JP5495322B2 - Liquid detergent composition for kitchen - Google Patents

Description

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

Zinc ions are excellent substrates that can impart various effects in a small amount in a liquid cleaning composition (Patent Documents 1 to 4). In order to stably dissolve zinc ions in a liquid cleaning composition, water-soluble zinc compounds in the form of chlorides and sulfates have been used (Patent Documents 1 to 4).
However, if zinc is used in the form of chloride or sulfate, even if the production tank of the liquid cleaning composition or the sink in a general household is made of stainless steel, it may be corroded by chloride ions, There is a problem that sulfate ions form sodium sulfate together with sodium ions present in the liquid detergent composition, and precipitate during storage, particularly at low temperature storage.
For this reason, it is necessary to make manufacturing equipment etc. corrosion-resistant, and the compounding quantity of the zinc compound to the liquid detergent composition was restricted.

JP-A-3-79700 Japanese Patent No. 4024446 JP 2004-277554 A JP 2005-336384 A

  The present invention provides a liquid detergent composition for kitchens that has a detergency equal to or better than that of a conventional liquid detergent composition for kitchens, has corrosion resistance and sterilization power, and has improved storage stability. The purpose is to provide.

As a result of intensive studies by the present inventors, it has been found that the above object can be achieved by employing zinc oxide or zinc hydroxide as the zinc compound and dissolving it in water in the presence of a specific ratio of sulfamic acid.
That is, the present invention comprises (A) zinc oxide or zinc hydroxide,
(B) sulfamic acid,
(C) an anionic surfactant;
(D) containing an amine oxide type surfactant,
The liquid detergent composition for kitchens wherein the molar equivalent ratio of the component (B) to the component (A) is (B) / (A) = 1.0 or more and the pH at 25 ° C. is 5.5 or more. Offer things.
The present invention also provides (I) (A) zinc oxide or zinc hydroxide and (B) sulfamic acid dissolved in water at a molar equivalent ratio of (B) / (A) = 1.0 or more. And (II) a method for producing a liquid detergent composition for kitchen, comprising the step of mixing the obtained mixture, (C) an anionic surfactant, and (D) an amine oxide type surfactant. provide.

  According to the present invention, it is possible to suppress the corrosion of the production equipment and the sink, improve the sterilization power and the storage stability, and have a cleaning power equivalent to or better than that of a conventional kitchen liquid cleaning composition, particularly an oil stain cleaning power. A liquid detergent composition for kitchen can be provided. The composition of the present invention is generally difficult to foam, and easily foams even in an environment where the concentration of the cleaning agent is low and the concentration of the oil is high. A large amount of tableware and the like can be washed as compared with the amount of other detergent compositions used.

[(A) component: zinc oxide and / or zinc hydroxide]
Zinc oxide used in the present invention is a compound insoluble in water, and zinc hydroxide is a compound insoluble in water. Zinc oxide and / or zinc hydroxide can improve the detergency of the liquid detergent composition for kitchens or impart sterilizing power to the composition.
Based on the total amount of the composition of the present invention, the component (A) is preferably 0.01 to 2% by mass, more preferably 0.05 to 1.5% by mass, and still more preferably 0.1 to 1.0%. It is preferably contained in an amount of mass%. When contained in such an amount, a sterilizing effect and a detergency improving effect can be sufficiently exhibited. If a larger amount is included, the viscosity increases.

[(B) component: sulfamic acid]
The sulfamic acid used in the present invention can dissolve zinc oxide and zinc hydroxide.
Based on the total amount of the composition of the present invention, the component (B) is preferably 0.025 to 5% by mass, more preferably 0.05 to 4% by mass, and still more preferably 0.1 to 3% by mass. Is preferably included. When such an amount is included, there is no undissolved residue that can be observed with the naked eye when zinc oxide or zinc hydroxide and sulfamic acid are mixed. In addition, corrosion of the production tank and sink can be suppressed.
If the molar equivalent ratio of (B) sulfamic acid to (A) zinc oxide and / or zinc hydroxide is less than 1.0, zinc oxide and / or zinc hydroxide may not dissolve. Moreover, since the tank for dissolving (A) zinc oxide and / or zinc hydroxide with (B) sulfamic acid may corrode when larger than 3.0, (B) / (A) is 3.0. It is preferable that: (B) / (A) is greater than 1.0 and more preferably 2.0 or less.
Here, the molar equivalent ratio is calculated by the following formula.

  For example, 0.65% by mass of (B) component sulfamic acid (molecular weight: 97.1, acid valence: 1) and (A) component zinc oxide (molecular weight: 81.4, base valence: 2) ) When containing 0.25% by mass,

[(C) component: anionic surfactant]
Any anionic surfactant that can be used in the present invention can be used without particular limitation as long as it is usually used in a liquid detergent composition for kitchens.
Specific examples include polyoxyalkylene alkyl ether sulfates, alkylbenzene sulfonates, alkyl sulfates, α-olefin sulfonates, alkane sulfonates, amino acid anionic surfactants, and the like. These can be used alone or in combination of two or more. The carbon chain length of the anionic surfactant used in the present invention is preferably 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms.
Examples of the salt constituting the anionic surfactant include metal salts such as sodium, potassium, magnesium and calcium, ammonium salts, and mono-, di- and tri-lower alkanolamine salts.
It is preferable to contain at least one selected from the group consisting of polyoxyalkylene alkyl ether sulfates, alkylbenzene sulfonates, alkyl sulfates, α-olefin sulfonates and alkane sulfonates. The liquid detergent composition for kitchens containing these anionic surfactants is excellent in detergency.
It is desirable to contain at least one selected from polyoxyalkylene alkyl ether sulfates and alkane sulfonates. The liquid detergent composition for kitchens containing these anionic surfactants is particularly excellent in detergency and also in low temperature stability.

The polyoxyalkylene alkyl ether sulfate has an alkyl group having 10 to 16 carbon atoms, preferably 12 to 14 carbon atoms, and an average of 0.1 to 5 oxyalkylene groups having 2 to 4 carbon atoms, preferably 2 carbon atoms. More preferably, 0.3 to 4 mol is added. If the average added mole number of the oxyalkylene group is out of these ranges, the detergency or low-temperature stability may decrease. A narrow polyoxyethylene group addition molar distribution as disclosed in JP-A-2001-172698 can be used, and a wide distribution can also be used. A narrow distribution width is preferred because the low temperature stability of the composition is excellent.
In particular, a polyoxyethylene alkyl ether sulfate ester salt having a distribution of the number of moles of ethylene oxide defined by the following formula having a narrow ratio of 55% or more is more preferable. When the narrow ratio is 55% or more, preferably 60% or more, more preferably 65% or more, the low-temperature stability of the composition of the present invention becomes better.
Narrow ratio = Y _max-2 + Y _max-1 + Y _max + Y _{max + 1} + Y _{max + 2}
(Here, the ratio in which the number of moles of ethylene oxide added is i is Y _i, and the maximum value Y _i takes is determined based on the total amount of polyoxyethylene alkyl ether sulfate salt represented by the formula (1)). Y _max
The value of the number of moles of ethylene oxide added when Y _i takes Y _max is n _max ,
n is the value of Y _i when an (n _max -2) and Y _max-2,
The value of Y _i when n is (n _max −1) is Y _max−1 ,
The value of Y _i when n is (n _max +1) is Y _{max + 1} ,
The value of Y _i when n is (n _max +2) is Y _{max + 2} .
However, when n _max−2 , n _max−1 or n _max is zero, Y _max−2 , Y _max−1 or Y _max is not counted. )

  As a method for producing such a polyoxyethylene alkyl ether sulfate having a high narrow ratio, that is, a polyoxyethylene alkyl ether sulfate having a narrow distribution of the number of added moles of ethylene oxide, for example, a higher alcohol and ethylene oxide can be produced by a conventional method. From the synthesized reaction product, a polyoxyethylene alkyl ether (alcohol ethoxylate) having a desired molecular weight range, that is, a desired number of moles of ethylene oxide added is fractionated by distillation or the like, and then subjected to a sulfation reaction. Obtained by summing. Further, by the method described in Example 1 of Japanese Patent No. 3312883, that is, a method using a specific catalyst, a polyoxyethylene alkyl ether having a narrow ethylene oxide addition mole number distribution with a narrow rate of 55% or more is obtained. Since it can be obtained, it can also be obtained by sulfating and neutralizing it.

As alcohol used as the raw material of the polyoxyethylene alkyl ether sulfate ester salt which can be used in this invention, the following are mentioned, for example.
(A) Product name Neodol 23 (branch rate: 20%) manufactured by Shell Chemicals. This is produced from an n-olefin by a modified oxo method and rectified.
(B) C13 alcohol obtained from butene trimer by oxo method (branching rate: 100%)
(C) Higher alcohol (branch rate 100%) obtained from a medium chain alcohol by garvet reaction
(D) Product name Safol 23 (branch rate 50%), manufactured by Sasol. In this method, an olefin obtained from gasification of coal is obtained by obtaining an alcohol by the oxo method and further hydrogenating it.
(E) Product name CO1270 (branch rate 0%) manufactured by P & G. This is a natural higher alcohol of C12 / C14 = 70% / 30% synthesized from natural fats and oils.
These alcohols are commercially available in industrial grade.

  The “branch ratio” described above will be described using a primary higher alcohol as a raw material for the polyoxyethylene alkyl ether sulfate salt as an example. The higher alcohol is a mixture of a branched higher alcohol represented by the following formulas (I) to (II) and a linear higher alcohol represented by the formula (III).

In the formulas (I) to (III), R ¹ , R ² and R ⁵ are linear alkyl groups having 1 or more carbon atoms, R ³ and R ⁴ are alkyl having 2 or more carbon atoms, and p is 1 Q is 2 to 3, r is an integer of 1 or more, and the total number of carbon atoms in each formula is equal to the carbon number of the alkyl group in the alkyl ether portion of the polyoxyethylene alkyl ether sulfate ester salt.
The “branch ratio” is the mass of the branched alkyl group in the compounds represented by the above formulas (I) to (III) with respect to the total mass of the hydrocarbon moiety in the compounds represented by the above formulas (I) to (III). Represents a percentage.

The branching rate can be measured under the following conditions using GC / MS.
<Measurement conditions for GC / MS>
Column: Ultra Alloy PY-1
Temperature: Oven; Temperature rising rate 10 ° C / min 50 → 310 ° C
Inlet; 310 ° C
Detector: 310 ° C
Carrier gas: He

  As the alkane sulfonate, a compound that can be represented by the following formula (1) can be used.

In the formula, m + n is 7 to 18, preferably 10 to 14.
M is an alkali metal, alkaline earth metal, alkanolamine or ammonium, specifically sodium, potassium, magnesium, ammonium, and mono, di and triethanolamine salts, for example. It is preferable that M is sodium, potassium, magnesium or ammonium because the detergency is improved.

As the component (C), it is particularly preferable to use a polyoxyethylene alkyl ether sulfate ester salt and an alkane sulfonate represented by the above formula (1) in combination. In this case, it is preferable that the former and the latter are contained in a mass ratio of 4/3 to 8/1.
The component (C) is preferably contained in an amount of 10 to 50% by mass, more preferably 10 to 30% by mass, particularly preferably 15 to 30% by mass based on the total amount of the composition of the present invention. . When it is contained in such an amount, it is possible to exhibit foam sustainability that is sufficiently satisfactory in dishwashing.

[(D) component: amphoteric or semipolar surfactant]
As the amphoteric or semipolar surfactant that can be used in the present invention, any amphoteric or semipolar surfactant can be used without particular limitation as long as it is usually used in a kitchen detergent composition. As the component (D), a semipolar surfactant is preferable.
The semipolar surfactant that can be used in the present invention is preferably an amine oxide surfactant. Examples of amine oxide surfactants include alkylamine oxides having 8 to 26 carbon atoms, alkylamidoamine oxides, and alkylhydroxyamine oxides. From the viewpoint of detergency, the alkyl group preferably has 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms. The most preferred amine oxide type surfactant is lauryl dimethylamine oxide, coconut alkyl dimethylamine oxide or lauryl amide propylamine oxide. For example, Aromox DM12D-W (manufactured by Lion Akzo) is commercially available.
Examples of the semipolar surfactant that can be used in the present invention include those represented by the following general formula (2), and these can be used alone or in combination of two or more.

R ₁ in the formula (2) is a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms. R ₂ and R ₃ are an alkyl group having 1 to ₃ carbon atoms or a hydroxyalkyl group. R ₄ is an alkyl group having 1 to 4 carbon atoms, A is a group selected from —CONH—, —NHCO—, —COO—, —OCO—, or —O—, and n is 0 or 1 Is a number.
From the viewpoint of further detergency, alkyldimethylamine oxide / alkylamidopropyldimethylamine oxide is preferable, and alkyldimethylamine oxide having 10 to 14 carbon atoms is particularly preferable.
Based on the total amount of the composition of the present invention, the component (D) is preferably contained in an amount of 1 to 15% by mass, more preferably 2 to 10% by mass, particularly preferably 2 to 8% by mass. . When contained in such an amount, it is possible to achieve both cleaning power and low-temperature stability. When there are few amphoteric / semipolar surfactants, detergency is reduced, and when there are many amphoteric / semipolar surfactants, low temperature stability is lowered. In order to achieve the high detergency of the present invention, the total weight ratio of the anionic surfactant and the amphoteric / semipolar surfactant is desirably 7/1 to 1/5, more preferably 6/1 to 1/4 is desirable.

The pH of the composition of the present invention is 5.5 or more at 25 ° C. Preferably it is 5.5-7.5, More preferably, it is 6.0-7.0.
The charge of component (D) changes depending on the pH, and the interaction with component (C) changes. When the pH is less than 5.5, the interaction between the component (D) and the component (C) is too strong, and gelation or solidification is liable to occur, resulting in a decrease in freezing / restoring property. Furthermore, the corrosion resistance of the manufacturing equipment and sink is reduced by the acidic substance. If it is greater than 7.5, the interaction becomes too weak, and the effect of improving the cleaning performance may be reduced. Moreover, the component (A) hydroxide may be generated by long-term storage, and the composition may become turbid.
The pH of the composition of the present invention is adjusted to 5.5 or more with a pH adjuster as necessary. As the pH adjuster, it is desirable to use an acid or an alkali agent having a hydrotrope effect that improves low-temperature stability. The acid is preferably an aromatic sulfonic acid and an aromatic carboxylic acid. More preferred are p-toluenesulfonic acid, cumenesulfonic acid, and metaxylenesulfonic acid. Examples of the alkali agent include monoethanolamine, diethanolamine, tritanolamine, sodium hydroxide, potassium hydroxide, and the like, preferably sodium hydroxide and potassium hydroxide. The pH of the composition of the present invention can be determined by measuring the pH using a glass electrode after filling the composition of the present invention into a glass bottle and adjusting it to 25 ° C. in a thermostatic bath at 25 ° C. it can.

[Optional ingredients]
The composition of this invention can contain the component normally contained in the liquid cleaning composition for kitchens in addition to the said (A)-(D) component. Examples of such components include nonionic surfactants; magnesium hydroxide; hydrotropes such as aromatic sulfonates; water-soluble solvents such as ethanol, isopropanol, and butyl carbitol; glycolic acid, lactic acid, malic acid, and citric acid. Hydroxycarboxylic acids such as tartaric acid and gluconic acid, polyvalent carboxylic acids such as oxalic acid, malonic acid, succinic acid, fumaric acid, ethylenediaminetetraacetic acid, nitriloacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine Polymeric carboxylic acid type chelating agents such as aminocarboxylic acids such as hexaacetic acid, polyacrylic acid, polymaleic acid, polyacrylic acid / polymaleic acid copolymer; viscosity modifiers, colorants, antioxidants, preservatives, Disinfectant, disinfectant, anti-inflammatory agent, medicinal ingredients, fragrance, natural extraction And the like.

[(E) component: nonionic surfactant]
By adding a nonionic surfactant, foaming power can be enhanced. Any nonionic surfactant that can be used in the present invention can be used without particular limitation as long as it is usually used in a liquid detergent composition for kitchens.
In particular, a compound represented by the following formula (3) or (4) is preferable.
_{R-CONH-CH 2 CH 2} O- (EO) n-H ··· (3)
[Wherein, R—CO is an acyl group having 6 to 18 carbon atoms, n represents the average number of moles of ethylene oxide added, and n is 0 to 5. ]
In the formula (3), R is a mixture of a linear or branched alkyl group or alkenyl group having 5 to 17 carbon atoms. A linear alkyl group is preferable, and a carbon number of 7-11 is preferable from the viewpoint of a good balance between detergency and solubility. Further, those having 9 carbon atoms are preferably 50% or more, more preferably 80% or more, with respect to the total component (E). n is preferably 0-5, more preferably 0-3, from the viewpoint of cleaning effect.
R—CH ₂ CH ₂ O— (EO) m—H (4)
[Wherein, R represents an alkyl group having 6 to 18 carbon atoms, m represents an average number of added moles of ethylene oxide, and m is 0 to 20. ]
In the formula (4), R- is a mixture of a linear or branched alkyl group or alkenyl group having 6-18 carbon atoms. A linear alkyl group is preferred, and a carbon number of 8-12 is preferred from the viewpoint of excellent balance between detergency and solubility.
(E) It is preferable that 2-20 mass% is contained on the basis of the total weight of the composition of this invention, It is more preferable that 3-15 mass% is contained, 4-10 mass% is especially preferable.

[(F) component: magnesium hydroxide]
Detergency can be improved by adding magnesium hydroxide.
Based on the total amount of the composition of the present invention, the component (F) is preferably 0.01 to 2% by mass, more preferably 0.015 to 1.5% by mass, and particularly preferably 0.02 to 1.0%. It is preferably contained in an amount of mass%. When contained in such an amount, the effect of improving the detergency can be sufficiently exhibited. If a larger amount is included, the viscosity increases.

  As for the viscosity (mPa * s) in 25 degreeC of the composition of this invention, 50-500 are good. Preferably it is 50-300, More preferably, 80-200 is good. When it is less than 50, a problem of dripping may occur. When it is larger than 500, the dischargeability from the container may deteriorate. As the viscosity modifier, a solvent, an organic salt, an inorganic salt, or a polymer having a hydrotrope effect for improving low-temperature stability is preferable. The viscosity of the composition of the present invention was filled with 90 g of the composition of the present invention in a PS11 bottle, adjusted to 25 ° C. in a 25 ° C. constant temperature bath, and No. . This can be determined by installing a 2-rotor, setting a constant temperature sample solution, first setting the rotational speed of the rotor to 60 rpm, and measuring the viscosity after 20 seconds.

[Method for producing liquid detergent composition for kitchen]
The composition of the present invention first comprises (I) (A) zinc oxide or zinc hydroxide and (B) sulfamic acid in water at a molar equivalent ratio of (B) / (A) = 1.0 or more. Dissolve to obtain a mixture. (F) When using magnesium hydroxide, it is mixed at the time of step (I), and in that case, the molar equivalent ratio is preferably (B) / ((A) + (F)) = 1.0 or more. . Subsequently, it can manufacture by mixing (II) the obtained mixture, (C) anionic surfactant, (D) amine oxide type | mold surfactant, and (E) nonionic surfactant.
In addition, when the pH at 25 ° C. after adding an optional component is less than 5.5, the pH is finally adjusted to 5.5 or more, preferably 5.5 to 7.5 with the pH adjusting agent or the like. I can do it.

The components used to prepare the compositions of the examples and comparative examples are shown below.
Component (A): Zinc oxide (molecular weight 81.4, base number 2)
・ Zinc hydroxide (molecular weight 99.4, base number 2)
・ Zinc sulfate heptahydrate (for comparison)
・ Zinc chloride (for comparison)
(B) component and sulfamic acid (molecular weight 97.1, acid number 1)
Hydrochloric acid (for comparison, molecular weight 36.5, acid number 1. Reagent Junsei Chemical Co., Ltd., 35%. The values in Tables 1 and 2 indicate the numerical values as pure)
・ Sulfuric acid (comparative, molecular weight 98.1, acid number 2. Reagent Junsei Chemical Co., Ltd., 95%. Values in Tables 1 and 2 indicate numerical values as pure components)

Component (N): NRES: Sodium C12-14 polyoxyethylene alkyl ether sulfate (average EO chain length 2 mol, narrow rate 55%)
As raw material alcohol, “Neodol23” (C12 / C13 = 40% / 60%, branching rate 20%) manufactured by Shell Chemicals Japan Co., Ltd. and “CO1270” (C12 / C14 = 70% / 30%) manufactured by P & G, (Branching rate 0%) and a mixture (alcohol having 12 carbons / alcohol having 13 carbons = 50% by mass / 50% by mass, branching rate: 20% by mass), and ethylene oxide was added thereto by a known method. Then, the sulfate ester salt was used.
-SAS: Secondary sodium alkanesulfonate (manufactured by Clariant Japan, trade name HOSTAPUR SAS 60, carbon number 14-17)

Component (D) AX: C12 alkyl dimethylamine oxide (manufactured by Lion Akzo, trade name: Aromox DM12D-W)
(E) Component E-1: Polyoxyethylene caprylic acid monoethanolamide (in formula (3), n = 1)
E-2: Polyoxyethylene capric acid monoethanolamide (in formula (3), n = 1)
E-3: Polyoxyethylene lauric acid monoethanolamide (in formula (3), n = 1)
E-4: Polyoxyethylene (EO = 15) lauryl ether (in formula (4), m = 15; manufactured by Lion Corporation, Leox LC-150)
E-5: Polyoxyethylene (2) lauric acid monoethanolamide (in formula (3), n = 2; manufactured by Kawaken Fine Chemical Co., Ltd., Amidette 2L-Y)

<Common component g> Mass% (based on the total amount of the composition)
pTS-H: 3.0
Citric acid-3Na: 0.3
Sodium benzoate: 1.0
Ethanol: 5.0
PEG1000: 2.0
Fragrance: 0.3
pH adjuster: Appropriate amount as needed Water: Balance <Common component h> Mass% (based on the total amount of the composition)
Cumenesulfonic acid Na: 3.5
Glycolic acid: 1.0
Ethanol: 7.0
Sodium benzoate: 1.0
PEG1000: 2.0
Fragrance: 0.2
pH adjuster: Appropriate amount as needed Water: Balance <Common component i> Mass% (based on the total amount of the composition)
Cumenesulfonic acid Na: 3.5
Citric acid-3Na: 0.3
Ethanol: 7.0
Sodium benzoate: 2.0
PEG1000: 2.0
Fragrance: 0.2
pH adjuster: Appropriate amount of water as needed: Balance

[Preparation of compositions of Examples and Comparative Examples]
Process (I)
The component (A) and the component (B) were dissolved in water to obtain a mixture. The appearance of the mixture thus obtained was evaluated as follows. The results are shown in Tables 1 and 2. In addition, the numerical value in Table 1 and Table 2 is the mass% on the basis of the whole quantity of a composition.
Process (II)
The obtained mixture and the remaining components were mixed to obtain a kitchen liquid cleaning composition. In addition, Examples 1-7, 11-13, and Comparative Examples 1-6, 8, and 10 adjusted pH with sodium hydroxide. In Examples 8 and 9, the pH was adjusted with p-toluenesulfonic acid.

(Evaluation method of appearance of mixture of (A) and (B))
The mixture obtained in step (I) was thoroughly stirred and allowed to stand at 25 ° C., and the appearance was observed with the naked eye.
Evaluation criteria ○: Transparent ×: Undissolved remaining In addition, since the composition of Comparative Example 7 does not contain sulfamic acid, the composition of Comparative Example 9 has a molar equivalent ratio of (B) / (A) of less than 1.0. Since the zinc oxide remained undissolved, the (C) component and the (D) component could not be mixed, and therefore the subsequent evaluation could not be performed.

The above-obtained liquid detergent composition for kitchen was evaluated for the corrosion resistance, freeze-recovery property, durability of the cleaning effect, cleaning power and sterilizing power as follows. The results are shown in Tables 1 and 2.
(Evaluation method for corrosion resistance)
The surface of the test piece (SUS304, 3 × 30 × 50 mm) was polished with sandpaper to remove the passive film, and then the oil was removed with a non-corrosive neutral detergent and ethanol. Next, the test piece was put in a 50 ml beaker, and 30 ml of the sample was put. The upper part other than the beaker mouth was covered with aluminum foil, placed in a thermostatic bath at 50 ° C., and the state of the test piece one day later was observed with the naked eye. The results are shown in Tables 1 and 2.
Evaluation criteria ○: Not corrosive ×: Rust on any part −: Not measurable

(Evaluation of freeze / restore (storage stability))
A PS11 bottle was filled with 80 g of sample, frozen at −20 ° C. for 24 hours and then left at 0 ° C. for 24 hours, and this cycle was repeated three times. Thereafter, the presence or absence of precipitates was confirmed visually. The results are shown in Tables 1 and 2.
Evaluation criteria ○: The whole sample is transparent and uniform, and there is no precipitate or starch. ×: Precipitate or starch is seen.

(Evaluation method of cleaning power)
1 g of beef tallow was uniformly applied to a 10 cm × 15 cm tapper container (a plastic container having a bottom surface of 10 cm × 15 cm and a height of 5 cm and having one flat open surface). To a dishwashing sponge of 11.5 cm × 7.5 cm × 3 cm, take 38 g of water and 2 g of the composition of the example or comparative example, and after squeezing by hand several times, Washing was carried out in the same manner as is usually done at home with tap water at 25 ° C. After washing, it was rinsed well with water at 25 ° C., and the cleaning power was evaluated based on the following criteria based on the touch when the surface of the tapper container was touched by hand. The results are shown in Tables 1 and 2. 3 points or more pass.
Evaluation criteria:
5 points: When touching any part of the tapper container, there is a feeling of friction that makes a crisp sound, and there is no feeling of luster due to residual oil.
4 points: When touching the bottom and side surfaces of the tapper container, there is a feeling of friction, and no sliminess due to residual oil is felt, but there is a slight slimness remaining at the corners.
3 points: There is a feeling of friction when the bottom surface of the tapper container is touched, and no oil remains, but some corners remain muggy.
2 points: The tapper container has a feeling of friction in part, but the side and bottom can be felt slim.
1 point: The whole tapper container feels slimy and clearly shows that oil remains.
-: Measurement not possible

(Evaluation of sterilization effect)
Staphylococcus aureus (NBRC 12732) cultured on an agar plate medium at 37 ± 1 ° C. for 18-24 hours is added to a 0.3% neutral medium, 3 ° DH hard water, and the bacterial concentration is about 1.0 × 10 ⁸ cfu. A bacterial solution of / ml was prepared.
Next, a sponge for tableware processed into a cylindrical shape having a diameter of 2.4 cm and a height of 3 cm was put into a screw mouth bottle having a capacity of 110 ml. Next, 0.5 ml of the above bacterial solution was added, and the mixture was uniformly mixed with the sponge using a sterilized glass rod. The screw mouth bottle was sealed and allowed to stand at 25 ± 1 ° C. for 1 hour, so that the bacterial solution was adapted to the sponge. Thereto, 0.5 ml each of the liquid detergent composition for kitchens of Examples and Comparative Examples was added, and the sponge was uniformly squeezed into the sponge using a new sterilized glass rod, which was then resealed and left at 25 ± 1 ° C. for 18 hours. did. After standing, 20 ml of SCDLP medium inactivating agent was added to the screw-mouth bottle, and the sponge was uniformly squeezed with a new sterile glass rod to stop the growth of the bacteria.
A 10-fold dilution series of this solution was prepared and subjected to pour plate culture on a tryptic soy agar medium. The number of colonies that appeared on the medium was measured, and the value obtained by subtracting the logarithm of the number of bacteria after the test from the logarithm of the initial number of bacteria (about 1.0 × 10 ⁸ cfu / ml) Judged by the criteria of. The results are shown in Tables 1 and 2.
Evaluation criteria Completely killed ◎
Bactericidal activity value of 5 or more ○
Bactericidal activity value 2 or more and less than 5 △
Bactericidal activity value less than 2 ×
Measurement impossible −

(Evaluation of durability of cleaning effect)
As an indicator of under what circumstances the cleaning composition can foam, and how long the cleaning effect lasts, a state where the concentration of the cleaning agent is low and oil is present is set. The amount of foam was evaluated.
First, diluted liquids were prepared by diluting the liquid detergent compositions of Examples and Comparative Examples with tap water so that the concentration was 0.2% by mass.
20 mL of the diluted solution prepared above was put into a glass cylindrical tube having an inner diameter of 3 cm and a height of 25 cm, and 2 g of commercially available olive oil (Ajinomoto Co., Inc.) was added.
Subsequently, after making it constant temperature at 25 degreeC, it shaked for 1 minute using the shaker. The height (mm) of the foam immediately after stopping was measured, and the amount of foam was evaluated based on the following evaluation criteria. The results are shown in Tables 1 and 2. 3 points or more pass 5 points: The height of the foam is 40 mm or more.
4 points: The height of the foam is 30 mm or more and less than 40 mm.
3 points: The height of the foam is 20 mm or more and less than 30 mm.
2 points: The height of the foam is 10 mm or more and less than 20 mm.
1 point: Bubble height is less than 10 mm −: Measurement is impossible

Claims (7)

(A) zinc oxide and / or zinc hydroxide;
(B) sulfamic acid,
(C) an anionic surfactant;
(D) an amphoteric or semipolar surfactant,
The liquid detergent composition for kitchens wherein the molar equivalent ratio of the component (B) to the component (A) is (B) / (A) = 1.0 or more and the pH at 25 ° C. is 5.5 or more. object.   The liquid cleaning composition for kitchens of Claim 1 whose quantity of (A) component in a composition is 0.01-2 mass%.   The liquid cleaning composition for kitchens of Claim 1 or 2 whose quantity of (B) component in a composition is 0.025-5 mass%.   (D) A component is an amine oxide type surfactant, The liquid cleaning composition for kitchens of any one of Claims 1-3.   Furthermore, the liquid cleaning composition for kitchens of any one of Claims 1-4 containing (E) nonionic surfactant.   Furthermore, the liquid cleaning composition for kitchens of any one of Claims 1-5 containing (F) magnesium hydroxide. (I) (A) zinc oxide or zinc hydroxide and (B) sulfamic acid are dissolved in water at a molar equivalent ratio of (B) / (A) = 1.0 or more to obtain a mixture, and ( II) A liquid detergent composition for kitchen having a pH of 5.5 or more, comprising a step of mixing the obtained mixture, (C) an anionic surfactant, and (D) an amine oxide type surfactant. Production method.