JP6611568B2 - Liquid detergent composition and cleaning method thereof - Google Patents

Description

  The present invention can be used mainly in cooking equipment and food processing equipment, has excellent cleaning properties, foamability, effective chlorine stability, dilute solution stability, storage stability, and defoaming properties during rinsing. The present invention relates to a liquid cleaning composition excellent in water and a cleaning method using the cleaning composition.

  Conventionally, when cleaning vertical hard surfaces such as kitchens, workplace walls, floors, etc. in schools, hospitals, employee cafeterias, food processing factories, etc. The foam cleaning method used is employed. In foam cleaning, a stock solution of a cleaning composition or a diluted solution diluted 2 to 100 times with water is put into a foam cleaning machine, and foams generated by water pressure or air pressure are sprayed onto the surface of the object to be cleaned. After being held for a certain period of time, it is cleaned and sterilized by rubbing with a brush or sponge or rinsing with water without rubbing. In such foam cleaning, by applying the cleaning agent in the form of foam, the residence time of the cleaning agent on the surface of the object to be cleaned becomes longer, and the cleaning / sterilization effect is improved.

  The detergent composition used in the foam cleaning method has been developed with an emphasis on foamability and foam stability. However, the conventional detergent composition has a large amount of foam that does not easily break when rinsing. It has a problem that it must be rinsed with rinsing water, and from the point of convenience of cleaning and water saving, sufficient foam is generated at the time of washing, but rinsing with water is good and foam is good It is demanded.

  A method of using a fatty acid or an alkali metal salt thereof in combination with another surfactant, a sequestering agent, or the like has been proposed as a method for improving rinsing properties. Patent Document 1 discloses a cleaning property, foaming property, A liquid detergent product excellent in rinsing properties, low-temperature stability and foam ejection properties is disclosed. Patent Document 2 discloses the provision of a foam cleaning method capable of maintaining good cleaning properties and rinsing properties when foam cleaning is performed using a former, and capable of forming good-quality foam during repeated cleaning. Has been. Metal soap, which is a salt other than alkali metals such as long-chain fatty acids and calcium and magnesium in tap water, is considered to have a defoaming effect because it is a salt insoluble in water.

JP 2012-131951 A JP 2014-5426 A

  However, these are all satisfactory in terms of the effective chlorine stability and storage stability of the stock solution, the stability of the diluted cleaning solution obtained by diluting the stock solution (preventing the turbidity of the diluted cleaning solution), and the anti-scale adhesion property. It was not a thing. The present invention was made to solve the above-mentioned problems of the prior art, and the object of the present invention is excellent in cleaning properties, foaming properties, effective chlorine stability, diluent stability, storage stability, and An object of the present invention is to provide a liquid detergent composition excellent in foaming property at the time of rinsing and a washing method using the detergent composition.

In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, (A) 0.1 to 10% by mass of an oxidizing agent and (B) a fatty acid having a hydrocarbon group having 14 to 22 carbon atoms and a salt thereof. 0.01 to 0.45 mass%, (C) 0.01 to 13.5 mass% of alkyldimethylamine oxide and / or alkenyldimethylamine oxide having a hydrocarbon group having 8 to 18 carbon atoms, (D) 0.01-10 mass% of at least 1 or more types chosen from organic phosphonic acid, condensed phosphoric acid, and these salts, and (E) water are contained, and mass ratio of (B) component and (C) component is ( B) / (C) = 3/10 to 1/50 It has been found that the above-mentioned conventional problems can be solved by using a liquid detergent composition, and the present invention has been completed.

That is, the present invention
(1) (A) 0.1 to 10% by mass of an oxidizing agent, (B) one selected from myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid and salts thereof 0.01 to 0.45 mass% of the above, (C) 0.01 to 13.5 mass% of alkyldimethylamine oxide and / or alkenyldimethylamine oxide having 8 to 18 carbon atoms, (D ) 0.01 to 10% by mass of at least one selected from organic phosphonic acid or a salt thereof, condensed phosphoric acid or a salt thereof, (E) water, and (B) component to (C) component mass ratio (B) / (C) = 3/10 to 1/50 , a liquid detergent composition,
(2) The component (A) is an alkali metal hypochlorite and contains 0.1 to 10% by mass of an effective chlorine content, the liquid detergent composition according to the above (1),
(3) The liquid cleaning composition according to (1) or (2) above, wherein the component (B) is a fatty acid having a hydrocarbon group having 14 carbon atoms and / or a salt thereof,
(4) Octyldimethylamine oxide having (C) component having a hydrocarbon group having 8 carbon atoms, lauryldimethylamine oxide having a hydrocarbon group having 12 carbon atoms, decyldimethylamine oxide having a hydrocarbon group having 10 carbon atoms Or a liquid detergent composition according to any one of (1) to (3) above, comprising any one or a combination of tetradecyldimethylamine oxide having a hydrocarbon group having 14 carbon atoms,
(5) The component (C) is a combination of octyldimethylamine oxide having a hydrocarbon group having 8 carbon atoms and other component (C) other than octyldimethylamine oxide, The liquid detergent composition according to any one of (1) to (4) above, wherein the blending amount is 0.1 to 10% by mass,
(6) It contains lauryl dimethylamine oxide as another component (C), and the mass ratio of lauryl dimethylamine oxide to octyl dimethylamine oxide is (lauryl dimethylamine oxide) / (octyl dimethylamine oxide) = 0.001. The liquid cleaning composition as described in (5) above, which is
(7) Component (D) is 2-phosphonobutane-1,2,4-tricarboxylic acid or a salt thereof, bis (poly-2-carboxyethyl) phosphinic acid or a salt thereof, a phosphinocarboxylic acid copolymer or a salt thereof Bis (poly-2-carboxyethyl) phosphinic acid or a salt thereof, tripolyphosphoric acid, sodium tripolyphosphate, or potassium tripolyphosphate according to any one of (1) to (6) above The liquid detergent composition as described,
(8) The liquid detergent composition according to any one of (1) to (7) above, further comprising (F) an alkali metal hydroxide,
(9) The liquid detergent composition according to any one of (1) to (8) above, further comprising (G) a silicate,
(10) A cleaning method, wherein the liquid cleaning composition according to any one of (1) to (9) above is jetted and washed in a foamed form on an object to be cleaned,
(11) The liquid cleaning composition is preliminarily diluted at a dilution ratio of more than 1 and less than or equal to 100 times, and / or described above (10), wherein the liquid detergent composition is jetted and washed in a foamed form while being diluted. (12) The cleaning method according to (10) above, wherein the stock solution of the liquid cleaning composition is jetted in a foamed manner on the object to be cleaned.
Is a summary.

  The liquid detergent composition of the present invention is excellent in storage stability, has no risk of separation or white turbidity during storage, is excellent in effective chlorine stability, and is excellent in stability of a diluted cleaning liquid. In addition, since the diluted cleaning liquid is excellent in detergency and foaming properties, and is excellent in defoaming property at the time of rinsing, the object to be cleaned can be effectively cleaned by foam cleaning according to the cleaning method of the present invention.

  The liquid detergent composition of the present invention comprises (A) 0.1 to 10% by mass of an oxidizing agent, and (B) 0.01 to 0 of a fatty acid having a hydrocarbon group having 14 to 22 carbon atoms and / or a salt thereof. .45% by mass, (C) 0.01 to 13.5% by mass of alkyldimethylamine oxide and / or alkenyldimethylamine oxide having a hydrocarbon group having 8 to 18 carbon atoms, (D) organic phosphonic acid, condensed phosphorus At least one or more selected from acids and / or salts thereof is contained in an amount of 0.01 to 10% by mass, and (E) water, and the mass ratio of the component (B) to the component (C) is (B) / ( C) = 1/1 to 1/50.

  The liquid detergent composition of the present invention is used for washing with a stock solution without dilution or as a diluted diluted washing liquid. When the component (A) in the liquid detergent composition is less than 0.1% by mass, washing is performed. It is not preferable in terms of cleanability and sterilization at the time, and if it exceeds 10% by mass, it is not preferable in terms of preventing metal corrosion during cleaning. In addition, when the component (B) is less than 0.01% by mass, it is not preferable in terms of foaming property at the time of rinsing, and when it exceeds 0.45% by mass, the storage stability and the washing when storing the cleaning composition are increased. It is not preferable in terms of the prevention of scale adhesion at the time and the stability of the diluted cleaning liquid when the cleaning composition is diluted.

  Further, if the component (C) is less than 0.01% by mass, it is not preferable in terms of detergency, foaming property, and stability of the diluted cleaning solution when diluted and used. Since the effective chlorine stability at the time of agent composition storage falls, it is not preferable. In addition, when the component (D) is less than 0.01% by mass, it is not preferable in terms of storage stability when storing the cleaning composition, prevention of scale adhesion during cleaning, and stability of the diluted cleaning solution. When it mixes exceeding it, the effective chlorine stability at the time of storage of a cleaning composition and the foaming out of a washing | cleaning liquid are bad, and it is unpreferable since rinse property falls.

  In the present invention, the liquid detergent composition preferably contains 0.4 to 8% by mass of the component (A), more preferably 1.5 to 6% by mass, and 2 to 5%. More preferably, it is contained by mass%. Moreover, it is preferable to contain 0.1-0.4 mass% of (B) component, and it is more preferable to contain 0.2-0.35 mass%. Furthermore, it is preferable to contain 0.1-12 mass% of (C) component, it is more preferable to contain 1-10 mass%, and it is further more preferable to contain 3-8 mass%. . Moreover, it is preferable to contain 0.1-8 mass% of (D) component, it is more preferable to contain 0.5-6 mass%, and it is more preferable to contain 1-4 mass%. .

  Examples of the oxidizing agent (A) that is the component (A) include hypochlorous acid, chlorous acid, salts thereof, and the like, and these can be used alone or in combination. From the standpoint of sterility and disinfection, hypochlorous acid or an alkali metal salt of chlorous acid is preferable, and sodium hypochlorite, potassium hypochlorite, or sodium chlorite is more preferable, and sodium hypochlorite is particularly preferable. Is particularly preferred. Specifically, sodium hypochlorite having a commonly used effective chlorine content of 12% by mass is preferred. Of these, low-sodium sodium hypochlorite having a salt concentration of 4% by mass or less is preferable.

  The fatty acid having 14 to 22 carbon atoms and the salt thereof as component (B) include myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, and salts thereof. These may be used alone or in combination. Usually, a fatty acid alkali metal salt is used, but when an alkali is present, such as when an alkali metal hydroxide described later is used in combination, it can also be used in the form of a fatty acid. As the component (B), myristic acid having 14 carbon atoms and a salt thereof are preferable from the viewpoint of the stability of the diluted cleaning solution and the foaming property during rinsing, and sodium myristic acid and potassium myristic acid are particularly preferable.

  In the alkyldimethylamine oxide and / or alkenyldimethylamine oxide having a C8-18 hydrocarbon group as the component (C), the C8-18 alkyl group or alkenyl group may be linear or branched. For example, octyldimethylamine oxide, decyldimethylamine oxide, dodecyldimethylamine oxide (lauryldimethylamine oxide), tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethyl Alkyldimethylamine oxide such as amine oxide, octadecyldimethylamine oxide, octenyldimethylamine oxide, decenyldimethylamine oxide, dodecenyldimethylamine oxide, tridecenyldimethylamine oxide, tetradecenyldimethylamine oxide, Pentadecenyldimethylamine oxide, hexadecenyldimethylamine oxide , Heptadecenyl dimethylamine oxide, the alkenyl dimethyl amine oxides such as octadecenyl dimethylamine oxide and the like. These can be used alone or in combination. Among these, hydrocarbon groups having 8 to 14 carbon atoms of alkyldimethylamine oxide and / or alkenyldimethyl in terms of detergency during washing, foaming of a diluting solution, storage stability of a detergent composition, and effective chlorine stability. Amine oxides are preferred, especially octyldimethylamine oxide having a hydrocarbon group having 8 carbon atoms, lauryldimethylamine oxide having 12 hydrocarbon groups, decyldimethylamine oxide having 10 hydrocarbon groups, or carbon More preferably, any one or a combination of tetradecyldimethylamine oxide having a hydrocarbon group of number 14 is included. Among these, as component (C), lauryldimethylamine oxide having a hydrocarbon group having 12 carbon atoms is preferable because it can improve the properties of the liquid detergent composition in a well-balanced manner.

A liquid detergent composition containing octyldimethylamine oxide as component C is preferable because of its excellent foamability, and particularly good foamability is exhibited even when the liquid detergent composition stock solution is used without dilution. . Therefore, according to the liquid detergent composition containing octyldimethylamine oxide as the C component, it is possible to form a good foam with a former or the like without the need for dilution.
From the viewpoint of realizing good foaming properties, the component (C) is a combination of octyldimethylamine oxide having a hydrocarbon group having 8 carbon atoms and other component (C) other than the octyldimethylamine oxide. It is more preferable that In the liquid detergent composition having the C component which is the combination, the foaming improvement effect due to the addition of octyldimethylamine oxide is remarkable when the blending amount of octyldimethylamine oxide is 0.1 to 10% by mass. It is. In addition, in the liquid cleaning composition, 0.01 to 13.5% by mass of (C) component contained, when octyldimethylamine oxide occupies 0.1 to 10% by mass, 13.5% by mass As an upper limit, other (C) component can be contained. Alternatively, the component (C) may be substantially only octyldimethylamine oxide.
The other component (C) to be combined with octyldimethylamine oxide can be appropriately selected from the various components (C) listed above. Especially, it is preferable to contain any 1 or more types of lauryl dimethylamine oxide (dodecyl dimethylamine oxide), decyl dimethylamine oxide, and tetradecyl dimethylamine oxide as another (C) component. By such a combination, it is possible to provide a liquid detergent composition having excellent balance of foamability and good balance of detergency, foaming property, stability of diluted washing liquid, and the like.
As a more specific preferred embodiment, the component (C) contains octyl dimethylamine oxide and lauryl dimethylamine oxide, and the mass ratio of lauryl dimethylamine oxide to octyl dimethylamine oxide is (lauryl dimethylamine oxide) / ( Octyldimethylamine oxide) = 0.001 to 130. According to the liquid detergent composition of this aspect, the effect of the stock solution foaming property is particularly good.

The organic phosphonic acid or salt thereof as component (D) is preferably a phosphonic acid having no amino group or a salt thereof from the viewpoint of effective chlorine stability in the detergent composition, and further having no hydroxyl group. More preferred is phosphonic acid or a salt thereof. Specific examples include 2-phosphonobutane-1,2,4-tricarboxylic acid or a salt thereof, a phosphinocarboxylic acid copolymer or a salt thereof, and particularly 2-sodium phosphonobutane-1,2,4-tricarboxylate. 2-phosphonobutane-1,2,4-tricarboxylate potassium is preferred. The phosphinocarboxylic acid copolymer is a compound having one or more phosphino groups and two or more carboxyl groups in the molecule, specifically, bis-poly (2-carboxyethyl) phosphinic acid, bis-poly (1,2-dicarboxyethyl) phosphinic acid, poly (2-carboxyethyl) (1,2-dicarboxyethyl) phosphinic acid, bis-poly [2-carboxy- (2-carboxymethyl) ethyl] phosphinic acid, And a reaction product of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and hypophosphorous acid, and preferably poly (2-carboxyethyl) (1,2-dicarboxyethyl) phosphinic acid and bis- Poly [2-carboxy- (2-carboxymethyl) ethyl] phosphinic acid. The phosphinocarboxylic acid copolymer is usually prepared by heating hypophosphorous acid and monoethylenically unsaturated carboxylic acid in the presence of a free radical initiator in an aqueous solvent. No. 29316, Japanese Patent Publication No. 5-57992 and Japanese Patent Publication No. 6-47113. Further, phosphinopolycarboxylic acids are commercially available from BWA under trade names such as Belsperse 164 (registered trademark) and Belclene 400 (registered trademark).
In addition, as an organic phosphonate mentioned above, a potassium salt or a sodium salt can be mentioned, for example. The organic phosphonate contained in the liquid detergent composition is an organic phosphonate at the time of preparation of the liquid detergent composition, and in the preparation process, such as organic phosphonic acid and sodium hydroxide or potassium hydroxide. Any of those formed by reaction with an alkali metal hydroxide may be used. In addition, the number of alkali metals contained in one molecule of the organic phosphonate described above is not particularly limited, and includes known compounds. For example, the above-mentioned potassium 2-phosphonobutane-1,2,4-tricarboxylate includes any one or a combination of two to five potassium salts.

  On the other hand, examples of the condensed phosphoric acid or salt thereof as component (D) include tripolyphosphoric acid or a salt thereof, pyrophosphoric acid or a salt thereof, and among them, sodium tripolyphosphate, potassium tripolyphosphate, and sodium pyrophosphate are preferable. Component (D) may be the above organic phosphonic acid or a salt thereof, condensed phosphoric acid or a salt thereof alone or in combination of two or more thereof, or one or more of organic phosphonic acid or a salt thereof and condensed phosphoric acid. Or you may use it in combination with 1 or more types of the salt.

  Examples of component (E) water include purified water, distilled water, ion-exchanged water, soft water, pure water, ultrapure water, and tap water. These may be used alone or in combination of two or more. The (E) component water is the balance of the liquid detergent composition containing the (A) component, the (B) component, the (C) component, the (D) component, and other components.

  In the liquid detergent composition of the present invention, an alkali metal hydroxide can be further blended as the component (F) in the components (A) to (E). Examples of the alkali metal hydroxide as component (F) include sodium hydroxide, potassium hydroxide and the like, and these can be used alone or in combination, and among these, effective chlorine in the detergent composition. From the viewpoint of the stability of the detergent composition and the storage stability of the detergent composition, it is preferable to blend sodium hydroxide or potassium hydroxide in the detergent composition in an amount of 0.1 to 10% by mass, and 0.5 to 8% by mass. It is more preferable to add 1 to 5% by mass. When the component (F) is used in combination, when a fatty acid is used as the component (B), the same effect as when a fatty acid alkali metal salt is used as the component (B) can be obtained.

In addition to the above components (A) to (E) or the above components (A) to (E) and (F), the liquid detergent composition of the present invention further contains silicate as a component (G) In addition, when silicate is added, the metal corrosion preventing property at the time of cleaning with the cleaning liquid can be improved. The silicate as the component (G) is represented by M ₂ O / nSiO ₂ (wherein M is sodium and potassium, and n is the number of moles of SiO ₂ ), specifically, orthosilicate Sodium, potassium orthosilicate, sodium sesquisilicate, potassium sesquisilicate, sodium metasilicate, potassium metasilicate, No. 1 sodium silicate, No. 1 potassium silicate, No. 2 sodium silicate, No. 2 potassium silicate, No. 3 sodium silicate, No. 3 Potassium silicate etc. are mentioned, These can be used individually or in mixture. Silicates are preferably blended in the detergent composition in an amount of 0.1 to 20% by mass in terms of metal corrosion prevention properties during washing, silicic acid scale prevention properties, and storage stability of the detergent composition. It is more preferable to mix | blend-10 mass%, It is still more preferable to mix | blend 0.5-6 mass%, It is most preferable to mix | blend 1-3 mass%.

  In the cleaning composition of the present invention, the mass ratio of the component (B) and the component (C) needs to be (B) / (C) = 1/1 to 1/50. ) / (C) = 1/2 to 1/30 is more preferable, and (B) / (C) = 1/5 to 1/20 is particularly preferable. When the component (B) and the component (C) are contained in a mass ratio of (B) / (C) = 1/1 to 1/50, a synergistic effect results in cleaning properties and foaming properties when cleaning with the cleaning liquid. And the foamability during rinsing is enhanced. However, if the component (B) is too small relative to the component (C) (if the ratio of the component (B) to the component (C) is smaller than the component (B) / (C) = 1/50), the foam during rinsing If the amount of the component (B) is too much with respect to the component (C) (the ratio of the component (B) to the component (C) than (B) / (C) = 1/1) In many cases, the storage stability of the cleaning composition is reduced, the stability of the diluted cleaning liquid is decreased when the cleaning composition is diluted and used, and the scale may adhere when cleaning with the cleaning liquid. .

  The liquid detergent composition of the present invention may contain other components that are usually used in the technical field as needed, as long as the effects of the present invention are not impaired. Examples of such components include water-soluble solvents, chelating agents, bactericides, pH adjusters, antifoaming agents, thickeners, fragrances, and dyes.

In the liquid detergent composition of the present invention, a stock solution or a diluted solution can be used for foam cleaning. That is, the cleaning method of the present invention can be carried out by spraying the liquid cleaning composition onto the object to be cleaned in the form of foam. According to the cleaning method of the present invention, in which a stock solution of a liquid detergent composition is jetted and washed on an object to be cleaned, the cleaning can be performed without the need to dilute the stock solution. Since it is not necessary to provide a dilution mechanism in a foamer or the like that generates bubbles, the apparatus can be simplified. In the cleaning method of the present invention, when the stock solution of the liquid cleaning composition is used for foam cleaning, the component (C) described above may contain octyldimethylamine oxide having a hydrocarbon group having 8 carbon atoms. preferable. Since the description of the (C) component of a liquid detergent composition is referred suitably for the aspect of a mixing | blending of an octyl dimethylamine oxide, description is omitted here.
In the cleaning method of the present invention, the liquid cleaning composition is preliminarily diluted at a dilution ratio of more than 1 time and not more than 100 times, and / or is sprayed and foamed onto the object to be cleaned while being diluted. Can also be implemented. In the cleaning method based on the premise of dilution, a liquid detergent composition (stock solution) having a high concentration can be obtained, which is excellent in terms of transportability and storage property of the stock solution. When diluting a liquid cleaning composition, it is usually diluted with water. When the dilution ratio exceeds 100 times, there is a possibility that good cleaning properties and foaming properties may not be obtained when the diluted cleaning liquid is jetted and cleaned. Therefore, in the cleaning method of the present invention, the liquid detergent composition described above is preferably diluted at a dilution ratio of more than 1 time and 100 times or less. When foam cleaning is performed using the liquid cleaning composition of the present invention, a diluted cleaning liquid obtained by diluting the cleaning composition is put into a foam cleaning machine, and foam generated by water pressure or air pressure is sprayed onto the object to be cleaned. The method and the liquid detergent composition are put into a foam washer, and the foam washer is connected to a water supply means such as tap water by a hose, etc. For example, a method of spraying on an object to be cleaned. Here, the water used for dilution is generally assumed to be water containing a hardness component such as tap water, and 1 to 20 ° DH is preferable from the viewpoint of the stability of the diluted solution. 1-10 degree DH is still more preferable.

After the foam in which the diluted cleaning liquid is bubbled is sprayed onto the object to be cleaned, the foam is held for a certain period of time. The time for holding the bubbles is 1 to 60 minutes, more preferably 1 to 30 minutes from the viewpoint of workability. While it is preferable to leave the foam in a state of being maintained, a slight amount of water or the like may be added.
After holding the foam for a certain time, the object to be cleaned is rinsed with water. The temperature of the rinsing water is preferably 10 to 70 ° C, more preferably 20 to 60 ° C. As the rinsing water, tap water can be used, and it may be heated and used to adjust to the preferable water temperature. Generally, a rinsing operation by a human hand is performed with a hose or the like.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Each component used for blending in Examples and Comparative Examples is shown below.

(A) Component A1: Sodium hypochlorite A2: Potassium hypochlorite A3: Sodium chlorite

(B) Component B1: Potassium myristate B2: Potassium palmitate B3: Potassium stearate B4: Myristic acid

(B ′) Component [Comparison Component of (B) Component]
B'1: Potassium laurate

(C) Component C1: Dodecyldimethylamine oxide (lauryldimethylamine oxide)
C2: Decyldimethylamine oxide C3: Tetradecyldimethylamine oxide C4: Octyldimethylamine oxide

(D) Component D1: 5-potassium 2-phosphonobutane-1,2,4-tricarboxylate D2: neutralized potassium bis (poly-2-carboxyethyl) phosphinate [Belsperse164 (registered trademark) (manufactured by BWA)] thing]
D3: sodium tripolyphosphate D4: sodium pyrophosphate D5: potassium 1-hydroxyethylidene-1,1-diphosphonate

(D ′) Component [Comparison Component of (D) Component]
D'1: Sodium polyacrylate (weight average molecular weight is 4,000)
D′ 2: Acrylic acid-maleic acid copolymer (weight average molecular weight is 50,000)

(E) Component E1: Ion exchange water

(F) Component F1: Sodium hydroxide F2: Potassium hydroxide

(G) Component G1: potassium orthosilicate (Korei Chemical Industry Co., Ltd., Choline S-458-K)
G2: No. 1 potassium silicate (A chemical potassium silicate manufactured by Nippon Chemical Industry Co., Ltd.)
G3: No. 3 sodium silicate (manufactured by ADEKA Corporation, sodium silicate No. 3)

Examples 1 to 71, Comparative Examples 1 to 16
Liquid detergent compositions were prepared based on the formulations shown in Tables 1-9. Tables 1 to 9 show the properties of each liquid detergent composition and the properties (test results) of a diluted washing solution obtained by diluting each liquid detergent composition. In addition, the numerical value of the mixing | blending of the Example and comparative example in a table | surface represents the mass% of a pure part.

* 1: Storage stability test method:
100 g of each liquid detergent composition was put in a polypropylene container and allowed to stand at −5 ° C. for 1 month, and then the appearance was observed.
Evaluation criteria:
○: No separation or turbidity is observed and stable Δ: There is no overall separation, but some turbidity is observed ×: Separation or turbidity is observed
And Δ and ○ were determined to be practical.

* 2: Effective chlorine stability test method:
Each liquid detergent composition was stored at 40 ° C. for 2 weeks, and the storage stability of hypochlorite or chlorite at that time was evaluated from the effective chlorine residual rate according to the following criteria. In addition, the effective chlorine residual rate was calculated | required by the formula shown below based on JIS method JIS K-0101.
Effective chlorine residual ratio (%) = (effective chlorine concentration in composition after storage) / (effective chlorine concentration in composition before storage) × 100
Evaluation criteria:
A: Effective chlorine residual rate of 80% or more ○: Effective chlorine residual rate of less than 80% to 65% or more Δ: Effective chlorine residual rate of less than 65% to 50% or more ×: Effective chlorine residual rate of less than 50%, Δ, ○, ◎ was judged as practical.

* 3: Test method for evaluation of foamability during rinsing:
Foam at the time of rinsing using a foamer equipped with an aspirator structure (Hydro Systems Company, Hydro Foamer Model 483AP) equipped with a mesh having a mesh size of 60 mesh defined by JIS G3555 (: 2004) at the injection port A cutting test was conducted.
Put 500g of each liquid detergent composition in the container attached to the former, attach Tan's Metering Tip (orifice with 18: 1 dilution factor in the catalog), connect the tap water tap and the aspirator inlet directly with a hose. Connected. The actual liquid detergent composition suction amount of the stock solution was 385 g / min, and the water flow rate was 8.2 L / min. Therefore, the dilution rate was 4.7% by mass. Moreover, the tap water used for dilution was 75 mg / L [German hardness 4.2 degree DH] in conversion of calcium carbonate.
Using this former, a diluted cleaning solution of each liquid detergent composition was sprayed into a sink having an inner diameter of 82 cm × 56 cm × 20 cm for 20 seconds, left for 1 minute, and then tap water (German hardness 5) Rinsing was carried out at ° DH), and the rinsing time until the bubbles disappeared visually was measured. The measured rinse time was determined on the following scale.
Evaluation criteria:
A: Less than 60 seconds O: More than 60 seconds to less than 90 seconds Δ: More than 90 seconds to less than 120 seconds x: More than 120 seconds, and Δ, ○, and ◎ were judged as practical.

* 4: Stability evaluation test method for diluted cleaning solution:
Each liquid detergent composition is diluted with 75 mg / L [German hardness 4.2 ° DH] hard water in terms of calcium carbonate to prepare a 3% by weight diluted cleaning liquid, and the diluted cleaning liquid becomes cloudy within 15 minutes from the preparation. Visual observation was made to determine whether it occurred, and dilution stability was determined on the following scale.
Evaluation criteria:
◯: No turbidity Δ: Somewhat turbidity ×: Turbidity occurred, and Δ and ◯ were judged as practical.

* 5: Detergency test (1) Detergency test (non-heated oil stain)
Test method:
A stainless steel piece coated with oil (beef tallow 10 g, soybean oil 10 g, monooleic acid glyceride 0.25 g, Sudan III 0.1 g dissolved in chloroform 60 ml) and dried at 25 ° C. for 2 hours as a test piece Was measured. This test piece was immersed in 200 ml of a diluted cleaning solution prepared by diluting each liquid detergent composition to 7% by mass with hard water of 75 mg / L [German hardness 4.2 ° DH] in terms of calcium carbonate, and left for 5 minutes. After rinsing with ion exchange water and air drying, the weight was measured. The cleaning rate of the non-heated oil stain was calculated from the change in the weight of the test piece before and after cleaning, and was shown on the following scale.
Evaluation criteria:
◎: Cleaning rate of 100% to 80% or more ○: Cleaning rate of less than 80% to 60% or more Δ: Cleaning rate of less than 60% to 40% or more ×: Cleaning rate of less than 40% Judged as being.
(2) Detergency test (heating oil stain)
Test method:
A stainless steel piece coated with oil (beef tallow 10 g, soybean oil 10 g, monooleic acid glyceride 0.25 g, Sudan III 0.1 g dissolved in chloroform 60 ml) and baked at 180 ° C. for 90 minutes was used as a test piece. It was measured. This test plate is immersed in 200 ml of a diluted cleaning solution prepared by diluting each liquid detergent composition to 5% by mass with hard water of 75 mg / L [German hardness 4.2 ° DH] in terms of calcium carbonate, and left for 5 minutes. After rinsing with ion exchange water and air drying, the weight was measured. The cleaning rate of the heated oil stain was calculated from the change in the weight of the test piece before and after cleaning, and was shown on the following scale.
Evaluation criteria:
◎: Cleaning rate of 100% to 80% or more ○: Cleaning rate of less than 80% to 60% or more Δ: Cleaning rate of less than 60% to 40% or more ×: Cleaning rate of less than 40% Judged as being.

* 6: Metal corrosion prevention test method:
The test piece [aluminum (A5052P)] is used after previously washed with a neutral detergent, treated with acetone and dried. In a diluted cleaning solution prepared by diluting each liquid detergent composition to 5% by mass with hard water of 75 mg / L [German hardness 4.2 ° DH] in terms of calcium carbonate, a test piece, 60 ml with a 70 ml capacity lid It put into the glass bottle, the test piece was immersed in it, and it preserve | saved for 30 minutes in a 25 degreeC thermostat. The test piece after storage was taken out, rinsed and dried with ion exchange water, the appearance of the surface of the test piece was visually observed, and corrosivity was determined according to the following criteria.
Evaluation criteria:
○: No corrosion
Δ: Corrosion is slightly observed, but there is no problem in use. ×: Corrosion is assumed, and Δ and ○ are determined to be practical.

* 7: Test method for foaming test of diluted cleaning solution:
A foaming device having an aspirator structure (Hydro Systems Company, Hydro Foamer Model 483AP) was tested for foamability using a former equipped with a mesh having a mesh size of 60 mesh defined by JIS G3555 (: 2004). Carried out.
Put 500g of each liquid detergent composition in the container attached to the former, attach Tan's Metering Tip (orifice with 18: 1 dilution factor in the catalog), connect the tap water tap and the aspirator inlet directly with a hose. Connected. The actual liquid detergent composition suction amount of the stock solution was 385 g / min, and the water flow rate was 8.2 L / min. Therefore, the dilution rate was 4.7% by mass. Moreover, the tap water used for dilution was 75 mg / L [German hardness 4.2 degree DH] in conversion of calcium carbonate.
Each liquid detergent composition was sprayed for 10 seconds onto a black polypropylene panel 70 cm × 120 cm standing vertically using this former, and the state of bubbles was visually observed and evaluated.
Evaluation criteria:
○: Fine bubbles that are not watery △: Coarse bubbles that are watery
×: No bubble was formed, and Δ and ○ were determined to be practical.

* 8: Test method for sterilization test:
To each 10 mL of diluted cleaning solution prepared by diluting each liquid detergent composition with ion-exchanged water to 1 mass%, 3 mass%, or 5 mass%, 0.1 mL of a bacterial solution obtained by culturing the test strain in an SCD broth medium was added. The test solution was contacted at 25 ° C. for 1 minute. 0.01 ml of this test solution was placed in 1 well of a microplate containing 1 ml of SCDLP broth medium containing 0.1% by mass of sodium thiosulfate and cultured at 37 ° C. for 24 hours. After completion of the culture, the turbidity of the microplate was evaluated by visual observation, and judged according to the following scale.
Test strain:
Escherichia coli NBRC 3972 (10 9th power CFU / mL level) and Staphylococcus aureus NBRC12732 (10 9th power CFU / mL level) of the Foundation for Fermentation Research Institute were used.
Evaluation criteria:
◎: 1% by mass, 3% by mass, and 5% by mass diluted cleaning solution do not cause turbidity. ○: Only 3% by mass, 5% by weight diluted cleaning solution does not cause turbidity. No x: All diluted cleaning solutions were considered to be turbid, and Δ, ○, and ◎ were judged as practical.

* 9: Test method for foaming test of undiluted solution:
The stock solution of each liquid detergent composition was filled in a trigger spray “TS01-F2” manufactured by Life Platec Co., Ltd., and sprayed once onto a black polypropylene panel placed perpendicular to the spray port. The condition was observed and evaluated.
Evaluation criteria:
○: Fine bubbles that are not watery △: Rough bubbles that are watery
×: No bubble was formed, and Δ and ○ were determined to be practical.

  Table 7 shows (C1) / (C4) as a mass ratio of (C1) dodecyldimethylamine oxide and (C4) octyldimethylamine oxide, which are C components.

Claims (12)

(A) 0.1 to 10% by mass of an oxidizing agent,
(B) 0.01 to 0.45% by mass of one or more selected from myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid and salts thereof,
(C) 0.01 to 13.5% by mass of alkyldimethylamine oxide and / or alkenyldimethylamine oxide having a hydrocarbon group having 8 to 18 carbon atoms,
(D) 0.01 to 10% by mass of at least one selected from organic phosphonic acid or a salt thereof, condensed phosphoric acid or a salt thereof,
(E) water,
And a mass ratio of the component (B) to the component (C) is (B) / (C) = 3/10 to 1/50 .   The liquid detergent composition according to claim 1, wherein the component (A) is an alkali metal hypochlorite and contains 0.1 to 10% by mass as an effective chlorine amount.   The component (B) is a fatty acid having a hydrocarbon group having 14 carbon atoms and / or a salt thereof, The liquid detergent composition according to any one of claims 1 and 2.   (C) The component is octyldimethylamine oxide having a C8 hydrocarbon group, lauryldimethylamine oxide having a C12 hydrocarbon group, decyldimethylamine oxide having a C10 hydrocarbon group, or carbon The liquid detergent composition according to any one of claims 1 to 3, comprising any one or a combination of tetradecyldimethylamine oxide having a hydrocarbon group of formula (14). The component (C) is a combination of an octyldimethylamine oxide having a hydrocarbon group having 8 carbon atoms and another component (C) other than octyldimethylamine oxide,
The liquid detergent composition according to any one of claims 1 to 4, wherein a blending amount of the octyldimethylamine oxide is 0.1 to 10% by mass. Including lauryldimethylamine oxide as the other component (C),
The liquid cleaning according to claim 5, wherein a mass ratio of the lauryl dimethylamine oxide to the octyl dimethylamine oxide is (lauryl dimethylamine oxide) / (octyl dimethylamine oxide) = 0.001 to 130. Composition.   (D) component is 2-phosphonobutane-1,2,4-tricarboxylic acid or a salt thereof, bis (poly-2-carboxyethyl) phosphinic acid or a salt thereof, a phosphinocarboxylic acid copolymer or a salt thereof, bis ( The liquid detergent composition according to any one of claims 1 to 6, which is any one of (poly-2-carboxyethyl) phosphinic acid or a salt thereof, tripolyphosphoric acid, sodium tripolyphosphate, and potassium tripolyphosphate. Stuff.   Furthermore, (F) alkali metal hydroxide is contained, The liquid cleaning composition as described in any one of Claims 1-7 characterized by the above-mentioned.   Furthermore, (G) Silicate is contained, The liquid detergent composition as described in any one of Claims 1-8 characterized by the above-mentioned.   A liquid cleaning composition according to any one of claims 1 to 9, wherein the liquid cleaning composition is jetted and foamed onto an object to be cleaned.   The cleaning method according to claim 10, wherein the liquid cleaning composition is diluted in advance at a dilution ratio of more than 1 and not more than 100 times and / or sprayed in a foam state on the object to be cleaned while being diluted.   The washing | cleaning method of Claim 10 which sprays the undiluted | stock solution of a liquid detergent composition to a to-be-washed object in foam shape, and wash | cleans.