SO}} 3 -M 1 (a1)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number of 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]

  ADVANTAGE OF THE INVENTION According to this invention, even when using hard water, while being excellent in the detergency with respect to the composite stain | pollution | contamination of a protein and a lipid, the liquid detergent composition for tableware which is excellent in low-temperature stability can be provided.

  The present inventors have found that the liquid detergent composition containing the component (a), the component (b), and the component (c) drastically improves the detergency against protein and lipid composite stains and is stable at low temperatures. It has been found that it is excellent in performance.

The component (a) of the present invention is an anionic surfactant represented by the following general formula (a1).
^{_{R 1 -O- (PO) m1 -SO}} 3 -M 1 (a1)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number of 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]

In the general formula (a1), R ¹ is an alkyl group or alkenyl group having 10 carbon atoms from the viewpoint of detergency, and may be linear or branched. R ¹ is preferably a linear alkyl group having 10 carbon atoms.

  m1 represents the average number of moles of PO added, and is 0 or more, and from the viewpoint of detergency and foam suppression, it is 1.5 or less, preferably 1.0 or less, more preferably 0.7 or less, and still more preferably 0. .5 or less, more preferably 0.3 or less, and still 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 that forms a salt include an alkali metal ion, an alkanol ammonium ion, and an ammonium ion. Examples of the alkali metal ion include sodium ion, potassium ion, and lithium ion, and examples of the alkanol ammonium ion include monoethanol ammonium ion, diethanol ammonium ion, and triethanol ammonium ion. Among these, sodium ion or potassium ion is preferable, and sodium ion is more preferable.

  Two or more different (a) components may be used.

Incidentally, the compound represented by the general formula (a1) ^is obtained by sulfating the raw material alcohol represented by _{R 1 O- (PO) m1 H} , as long as they do not impair the present ^{invention, R} 1 O -(PO) _m1 H may be used a raw alcohol obtained by slightly adding ethylene oxide.

  (B) component of this invention is a polymer containing the structural unit derived from the carboxylic acid which has a C3-C6 reactive unsaturated group, or its salt.

  The component (b) is a heavy component containing a structural unit derived from a carboxylic acid having a reactive unsaturated group having 3 to 5 carbon atoms, preferably having 3 to 5 carbon atoms or a salt thereof (hereinafter referred to as the component (b1)). It is a coalescence. In addition, the said carbon number of (b1) component is the total carbon number of carboxylic acid.

  The component (b1) is one or two selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, citraconic acid, salts thereof, and acid anhydrides thereof. More than a seed.

  The component (b1) is preferably one or more selected from acrylic acid, methacrylic acid, maleic acid, salts thereof and maleic anhydride, more preferably acrylic acid and maleic acid, from the viewpoint of detergency. And one or more selected from the salts thereof. The salt is at least one selected from a sodium salt, a potassium salt, an alkanolamine salt, and an ammonium salt. The salt may be formed using a salt-type compound as a monomer or may be formed by neutralization after polymerization.

  From the viewpoint of detergency, the proportion of the component (b1) in the total monomer of the component (b) is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and Preferably it is 100 mol% or less.

The component (b) includes a structural unit derived from acrylic acid or a salt thereof (hereinafter referred to as a structural unit ( _bAA )) and a structural unit derived from maleic acid, a salt thereof or maleic anhydride (hereinafter referred to as a structural unit ( _bMA )). Is preferably included. That is, the component (b1) preferably contains acrylic acid or a salt thereof and maleic acid or a salt thereof or maleic anhydride. The total proportion of the structural unit (b _AA ) and the structural unit (b _MA ) is preferably 90 mol% or more, more preferably in the structural unit derived from the component (b1), from the viewpoint of storage stability and detergency. Is 95 mol% or more, more preferably 98 mol% or more, and preferably 100 mol% or less, and may be 100 mol%.

(B) If component comprises a structural unit _{(b AA)} and the structural unit _{(b MA),} the molar ratio of the structural units _{(b AA)} / structural unit _{(b MA),} from the viewpoint of detergency, preferably 0 .6 or more, more preferably 1 or more, still more preferably 1.5 or more, and preferably 9 or less, more preferably 4 or less, still more preferably 3 or less.

  The component (b) is a polymer including a structural unit derived from the component (b1), but may include a structural unit other than the structural unit derived from the component (b1). That is, the component (b) is a copolymer that includes a monomer copolymerizable with the component (b1), specifically, a structural unit derived from the component (b1) and a structural unit derived from the component (b2) described later. It may be a coalescence.

The component (b2) is an olefin having 2 to 12 carbon atoms, an alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, and one or more monomers selected from styrene. .
The olefin having 2 to 12 carbon atoms is one or more selected from ethylene, propylene, butylene, isobutylene, diisobutylene, pentene, and hexene, preferably butylene, isobutylene, diisobutylene, pentene, and hexene. It is 1 type, or 2 or more types chosen from, More preferably, it is diisobutylene. The number of carbon atoms of the olefin is 2 or more, preferably 4 or more, and 12 or less, preferably 6 or less.
The alkyl group of the alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms preferably has 2 or more, more preferably 4 or more, and preferably 12 or less, more preferably 8 or less. .

  The molar ratio of the component (b1) to the component (b2) The component (b1) / (b2) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably It is 10 or less, more preferably 5 or less, and still more preferably 3 or less.

  In the component (b), the total proportion of the structural unit derived from the component (b1) and the structural unit derived from the component (b2) is preferably 90 mol% or more, more preferably 95 mol, from the viewpoint of storage stability. % Or more, more preferably 98 mol% or more, and preferably 100 mol% or less, and may be 100 mol%.

  The weight average molecular weight of the component (b) is preferably 3000 or more, more preferably 5000 or more, still more preferably 10,000 or more, still more preferably 20000 or more, and from the viewpoint of detergency and low-temperature stability, from the viewpoint of detergency. Therefore, it is preferably 250,000 or less, more preferably 200000 or less, still more preferably 150,000 or less, still more preferably 100000 or less, still more preferably 80000 or less, still more preferably 65000 or less, still more preferably 50000 or less, even more preferably. Is 40000 or less.

In addition, the weight average molecular weight of the component (b) is the mixed solvent of acetonitrile and water (phosphoric acid) when the polymer of the component (b) is a copolymer of acrylic acid and / or methacrylic acid and maleic acid or a salt thereof. Buffer solution) can be used as a developing solvent, and polyethylene glycol can be used as a standard substance by gel permeation chromatography.
When the polymer of component (b) is a copolymer of components (b1) and (b2), for example, a diisobutylene-maleic acid copolymer, the weight average molecular weight is acetonitrile and 0.1 M sodium chloride. A mixture with an aqueous solution (acetonitrile: sodium chloride aqueous solution (volume ratio) = 30: 70) can be obtained by gel permeation chromatography using a developing solvent and polyethylene glycol as a standard substance.

  The viscosity of component (b) was adjusted to pH 7.0 with sodium hydroxide in a 1% by weight aqueous solution of component (b) at 20 ° C. using a Brookfield viscometer (rotor no. Depending on the viscosity measurement range). 1 to No. 3, the rotational speed of 60 r / m) is preferably less than 1000 mPa · s, more preferably 500 mPa · s or less, still more preferably 100 mPa · s or less, and preferably It is 0.1 mPa · s or more.

  The component (b) is preferably polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, an acrylic acid-maleic acid copolymer or a salt thereof, a methacrylic acid-maleic acid copolymer or a salt thereof from the viewpoint of detergency. A salt, and one or more polymers selected from diisobutylene-maleic acid copolymers or salts thereof, more preferably polyacrylic acid or salts thereof, polymethacrylic acid or salts thereof, acrylic acid-maleic acid copolymer One or more polymers selected from a polymer or a salt thereof, and a methacrylic acid-maleic acid copolymer or a salt thereof, more preferably an acrylic acid-maleic acid copolymer or a salt thereof. Further, as the component (b), two or more of the above polymers may be mixed and used.

  (C) component of this invention is 1 or more types chosen from aromatic sulfonic acid, aromatic carboxylic acid, and those salts.

  Component (c) is preferably benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, sulfobenzoic acid, benzoic acid, sulfophthalic acid, naphthalene sulfonic acid, and these from the viewpoint of low temperature stability and detergency From the viewpoint of detergency, more preferably at least one selected from toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, benzoic acid, and salts thereof, and more preferably Is at least one selected from toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, and salts thereof. The salt is preferably at least one selected from alkali metal salts such as sodium salt and potassium salt, ammonium salts, and alkanol ammonium salts such as monoethanolamine salts, more preferably selected from potassium salts and sodium salts. More than a seed.

The component (c) is preferably an aromatic sulfonic acid represented by the following general formula (c1) or a salt thereof.

[Wherein, X ¹ and X ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. M ² represents a hydrogen atom or a cation. ]

In the general formula (c1), X ¹ and X ² are preferably X ¹ is a methyl group or an isopropyl group, X ² is a methyl group or a hydrogen atom, and more preferably X ¹ is from the viewpoint of low temperature stability. A methyl group, X ² is a methyl group or a hydrogen atom. From the viewpoint of low temperature stability, M ² is preferably a hydrogen atom, an alkali metal ion such as sodium or potassium, an alkanol ammonium ion such as an ammonium ion or a monoethanolammonium ion, and more preferably a hydrogen atom.

  The liquid detergent composition for tableware of the present invention preferably contains or blends a compound represented by the following general formula (d1) (hereinafter referred to as component (d)) from the viewpoint of low-temperature stability.

[Wherein, R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, at least one of which is a carbon number. 1 to 3 hydroxyalkyl groups. ]

In the general formula ^(d1), R 2, ^{R 3} and ^{R 4} are, from the viewpoint of low-temperature stability, preferably ^{R 2} is a hydroxyalkyl group having 1 to 3 carbon atoms, ^{R 3} and ^{R 4} is a hydrogen atom or A hydroxyalkyl group having 1 to 3 carbon atoms, more preferably R ² is a hydroxyalkyl group having 1 to 3 carbon atoms, R ³ is a hydrogen atom or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ⁴ is A hydrogen atom, more preferably R ² is a hydroxyalkyl group having 1 to 3 carbon atoms, R ³ and R ⁴ are hydrogen atoms, still more preferably R ² is a hydroxyethyl group, and R ³ and R ⁴ are , A hydrogen atom.

The specific component (d) is more preferably one or more selected from monoethanolamine, diethanolamine, and triethanolamine, and even more preferably monoethanolamine, from the viewpoint of low-temperature stability.
Incidentally, (d) component may contain, or formulated as ^{M 1,} M ³ in the general formula (c1) M ^2, or later to the general formula in (f1) in the general formula of the aforementioned (a1) The liquid detergent composition containing the component (a), the component (b), and the component (c) may be added to the component (d) and contained or blended. In that case, the component (d) can also be used as a pH adjuster.

<Water>
The tableware cleaning composition of the present invention is a liquid cleaning composition containing water. Any of the above-described components dissolved, dispersed, or emulsified in water may be used. As the water, ion-exchanged water or distilled water from which metal components have been removed, or hypochlorous acid-sterilized water in which hypochlorous acid is dissolved in an amount of 0.5 ppm or more and 10 ppm or less can be used. Water is the balance of the composition and is contained in an amount that makes the whole 100% by mass.

<Composition of liquid detergent composition for tableware>
In the liquid detergent composition for tableware of the present invention, the component (a) is preferably 1.5% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, from the viewpoint of detergency. More preferably 4% by mass or more, still more preferably 6% by mass or more, and from the viewpoint of foam suppression, it is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, more More preferably, it is 8 mass% or less, More preferably, it contains 6 mass% or less. Incidentally, (a) the content of the component (mass%), sodium salt conversion, i.e., M ¹ in the general formula (a1) is calculated based on the amount of compound in terms of sodium ion.

  In the liquid detergent composition for tableware of the present invention, the component (b) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and still more preferably, from the viewpoint of detergency. Is 4% by mass or more, more preferably 6% by mass or more, still more preferably 8% by mass or more, still more preferably 8.5% by mass or more, and from the viewpoint of low temperature stability, preferably 20% by mass or less. More preferably, it is 15 mass% or less, More preferably, it is 12 mass% or less, More preferably, it is 11 mass% or less, More preferably, it contains 10 mass% or less.

  In the liquid detergent composition for tableware of the present invention, the component (c) is preferably 0.15% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5%, from the viewpoint of low temperature stability. % By mass, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, still more preferably 2% by mass or more, and from the viewpoint of detergency, preferably 15% by mass or less, more preferably Is 12% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 6% by mass or less, and still more preferably 3% by mass or less. In addition, content (mass%) of (c) component is computed based on the quantity of acid conversion.

  In the liquid detergent composition for tableware of the present invention, the mass ratio (c) / (a) of the component (c) to the component (a) is preferably 0.1 or more, more preferably from the viewpoint of low temperature stability. 0.2 or more, more preferably 0.3 or more, and from the viewpoint of detergency, preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, even more preferably 2 or less, and even more preferably 1 Hereinafter, it is more preferably 0.5 or less.

  In the liquid detergent composition for tableware of the present invention, the mass ratio (b) / (c) of the component (b) to the component (c) is preferably 0.1 or more, more preferably 0, from the viewpoint of detergency. .3 or more, more preferably 0.5 or more, further preferably 1 or more, more preferably 2 or more, and from the viewpoint of low temperature stability, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, More preferably, it is 8 or less, More preferably, it is 6 or less.

  In the liquid detergent composition for tableware of the present invention, the component (d) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% from the viewpoint of low temperature stability. From the viewpoints of mass% or more and low temperature stability, it is preferably 10 mass% or less, more preferably 8 mass% or less, still more preferably 5 mass% or less.

  The pH at 20 ° C. of the liquid detergent composition for tableware of the present invention is preferably 5 or more, more preferably 6 or more, and preferably 11 or less, more preferably 10 or less, from the viewpoint of low-temperature stability and detergency. More preferably, it is 9 or less, more preferably 8 or less.

  The liquid detergent composition for tableware of the present invention preferably contains a nonionic surfactant as component (e) from the viewpoint of storage stability and cleanability.

  Nonionic surfactants include (1) polyoxyalkylene monoalkyl or alkenyl ether, (2) alkyl polyglycoside (glycoside type nonionic surfactant), (3) aliphatic alkanolamide, (4) sorbitan One or more selected from the group consisting of a nonionic surfactant, (5) alkyl monoglyceryl ether, (6) fatty acid monoglyceride, and (7) sucrose fatty acid ester are preferable, and two or more may be used.

  In the liquid detergent composition for tableware of the present invention, the component (e) is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and still more preferably, from the viewpoint of storage stability and detergency. 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass from the viewpoints of detergency and foam suppression. % Or less, more preferably 1% by mass or less, still more preferably 0.7% by mass or less.

The liquid detergent composition for tableware of the present invention does not contain an anionic surfactant represented by the following general formula (f1) as the component (f) from the viewpoint of detergency and foam suppression, Or even if it contains, it is preferable that the content is limited.
^{_{R 5 -O- (PO) m2 -SO}} 3 -M 3 (f1)
[Wherein, R ⁵ represents an alkyl group or alkenyl group having 12 to 14 carbon atoms, PO represents a propyleneoxy group, m2 represents the average number of moles of PO added, and is a number of 0 to 1.5. It is. M ³ represents a hydrogen atom or a cation. ]

In the general formula (f1), R ⁵ is an alkyl group or an alkenyl group having 12 to 14 carbon atoms from the viewpoint of detergency and foam suppression, and may be linear or branched. . R ⁵ is preferably a linear alkyl group.

  m2 represents the average added mole number of PO and is 0 or more, and from the viewpoint of detergency and foam suppression, 1.5 or less, preferably 1.0 or less, more preferably 0.7 or less, and still more preferably 0. .5 or less, more preferably 0.3 or less, and still more preferably 0.1 or less. It is also preferable that m2 is 0.

M ³ is a hydrogen atom or a cation, and examples of the cation that forms a salt include an alkali metal ion, an alkanol ammonium ion, and an ammonium ion. Examples of the alkali metal ion include sodium ion, potassium ion, and lithium ion, and examples of the alkanol ammonium ion include monoethanol ammonium ion, diethanol ammonium ion, and triethanol ammonium ion. Among these, sodium ion or potassium ion is preferable, and sodium ion is more preferable.

In the liquid detergent composition for tableware of the present invention, the component (f) is 0% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass from the viewpoints of detergency and foam suppression. Hereinafter, it is more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and further preferably 0% by mass, that is, not contained. The content of the component (f) (mass%), sodium salt conversion, i.e., the general formula (f1) M ³ in is calculated based on the amount of compound in terms of sodium ion.

  The content of water in the dishwashing liquid detergent composition of the present invention is preferably 65% by mass or more, more preferably 68% by mass or more, still more preferably 70% by mass or more, and preferably 98% by mass. Hereinafter, it is more preferably 93% by mass or less, and still more preferably 90% by mass or less.

  The viscosity at 20 ° C. of the liquid detergent composition for tableware of the present invention is preferably 3 mPa · s or more, more preferably 5 mPa · s or more, and preferably 100 mPa · s or less, more preferably from the viewpoint of low temperature stability. Is 90 mPa · s or less.

  The liquid detergent composition for tableware of the present invention includes a solvent, a hydrotrope, a dispersant, a thickener, a viscosity modifier, a fragrance, a colorant, an antioxidant, an antiseptic, as long as the object of the present invention is not impaired. Ingredients such as an agent, a foam suppressor, a bleaching agent, a bleaching activator, and a pH adjuster (however, those not corresponding to the components (a) to (f)) can be blended.

The liquid detergent composition for dishwashing of the present invention can be used for both dishwashers, automatic dishwashers, and hand-washing. The liquid detergent composition for dishwashers and further automatic dishwashers It is suitable as a liquid detergent composition. Furthermore, it is suitably used for washing with a commercial dishwasher. The tableware includes cooking utensils, cleaning utensils and the like.
When washing with a dishwasher, and further with a commercial dishwasher, the liquid detergent composition for tableware of the present invention is used as a washing liquid mixed with water. At that time, the composition is arbitrarily transferred to the inside of the dishwasher by the supply device to maintain the proper concentration of the cleaning liquid. The liquid detergent composition for tableware of the present invention in a liquid state is supplied by, for example, inserting a tube exclusively for a commercial dishwasher into a plastic container filled with the composition and sucking it up. Thereafter, the cleaning liquid is supplied into the commercial dishwasher.

  From the viewpoint of economy, the cleaning liquid prepared from the dishwashing liquid detergent composition of the present invention is usually preferably prepared by maintaining a constant concentration in a storage tank provided in an automatic cleaning machine.

  INDUSTRIAL APPLICABILITY According to the present invention, a cleaning liquid for an automatic cleaning machine obtained by diluting the liquid detergent composition for tableware of the present invention with water to 320 times (mass ratio, the same applies hereinafter) to 770 times or less, and automatic cleaning using the cleaning liquid A cleaning method for cleaning tableware by a machine is provided. In this cleaning method, the step of diluting the liquid detergent composition for dishwashing 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, The step of washing the dishes with an automatic dishwasher may be included. The dilution factor when using the liquid detergent 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, and even more preferably 550 times. Hereinafter, 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, and further preferably 470 times or more.

  The concentration in the cleaning liquid during use of the tableware liquid detergent composition of the present invention is preferably 0.13% by mass or more, more preferably 0.14% by mass or more, and still more preferably, from the viewpoints of economy and detergency. Is 0.17% by mass or more, more preferably 0.18% by mass or more, further preferably 0.19% by mass or more, and from the same viewpoint, preferably 0.31% by mass or less, more preferably 0 .25% by mass or less, more preferably 0.22% by mass or less, and still more preferably 0.21% by mass or less.

  The washing time is preferably 10 seconds or more, more preferably 20 seconds or more, still more preferably 30 seconds or more from the viewpoint of detergency, and preferably 3 minutes or less from the viewpoint of productivity and economy. More preferably, it is 2 minutes or less, More preferably, it is 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 detergency, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, from the viewpoint of detergency. It is.
After the dishes are washed, they are usually promptly washed with water, hot water or hot water, for example, hot water at 60 ° C. or higher and 80 ° C. or lower for 5 minutes or more and 40 minutes with the same dishwasher or automatic dishwasher. Thereafter, rinsing is performed.

  In a dishwasher, the cleaning liquid is usually used repeatedly by circulating it with a pump.

  The liquid detergent composition for tableware shown in Table 1 was prepared, and the following items were evaluated. The results are shown in Table 1. The liquid detergent composition for tableware of Table 1 was prepared at room temperature (20 degreeC) by the conventional method. That is, the component (c) is added to an appropriate amount of ion-exchanged water to prepare an acidic aqueous solution, the component (b) is added to the aqueous solution, and a disperser (TK Robotics: manufactured by PRIMIX) is used at 3500 rpm. Stir for 5 minutes to solubilize, add component (a), stir at 9500 rpm for 3 minutes using a homomixer (TK Robotics: manufactured by PRIMIX), add component (d) to pH ( 20 ° C.).

<Evaluation method>
(1) Detergency of protein / lipid composite soil 0.1 g (dry weight) of soft-boiled egg yolk heated to 70 ° C. was applied to a 5 cm × 2.5 cm glass slide and dried for 1 day to attach the protein / lipid composite soil. A slide glass was prepared. A plurality of slide glasses with the dirt adhered thereto were prepared. The liquid detergent composition for tableware shown in Table 1 was diluted with 5 ° DH hard water so as to be a 0.2% by mass aqueous solution to obtain a cleaning liquid. A cleaning test was performed using this cleaning solution and the three slide glasses on which the dirt was adhered, by a method using a peanut tester (JIS K3362: 2008 9.2). The washing time was 7 minutes and the washing temperature was 40 ° C. After washing, the washing rate was calculated for each slide glass by the following formula, and the average value was taken as the result of each example and each comparative example.
Washing rate (%) = [(mass of slide glass before washing−mass of slide glass after washing) /0.1] × 100
The cleaning rate (%) indicates that the higher the value, the better the cleaning power.

(2) Low temperature stability 30 g of the liquid detergent composition for tableware shown in Table 1 was added to PS-No. A 6-standard glass bottle was placed and allowed to stand at −5 ° C. for 20 days. Similarly, the glass bottle containing the liquid detergent composition for tableware is allowed to stand, and the cycle for changing the storage temperature in the order of 1 day at −15 ° C. for 1 day and 5 ° C. is set as 1 cycle, for a total of 10 cycles, Follow-up observations were made regarding the appearance change of each composition.
Table 1 shows the number of days until the appearance of the composition such as separation was visually observed during the storage stability test. 20 days or more and 10 cycles or more in the table mean that the composition appearance was stable without any change during the storage stability test period, such as translucent or partially turbid.

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 2009-035714 A except that the raw 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, after adding an average of 0.6 moles of propyleneoxy group to 1 mole of natural alcohol having 10 carbon atoms in the alkyl chain, it is sulfated with sulfur trioxide and neutralized with an aqueous sodium hydroxide solution. An activator was obtained.

Component (b): Salt of maleic acid acrylate copolymer (1): Kao Corporation, Pois 520, Na acrylate / Na maleate = 2.3 (molar ratio), Weight average molecular weight 21000
Further, in a 1% by mass aqueous solution of the component (b) adjusted to pH 7.0 with sodium hydroxide, the viscosity measured with a Brookfield viscometer (rotor No. 1, rotation speed 60 r / m) at 20 ° C. 1 mPa · s.

The weight average molecular weight of the component (b) was measured by gel permeation chromatography (GPC) under the following conditions.
Column: G4000PWXL + G2500PWXL (two linked) manufactured by Tosoh Corporation
Detector: Differential refractometer Eluent: 0.2 M phosphate buffer (KH ₂ PO ₄ , Na ₂ HPO ₄ , pH = 7) / acetonitrile = 9/1 (volume ratio)
Sample: polyethylene glycol Conditions: column temperature: 40 ° C., flow rate: 0.5 mL / min, concentration: 0.05 mg / mL

  In addition, content of (b) component in a table | surface is an effective amount.

(C) Component / m-xylene sulfonic acid: manufactured by ITOCHU CHEMICAL FRONTIER CORPORATION, p-toluenesulfonic acid: manufactured by Meiyu Sangyo Co., Ltd., p-cumene sulfonic acid: manufactured by Teika Co., Ltd., benzoic acid: Wako Pure Chemical Industries, Ltd. Made by company

(D) Component / monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.

Other (pH adjuster)
-Sodium hydroxide: 1M aqueous solution manufactured by Wako Pure Chemical Industries, Ltd. The amount of sodium hydroxide in the table is the content of 1M aqueous solution.

(Discussion)
When Examples 1-14 are compared with Comparative Examples 1-8, it can be seen that Examples 1-14 are superior from the viewpoints of detergency and low temperature stability.
Among Examples, when Examples 1 to 4 are compared, it can be seen that Example 2 in which (c) / (a) is 0.4 is superior from the viewpoint of detergency and low-temperature stability. .
Moreover, when Examples 1, 2, 5, and 6 are compared, it can be seen that Example 2 in which (b) / (c) is 5 is more excellent in terms of detergency and low-temperature stability.
Moreover, when Examples 1, 9, 10, and 14 are compared, it turns out that aromatic sulfonic acid is more excellent in the detergency.
Moreover, when Examples 2 and 12 are compared, it can be seen that Example 2 using alkanolamine as a neutralizing agent is superior in detergency and low-temperature stability.

Claims (7)

(A) an anionic surfactant represented by the following general formula (a1) [hereinafter referred to as component (a)], (b) a carboxylic acid having a reactive unsaturated group having 3 to 6 carbon atoms, or its Polymer containing structural unit derived from salt [hereinafter referred to as component (b)], (c) one or more selected from aromatic sulfonic acid, aromatic carboxylic acid and salts thereof [hereinafter referred to as component (c)] A liquid detergent composition for tableware, containing water.
^{_{R 1 -O- (PO) m1 -SO}} 3 -M 1 (a1)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number of 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]   The liquid detergent composition for tableware of Claim 1 whose mass ratio (c) / (a) of (c) component and (a) component is 0.1-10.   The component (b) is selected from the group consisting of polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, an acrylic acid-maleic acid copolymer or a salt thereof, and a methacrylic acid-maleic acid copolymer or a salt thereof. The liquid detergent composition for tableware according to claim 1 or 2 which is one or more kinds of polymers. The liquid detergent composition for tableware according to any one of claims 1 to 3, wherein the component (c) is an aromatic sulfonic acid represented by the following general formula (c1) or a salt thereof.

[Wherein, X ¹ and X ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. M ² represents a hydrogen atom or a cation. ]   The liquid detergent composition for tableware of any one of Claims 1-4 whose content of (a) component is 1.5 mass% or more and 20 mass% or less. The liquid detergent composition for tableware of any one of Claims 1-5 containing the compound represented by the following general formula (d1).

[Wherein, R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, at least one of which is a carbon number. 1 to 3 hydroxyalkyl groups. ]   The liquid detergent composition for tableware according to any one of claims 1 to 6, wherein the pH is 5 or more and 11 or less at 20 ° C.