WO2012070307A1

WO2012070307A1 - Hard surface liquid cleaner composition

Info

Publication number: WO2012070307A1
Application number: PCT/JP2011/072207
Authority: WO
Inventors: 勝幸高野
Original assignee: 花王株式会社
Priority date: 2010-11-24
Filing date: 2011-09-28
Publication date: 2012-05-31
Also published as: JP5819685B2; TW201221638A; JP2012126884A; CN103221528A; TWI548736B

Abstract

A hard surface liquid cleaner composition containing (a) a polyalkylene glycol monoalkyl ether in the amount of 1-15 mass%, (b) amine oxide, (c) at least one type of surfactant selected from a group consisting of an ampholytic surfactant and an anionic surfactant excluding soaps and present in the amount of 0.01-15 mass%, and water. The mass ratio of (c)/((b)+(c)) is 0.01/1-1/1. 60-100 mass% of the (a) component is a dipropylene glycol (C4-8 alkyl group) monoalkyl ether. The pH at 25°C is 6-14. This hard surface liquid cleaner composition not only exhibits strong cleaning power against cooking oil buildup, but also has the effect of remaining in a uniform liquid state with no turbidity or separation, and having excellent storage stability at high or low temperatures.

Description

Liquid detergent composition for hard surfaces

The present invention relates to a liquid cleaning composition for hard surfaces.

Generally, as cleaning agents for hard surfaces, those having a composition suitable for each of them are used in order to remove different stains to be treated such as bathrooms, kitchens and floors. For example, kitchen cleaners used around kitchens such as ovens, ovens, walls and floors around the range, and exhaust fans are used to remove oil stains that have been altered by the action of heat, sunlight, oxygen in the air, etc. A cleaning agent containing an activator, a solvent, an alkali agent and the like is used. Also, as bathroom cleaners used in bathrooms such as bathtubs, bathroom walls and floors, metal soaps, especially detergents containing detergents, metal ion sequestering agents, etc., are used to remove dirt from fatty acid calcium salts. The agent is used.

Of these cleaning agents, the cleaning agents used in the kitchen are applied to a part of the hard surface such as a wall around the range and a cooking table. After application to a hard surface, it is spread over a wide area using tools such as towels and sponges, and dirt such as oil and dust is removed. Oil smoke generated by daily cooking work adheres to hard surfaces such as the walls around the range and the cooking table, but most of these stains exist in a state that is less susceptible to oxidation and heat denaturation for about a week. ing. In order to remove such cooking oil stains, it is necessary to use the solubilizing and emulsifying power of the surfactant, the dissolving power and swelling power of the solvent, etc., but the solvent is a dialkylene (2 to 4 carbon atoms). Glycol monoalkyl (4 to 8 carbon atoms) ethers, particularly dipropylene glycol monoalkyl ethers having 4 to 8 carbon atoms in the alkyl group, are excellent in the removal of cooking oil stains with a low degree of modification described above. There is a demand for a detergent containing this. Since the above solvent alone does not dissolve in water, if there is no surfactant, it becomes a two-layer separation system and is very inconvenient.

Patent Document 1 discloses a hard surface detergent composition containing dipropylene glycol monobutyl ether as a glycol solvent and having excellent detergency against stubborn modified oil stains. There is no suggestion regarding the removal of low cooking oil stains.

Patent Document 2 discloses a liquid detergent composition for air conditioning fins containing dipropylene glycol monobutyl ether and a surfactant as a glycol solvent. However, it does not suggest a cleaning effect or workability for oil stains generated in the kitchen.

Patent Document 3 discloses a hard surface cleaning agent containing dipropylene glycol monobutyl ether as a lipophilic substance and comprising two or more layers. Each prescription described in the example of Patent Document 3 is in a state of being separated into two layers, and the contents of the container must be mixed and temporarily changed to an emulsified state every time it is washed.

Since the composition shown in the Example of Patent Document 3 is mixed immediately before use, and the operation becomes complicated, a method that can be easily used in a squeeze container or a spray container using a single layer of liquid is preferable. . Although a method of using in combination with a surfactant is also conceivable, when a large amount of surfactant is used, not only the original cleaning effect of the above-mentioned solvent is lost, but also the cleaning and wiping work performed so that no detergent remains after use is time consuming. It is necessary and not preferable for consumers. Therefore, it is required to uniformly dissolve the solvent with as little surfactant as possible. However, when a small amount of surfactant is used, even if it can be uniformly dissolved at room temperature, the layer becomes turbid or separated at a high temperature during storage. If the composition is used without being sufficiently mixed with turbidity or separation, the composition composition cannot be kept constant until the end, which causes a decrease in performance.

Patent Document 4 discloses an aqueous cleaning composition suitable for removing dirt encountered in a bathroom containing dipropylene glycol monobutyl ether as a lipophilic substance. However, dipropylene glycol monobutyl ether is blended as a hydrotrope for increasing the viscosity of the composition, and Patent Document 5 does not suggest any cleaning effect of the lipophilic substance.

Patent Document 5 discloses a hard surface cleaning composition containing a nonionic surfactant, dipropylene glycol monobutyl ether as a hydrophobic solvent, and an anionic surfactant. No suggestion regarding sex.

Patent Document 6 discloses a phase-stable liquid fabric refreshing composition comprising a solvent such as butoxypropoxypropanol, but does not suggest any removability of cooking oil stains having a low degree of modification.

JP 2008-45108 A JP 2000-290699 A Special table 2003-506561 Special table 2001-524592 WO93 / 04151 JP 11-511800 A

As a result of intensive studies by the present inventors, polyalkylene glycol monoalkyl ether represented by the following formula (a1) [component (a)]], amine oxide [component (b)], and anionic properties excluding soap One or more surfactants selected from surfactants and amphoteric surfactants (component (c)) are contained as essential components, and the mass ratio of (c) component / ((b) component + (c) component) Is 0.01 / 1 to 1/1, and 60 to 100% by mass of the component (a) is a monoalkyl ether having 4 to 8 carbon atoms in the alkyl group of dipropylene glycol [component (a-1)]. In certain compositions, a uniform liquid phase with no turbidity or separation is formed, and it also has excellent detergency against oil stains and storage stability, and particularly exhibits excellent detergency against cooking oil stains with a low degree of modification. Heading to The present invention has been completed.

R ^1a (OR ^2a ) _l OH (a1)
[Wherein R ^1a is an alkyl group having 4 to 8 carbon atoms, 1 is a number having 1 to 4 and R ^2a is an alkylene group having 2 to 4 carbon atoms. ]

The present invention relates to a hard surface cleaning having excellent detergency against cooking oil stains, which contains a polyalkylene glycol monoalkyl ether having 2 to 4 carbon atoms in an alkylene group and 4 to 8 carbon atoms in an alkyl group. The present invention relates to providing a composition capable of forming a uniform liquid composition with as little surfactant as possible.

Furthermore, the present invention provides a hard surface liquid detergent composition that is excellent in cooking oil stain detergency, forms a uniform liquid phase without turbidity or separation, and has excellent storage stability at high and low temperatures. About that.

Furthermore, the present invention relates to providing a liquid detergent composition for hard surfaces that exhibits excellent detergency against cooking oil stains having a particularly low degree of modification.

The liquid detergent composition for hard surfaces of the present invention not only has a high detergency against cooking oil stains, but also exists as a uniform liquid phase without turbidity or separation, and excellent storage at high and low temperatures Has the effect of exhibiting stability. Although the liquid detergent composition for hard surfaces of this invention can be applied to various hard surfaces, since it is especially suitable for the hard surface around a kitchen, it is suitable as a liquid detergent composition for kitchens. Since the liquid detergent composition for hard surfaces of the present invention exhibits excellent detergency against oil stains having a low degree of modification, it can be preferably applied to hard surfaces around kitchens where such oil stains are present. it can. In the present specification, the state in which the composition “is present as a homogeneous liquid phase” means that the composition is stirred and allowed to stand at room temperature (for example, 25 ° C.) for 1 hour, and then turbidity and separation cannot be visually confirmed. It is a state.

The liquid detergent composition for hard surfaces of the present invention contains a monoalkyl ether of polyalkylene glycol represented by the following formula (a1) from the viewpoint of detergency as the component (a). From the viewpoint of detergency against oil stains and storage stability, particularly from the viewpoint of detergency against low-denatured oil, the content of component (a) is 1 to 15% by mass, preferably 2 to 10% by mass of the composition of the present invention. %. 1 mass% or more is preferable from a viewpoint of the detergency with respect to oil stains, 2 mass% or more is more preferable, 15 mass% or less is preferable from a viewpoint of storage stability, and 10 mass% or less is more preferable. Examples of R ^1a in formula (a1) include butyl group, isobutyl group, hexyl group, 2-ethylhexyl group and the like from the viewpoint of detergency against oil stains and storage stability, and butyl group or hexyl group is preferable. Groups are more preferred. R ^2a in formula (a1) is preferably an ethylene group, a propylene group, or a butylene group, more preferably an ethylene group or a propylene group, and even more preferably a propylene group, from the viewpoints of detergency against oil stains and storage stability. Furthermore, from the viewpoint of detergency against oil stains and storage stability, l is 1 to 4, more preferably a number of 2 to 3, and still more preferably a number of 2.

Furthermore, as component (a), (a-1) monoalkyl ethers having 4 to 8 carbon atoms in the alkyl group of dipropylene glycol are particularly suitable for low-modified oils from the viewpoint of detergency against oil stains and storage stability. From the viewpoint of detergency, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono (2-ethylhexyl) ether are more preferred, dipropylene glycol monobutyl ether, dipropylene glycol Monoisobutyl ether and dipropylene glycol monohexyl ether are more preferred, dipropylene glycol monobutyl ether and dipropylene glycol monohexyl ether are still more preferred, Glycol monobutyl ether are especially preferred. Component (a) may be a single compound or a mixture of a plurality of compounds, but from the viewpoint of detergency against oil stains, component (a-1) in component (a) is 60 to 100% by mass, preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 100% by mass.

The liquid detergent composition for hard surface of the present invention has, as component (b), high temperature storage stability, low temperature storage stability, from the viewpoint of detergency against low-modified oil, particularly from the viewpoint of detergency against low-modified oil, Contains amine oxide. The content of component (b) is preferably 0.05 to 15% by mass of the composition of the present invention, more preferably 0.06 to 5% by mass, still more preferably 0.08 to 4% by mass, and still more preferably. 0.1 to 3.5% by mass. From the viewpoint of storage stability, 0.05% by mass or more is preferable, 0.06% by mass or more is more preferable, 0.08% by mass or more is further preferable, 0.1% by mass or more is more preferable, 15 mass% or less is preferable from a viewpoint of component persistence, 5 mass% or less is more preferable, 4 mass% or less is further more preferable, and 3.5 mass% or less is still more preferable.

The mass ratio of the component (a) to the total amount of the component (b) and the component (c) described later is preferably (a) / ((b) + (c)) = 1/1 to 15/1. 1.2 / 1 to 14/1 is more preferable, and 1.5 / 1 to 13/1 is still more preferable. From the viewpoint of detergency against oil stains, 1/1 or more is preferable, 1.2 / 1 or more is more preferable, 1.5 / 1 or more is more preferable, and from the viewpoint of high-temperature storage stability, 15/1 or less is preferable. / 1 or less is more preferable, and 13/1 is still more preferable.

Examples of the component (b) include the following.

From the viewpoint of detergency against oil stains, an alkyl or alkenylamine oxide having preferably a hydrocarbon group having 8 to 18 carbon atoms, more preferably a linear or branched alkyl group or alkenyl group can be mentioned. More preferable amine oxides include alkyl or alkenyl amine oxides represented by the following general formula (b1).

(In the formula, R ^1b is preferably a hydrocarbon group having 8 to 18 carbon atoms, more preferably an alkyl group or an alkenyl group, R ^2b and R ^3b are the same or different alkyl groups having 1 to 3 carbon atoms, D represents an —NHC (═O) — group or —C (═O) NH— group, E represents an alkylene group having 1 to 5 carbon atoms, and m and n are m = 0 and n = 0 or m = 1 and n = 1.)

In the general formula (b1), R ^1b is preferably a hydrocarbon group having 8 to 18 carbon atoms, more preferably an alkyl group or an alkenyl group, from the viewpoint of detergency against oil stains. An alkyl group is preferred, an alkyl group having 12 to 14 carbon atoms is more preferred, and an alkyl group having 12 carbon atoms is still more preferred. R ^2b and R ^3b are alkyl groups having 1 to 3 carbon atoms, and methyl groups having 1 carbon atom are more preferable.

Preferable examples of the alkyl or alkenylamine oxide represented by the general formula (b1) include alkyldimethylamine oxide in which R ^1b is an alkyl group having 8 to 18 carbon atoms from the viewpoint of detergency against oil stains. Specific examples include caprylyl dimethylamine oxide, capryl dimethylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, and the like. Furthermore, lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, palmitic acid amidopropyl dimethylamine oxide and the like are also included in preferred examples.

The liquid detergent composition for hard surfaces of the present invention is one or more surfactants selected from anionic surfactants and amphoteric surfactants excluding soap as component (c) from the viewpoint of high-temperature storage stability. Containing.

Anionic surfactants excluding soap include alkylbenzene sulfonate, alkane sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester, α-olefin sulfonate, α-sulfo fatty acid methyl ester salt, Examples include polyoxyethylene alkyl (or alkenyl) ether carboxylate and polyoxyethylene amido alkyl (or alkenyl) ether carboxylate. The anionic surfactant may be a single compound or a mixture of a plurality of compounds.

The alkyl or alkenyl carbon chain length in the anionic surfactant is preferably from 8 to 18, and more preferably from 10 to 14.

EO addition mole number in polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkyl (or alkenyl) ether carboxylate salt, polyoxyethylene amido alkyl (or alkenyl) ether carboxylate salt is from the viewpoint of detergency against oil stains An average of 1 to 10 is preferred.

As the counter ion of the anionic surfactant, sodium, potassium, magnesium, calcium, alkanolamine, and ammonium are preferable, and sodium, potassium, and alkanolamine are preferable from the viewpoint of detergency against oil stains.

Although it does not specifically limit as an amphoteric surfactant, In this invention, 1 type, or 2 or more types chosen from the betaine represented by the following general formula (c1), (c2), (c3) and (c4) is mentioned. be able to. The amphoteric surfactant may be a single compound or a mixture of a plurality of compounds.

(Wherein R ^1c represents a hydrocarbon group having 8 to 18 carbon atoms, preferably a linear or branched alkyl group or alkenyl group, and R ^2c and R ^3c may be the same or R 1 represents a different alkyl group having 1 to 5 carbon atoms, R ^4c represents a hydrocarbon group having 7 to 17 carbon atoms, preferably a linear or branched alkyl group or alkenyl group, Y represents a hydrogen atom or a hydroxyl group, (r, s, and t are numbers from 1 to 3, u is a number from 1 to 5, v is a number greater than 1, and w and x are numbers that satisfy 0 ≦ w + x ≦ 4.)

In general formula (c1), R ^1c is preferably an alkyl group having 8 to 18 carbon atoms, and more preferably an alkyl group having 10 to 16 carbon atoms in terms of detergency against oil stains. For the same reason, R ^2c and R ^3c are each preferably a methyl group, an ethyl group or a hydroxyethyl group, and r is preferably 1.

In general formula (c2), R ^1c is preferably an alkyl group having 8 to 18 carbon atoms, more preferably an alkyl group having 10 to 16 carbon atoms, from the viewpoint of detergency against oil stains. For the same reason, R ^2c and R ^3c are each preferably a methyl group, an ethyl group or a hydroxyethyl group, s is preferably 1, and t is preferably 1.

In general formulas (c3) and (c4), R ^4c is preferably an alkyl group having 9 to 15 carbon atoms from the viewpoint of detergency against oil stains. For the same reason, R ^2c and R ^3c are each preferably a methyl group, an ethyl group or a hydroxyethyl group, u is preferably 2 or 3, v is preferably 1, w is preferably 1, and x is preferably 1.

Specific examples of the betaine represented by the general formula (c1), (c2), (c3) or (c4) include fatty acid amidopropyl-N, N-dimethylacetic acid betaine, fatty acid amidopropyl-N, N-dimethyl-2 -Hydroxypropylsulfobetaine, fatty acid amidopropyl-N, N-dimethyl-propylsulfobetaine, alkyl-N, N-dimethyl-2-hydroxypropylsulfobetaine, and the like. Among these, in terms of detergency against oil stains and foaming power, amidopropyl laurate-N, N-dimethylacetate betaine, amidopropyl myristate-N, N-dimethylacetate betaine, cocamidopropyl-N, N -Dimethyl acetate betaine, lauryl-N, N-dimethyl-2-hydroxypropylsulfobetaine, amidopropyl laurate-N, N-dimethyl-2-hydroxypropyl betaine and the like are preferable.

The content of the component (c) is 0.01 to 15% by mass in the hard surface liquid detergent composition of the present invention, preferably in the range of 0.05 to 1% by mass, and preferably 0.1 to 0.001%. The range of 7% by mass is more preferable, and the range of 0.1 to 0.5% by mass is particularly preferable. From the viewpoint of storage stability, it is 0.01% by mass or more, preferably 0.05% by mass, more preferably 0.1% by mass or more, from the viewpoint of detergency, 15% by mass or less, and 1% by mass or less. Preferably, 0.7 mass% or less is more preferable, and 0.5 mass% or less is particularly preferable. When an anionic surfactant excluding soap is used as the component (c), the content is more preferably 0.02 to 0.6% by mass, still more preferably 0.1 to 0.5% by mass. When an amphoteric surfactant is used as the component (c), the content is more preferably 0.1 to 0.6% by mass, still more preferably 0.3 to 0.5% by mass.

The component (c) is a component necessary for making the composition of the present invention a stable homogeneous liquid phase under storage conditions. Furthermore, from the viewpoint of cleaning performance and storage stability, (c) / ((b) + (c)) = as a mass ratio between the component (c) and the total amount of the component (b) and the component (c) 0.01 / 1 to 1/1, preferably 0.04 / 1 to 0.6 / 1, more preferably 0.07 / 1 to 0.5 / 1, and 0.079 / 1 to 0.5. / 1 is more preferable, and 0.2 / 1 to 0.35 / 1 is particularly preferable.

The reason why the high-temperature stability and low-temperature stability of the composition, particularly high-temperature storage stability, is improved by blending the component (c) is not clear at present, but a possible mechanism will be described below.

(B) The dipole force, which is the main interaction between the hydrophilic group of the component and water, decreases with increasing temperature. Therefore, the component (b) has a tendency to cause layer separation with water as the temperature rises. Then, the component (b) cannot solubilize the component (a) as a surfactant.

However, since the oxygen in the amine oxide part of the component (b) is electron withdrawing, it is considered that the nitrogen atom adjacent to the oxygen in the hydrophilic group of the component (b) is slightly positively charged. Therefore, it is considered that a weak electrical interaction acts between the component (b) and the component (c) having an anionic portion. For this reason, when the component (c) is blended, the component (b) is less likely to cause layer separation with water, the component (b) can function as a surfactant, and the component (a) (B) It is thought that separation of the component and water can be suppressed.

When the above mechanism is estimated, it is estimated that the component (c) has a higher effect of a strong anionic component. The fact that the anionic surfactant tends to exert its effect in a smaller amount than the amphoteric surfactant suggests that the above-mentioned stabilization mechanism may have occurred. Therefore, as the component (c), an anionic surfactant excluding soap is more preferable.

Also, as one of the characteristics of the component (c), the presence of a hydrophobic group long enough to form mixed micelles is considered important. This hypothesis is that an anionic compound containing only an alkyl group having 6 or less carbon atoms of a hydrophobic group or an aryl group having 10 or less carbon atoms (for example, an acid such as citric acid, propionic acid, benzoic acid, p-toluenesulfonic acid, and the like) The salt) is estimated from the fact that the effect as the component (c) in the present invention tends to be weak.

The liquid detergent composition for hard surface of the present invention preferably contains alkanolamine and / or alkali hydroxide as the component (d) from the viewpoint of further improving the cleaning performance. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine, and monoethanolamine is more preferable from the viewpoint of detergency against oil stains. In this specification, the alkali hydroxide is an alkali metal or alkaline earth metal hydroxide. Examples of the alkali hydroxide include sodium hydroxide and potassium hydroxide.

The content of the component (d) is preferably 0.01 to 20% by mass, more preferably 0.05 in the hard surface liquid detergent composition of the present invention in order to provide sufficient detergency against oil stains. -15% by mass, more preferably 1.5-15% by mass, still more preferably 2-10% by mass, still more preferably 3-7% by mass, and even more preferably 3-5% by mass. The component (d) may be a single compound or a mixture of a plurality of compounds.

In the liquid detergent composition for hard surface of the present invention, a builder component can be blended as the component (e) from the viewpoint of further improving the cleaning performance. As a builder component, the following 1 type (s) or 2 or more types can be used.

(1) aminopolyacetic acid such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, diencoric acid Alkali metal salt or alkanolamine salt.

(2) Alkali metal salts or alkanols of organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid Amine salt.

Among these, citric acid, malic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid or salts thereof are preferable. The salt form is preferably a sodium salt, potassium salt, ammonium salt or alkanolamine salt.

The content of the component (e) in the composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and further preferably 0.2 to 0.2% by mass from the viewpoint of detergency against oil stains. 1% by mass.

In addition to the above components, the liquid detergent composition for hard surface of the present invention may contain other components in a range that does not impair the object or effect of the present invention. For example, surfactants such as polyoxyethylene alkyl ether and alkyl (poly) glycoside, ethanol, propanol, glycerin, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, alkyl monoglyceryl ether having an alkyl group with 3 to 8 carbon atoms And EO average added mole number of 1 to 5 solvents such as polyoxyethylene phenyl ether or benzyl ether, antioxidants such as BHT, antibacterial and antifungal agents, and antiseptics. In the liquid detergent composition for hard surface of the present invention, polyacrylic acid and a salt thereof, a copolymer of olefin and maleic anhydride and a salt thereof as optional components, and other paragraphs of JP-A-7-292398 A dispersing agent such as a carboxylic acid polymer or a sulfonic acid polymer described in 0035 to 0038 can also be blended.

Examples of the polyoxyethylene alkyl ether include the following (1) or (2).
(1) A polyoxyethylene alkyl ether or alkenyl ether, wherein the average carbon number of the alkyl group or alkenyl group is 10 to 18, preferably 10 to 16, from the viewpoint of detergency against oil stains, and ethylene oxide (hereinafter referred to as EO). The number of moles added is 1 to 30 moles on average, preferably 6 to 20 on average. Preferable examples of such (1) include polyoxyethylene alkyl ethers having 8 to 18 carbon atoms in the alkyl group.

(2) A polyoxyethylene alkyl phenyl ether having an average alkyl group carbon number of 6 to 12 from the viewpoint of detergency against oil stains and an average number of EO addition moles of 1 to 25 moles.

The alkyl (poly) glycoside is preferably an alkyl (poly) glycoside represented by the following general formula (b2) from the viewpoint of detergency against oil stains.

R ^4b (OR ^5b ) _x G _y (b2)
(Wherein R ^4b represents a hydrocarbon group, preferably a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group or an alkylphenyl group, and R ^5b represents an alkylene group having 2 to 4 carbon atoms. G represents a residue derived from a reducing sugar having 5 to 6 carbon atoms, x represents 0 to 5, and y represents 1 to 5.)

In the liquid detergent composition for hard surface of the present invention, water is blended together with the above components. The blending amount of water is an amount adjusted to be 100% by mass in total. That is, the balance of the composition is water. The amount of water is preferably from 70 to 98% by mass, more preferably from 75 to 96% by mass, and still more preferably from 80 to 94% by mass, from the viewpoint of detergency against oil stains and high-temperature stability. The pH of the liquid detergent composition for hard surface of the present invention at 25 ° C. is 6 to 14, preferably 7.5 to 14 from the viewpoint of detergency against oil stains and ensuring safety during use. In order to obtain high detergency, the pH is 6 or more, preferably 8 or more, more preferably 8.5 or more, more preferably 9 or more, and further preferably 10 or more. On the other hand, from the viewpoint of ensuring safety during use, the pH is 14 or less, preferably pH 13 or less, more preferably 12 or less, and particularly preferably pH 11.5 or less. That is, the pH of the liquid detergent composition for hard surface of the present invention at 25 ° C. is preferably 7.5 to 14, more preferably 8 to 13, more preferably 9 to 12, The preferred range is 10 to 11.5. The pH was measured using a pH meter D-52S manufactured by HORIBA, Ltd. and a pH electrode 6367-10D.

The liquid detergent composition for hard surface of the present invention can be produced by appropriately mixing each component.

The present invention relates to a liquid detergent composition for a hard surface. Here, the “hard surface” maintains a certain shape regardless of whether it is planar or three-dimensional. The degree of hardness is not limited as long as it can be washed. This hard surface includes fixed objects such as floors, stairs and walls made of plastic, rubber, metal, tile, brick, concrete, cement, glass, wood, etc., as well as various instruments, instruments, tools, furniture, List all things that people touch, such as tableware. More preferably, a plastic, a metal, glass, etc. can be mentioned.

Therefore, the liquid detergent composition for hard surfaces of the present invention includes a kitchen cleaner, a bathroom cleaner, a floor cleaner, a dish cleaner, a fully automatic washing machine washing tub cleaner, and a drain pipe cleaner. It can be applied as a cleaning agent for small items in kitchens and bathrooms, and more preferably as a cleaning agent for kitchens.

Embodiments of the present invention are exemplified below.
[1] (a) 1 to 15% by mass, preferably 2 to 10% by mass, of a monoalkyl ether of polyalkylene glycol represented by the following formula (a1),
(B) amine oxide,
(C) 0.01 to 15% by mass, preferably 0.1 to 0.7% by mass of one or more surfactants selected from the group consisting of anionic surfactants excluding soap and amphoteric surfactants More preferably 0.1 to 0.5% by weight, as well as water,
The mass ratio of component (c) / (component (b) + component (c)) is 0.01 / 1 to 1/1, and is 60 to 100% by mass, preferably 80 to 100% by mass of component (a). More preferably 90 to 100% by mass, more preferably 100% by mass is (a-1) a monoalkyl ether in which the alkyl group of dipropylene glycol has 4 to 8 carbon atoms,
A liquid detergent composition for hard surfaces having a pH of 6 to 14 at 25 ° C.
R ^1a (OR ^2a ) _l OH (a1)
[Wherein R ^1a is an alkyl group having 4 to 8 carbon atoms, l is a number of 1 to 4, preferably 2 to 3, more preferably 2, and R ^2a is a number of 2 to 4 is an alkylene group, preferably a propylene group. ]
[2] The mass ratio of (a) component / ((b) component + (c) component) is 1/1 to 15/1, preferably 1.2 / 1 to 14/1, more preferably 1.5 / [1] The composition according to [1], which is 1 to 13/1.
[3] The composition according to [1] or [2], wherein the component (b) is an alkyl or alkenylamine oxide represented by the following general formula (b1).

(In the formula, R ^1b is preferably a hydrocarbon group having 8 to 18 carbon atoms, more preferably an alkyl group or an alkenyl group, R ^2b and R ^3b are the same or different alkyl groups having 1 to 3 carbon atoms, D represents an —NHC (═O) — group or —C (═O) NH— group, E represents an alkylene group having 1 to 5 carbon atoms, and m and n are m = 0 and n = 0 or m = 1 and n = 1.)
[4] The composition according to any one of [1] to [3], wherein the component (b) is an alkyldimethylamine oxide having 8 to 18 carbon atoms in the alkyl group.
[5] Component (b) is contained in an amount of 0.05 to 15% by mass, preferably 0.06 to 5% by mass, more preferably 0.08 to 4% by mass, and more preferably 0.1 to 3.5% by mass. The composition according to any one of the above [1] to [4].
[6] The composition according to any one of [1] to [5], wherein the component (c) is an anionic surfactant excluding soap.
[7] The component (c) is an alkylbenzene sulfonate, alkane sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, α-olefin sulfonate salt, α-sulfo fatty acid methyl ester salt, polyoxy The composition according to any one of [1] to [6], which is an ethylene alkyl (or alkenyl) ether carboxylate or a polyoxyethylene amido alkyl (or alkenyl) ether carboxylate.
[8] The component (c) is one or more amphoteric surfactants selected from betaines represented by the following general formulas (c1), (c2), (c3) and (c4). The composition according to any one of [1] to [7].

(Wherein R ^1c represents a hydrocarbon group having 8 to 18 carbon atoms, preferably a linear or branched alkyl group or alkenyl group, and R ^2c and R ^3c may be the same or R 1 represents a different alkyl group having 1 to 5 carbon atoms, R ^4c represents a hydrocarbon group having 7 to 17 carbon atoms, preferably a linear or branched alkyl group or alkenyl group, Y represents a hydrogen atom or a hydroxyl group, (r, s, and t are numbers from 1 to 3, u is a number from 1 to 5, v is a number greater than 1, and w and x are numbers that satisfy 0 ≦ w + x ≦ 4.)
[9] As component (d), alkanolamine, preferably monoethanolamine and / or alkali hydroxide is 0.01 to 20% by mass, preferably 0.05 to 15% by mass, more preferably 1.5 to 15%. The composition according to any one of the above [1] to [8], which is contained by mass%, more preferably 2 to 10 mass%, more preferably 3 to 7 mass%, more preferably 3 to 5 mass%.
[10] The composition according to any one of [1] to [9], wherein the component (a-1) is dipropylene glycol monobutyl ether.
[11] The composition according to any one of [1] to [10] above, wherein the component (a) comprises the component (a-1).
[12] The mass ratio of (c) component / ((b) component + (c) component) is 0.04 / 1 to 0.6 / 1, preferably 0.07 / 1 to 0.5 / 1. The composition according to any one of [1] to [11], which is preferably 0.079 / 1 to 0.5 / 1, more preferably 0.2 / 1 to 0.35 / 1.
[13] The composition according to any one of [1] to [12] above, containing 70 to 98% by mass of water, preferably 75 to 96% by mass, more preferably 80 to 94% by mass.
[14] Any one of [1] to [13] above, wherein the pH at 25 ° C. is 7.5 to 14, preferably 8 to 13, more preferably 9 to 12, and more preferably 10 to 11.5. A composition according to 1.
[15] The composition according to any one of [1] to [14], which exists as a homogeneous liquid phase.
[16] The composition according to any one of [1] to [15] above, wherein the pH at 25 ° C. is 8 to 13.
[17] The composition according to any one of [1] to [16], which can be applied as a kitchen cleaner.
[18] A cleaning method in which the composition according to any one of [1] to [17] is applied to a hard surface on which oil stains are present for cleaning.

Examples 1 to 14 and Comparative Examples 1 to 16
In the following, aspects of the invention will be further described and disclosed by means of examples. Such examples are merely illustrative of the present invention and are not intended to be limiting in any way. Using each component shown in the following table, liquid detergent compositions for hard surfaces of Examples and Comparative Examples were obtained. The numerical value for the amount of each component in the table was mass%, and the balance was deionized water. The mass ratio values of the components in the table are shown with the denominator (/ 1) omitted.

Each of the prepared Examples and Comparative Examples 1 to 4, 6 and 8 to 16 was present as a uniform liquid phase without turbidity or separation. On the other hand, in each composition of Comparative Examples 5 and 7, a uniform liquid composition could not be obtained, and evaluation could not be performed. Therefore, F was described as the evaluation of Comparative Examples 5 and 7.

The pH (25 ° C.) of the composition was adjusted with a 6N sodium hydroxide aqueous solution or 6N hydrochloric acid as necessary. Each test of cleaning performance and storage stability was performed by the following method using each liquid detergent composition for hard surfaces. The results are shown in the table below.

(Cleaning performance I)
The cleaning effect on the modified soybean oil soil was evaluated using the composition stock solution.
1 g of the composition was applied in a circular shape having a diameter of about 35 mm to the following stainless steel plate previously coated with modified soybean oil stain. After contact at room temperature for 5 minutes, a rinsing operation was performed with deionized water. The sample having been subjected to the above washing operation and the following stainless steel plate (reference) not being washed were photographed with a digital camera. The area of the dirt removal portion of the circular portion of the sample after rinsing was quantified. That is, 100 was set when the dirt of the circular part was completely removed, and 0 was set when the dirt was not removed at all.

[How to make modified soybean oil stains]
Add 40 mL of commercially available soybean oil (using Wako Pure Chemical Industries, within 3 months after purchase) to a stainless steel 50 mL beaker, and heat at 180 ° C. for 1 hour with the top open to the atmosphere. (5 ° C.). 1 part by weight of Oil Orange SS was added to 99 parts by weight of this heat-treated oil and mixed well at room temperature. This model stain was applied as uniformly as possible to 1.4 to 1.6 mg per square centimeter on a stainless steel plate and allowed to stand at room temperature for 1 week. This soil was used for cleaning evaluation.

(Cleaning performance II)
Add 40 mL of commercially available soybean oil (using Wako Pure Chemical Industries, within 3 months of purchase) to a 50 mL stainless steel beaker and heat-treating it at 180 ° C for 50 hours (using an electric thermostat) with the top open to the atmosphere. Cooled naturally to room temperature. 1 part by weight of Oil Orange SS was added to 99 parts by weight of this heat-treated oil and mixed well at room temperature (25 ° C. ± 5 ° C.). This model stain was applied as evenly as possible to a stainless steel plate so as to be 1.4 to 1.6 mg per square centimeter, and immediately the same cleaning evaluation as described above was performed.

[Numericalization method of dirt removal area]
The image photographed with the digital camera was subjected to graying processing using image processing software (Win ROOF Ver.3.30 (MITANI Corporation)). By binarizing the processed image, the dirt removal portions were counted and the stain removal portion area was digitized. As the threshold value used for binarization in each image, a value that does not count all reference smudge parts in the image was used.

(Storage stability)
About the liquid detergent composition shown in the following table | surface, the external appearance change at 5 degreeC and 50 degreeC storage was investigated. Appearance was confirmed every week. A storage test was conducted by putting 40 g of the composition in a 50 mL container (Marem screw tube No. 7), and the following criteria were evaluated.

4: Turbidity and / or separation does not occur at 4 weeks after storage.
3: Turbidity and / or separation occurs at 3 weeks after storage.
2: Turbidity and / or separation occurs at 2 weeks after storage.
1: Turbidity and / or separation occurs at 1 week after storage

From the results summarized in the above table, the following was found.

The product of the present invention was found to be excellent in cleaning performance, high temperature and low temperature storage stability.
From Comparative Examples 1 and 3 to 5, when the component (a) was not contained, the detergency against oil stains was not sufficient. From Comparative Example 7, when the component (a) was excessively contained, a uniform liquid composition could not be obtained. From Comparative Examples 2 and 6, when the component (a-1) in the component (a) was too small, the detergency was not sufficient. From Example 14 and Comparative Example 12, it was found that when the pH of the composition was 7.5 or more, there was a tendency for the cleaning performance to increase. Further, from Comparative Examples 9 to 11 and 13 to 16, it was found that when polyoxyethylene alkyl ether or alkyl (poly) glycoside was used instead of the component (b), the cleaning performance with respect to the low-modified oil was inferior.

Comparative Example 13 and Comparative Example 8 were compared, and it was found that the high-temperature storage stability was not sufficient when component (c) was not contained.

The components (a) and non- (a) in each table are as follows.
a-1-1: dipropylene glycol monobutyl ether a-1-2: dipropylene glycol monohexyl ether a-2: diethylene glycol monobutyl ether DPG: dipropylene glycol PG: propylene glycol

The components (b) and non- (b) in each table are as follows.
b-1: polyoxyethylene (EO average addition mole number = 8) lauryl ether b-2: polyoxyethylene (EO average addition mole number = 7) secondary alkyl (mixture of 12 to 14 carbon atoms) ether b-3 : Lauryldimethylamine oxide b-3 ′: Capryldimethylamine oxide b-3 ″: Stearyl dimethylamine oxide b-4: Amidopropyl dimethylamine oxide lauric acid b-5: Alkyl (mixed of 10 to 14 carbon atoms) glycoside (Average condensation degree of glucoside = 1.3)

The component (c) in each table is as follows.
c-1: linear alkyl (mixed with 10 to 14 carbon atoms) sodium benzenesulfonate c-2: amidopropyl laurate-N, N-dimethylacetate betaine c-3: lauryl-N, N-dimethyl-2- Hydroxypropyl sulfobetaine

The liquid detergent composition for hard surfaces of the present invention can be applied to various hard surfaces, but is more suitable for hard surfaces around kitchens, and is therefore suitable as a liquid detergent composition for kitchens.

Claims

(A) 1 to 15% by mass of a polyalkylene glycol monoalkyl ether represented by the following formula (a1):
(B) amine oxide,
(C) 0.01 to 15% by mass of one or more surfactants selected from the group consisting of an anionic surfactant excluding soap and an amphoteric surfactant, and water,
The mass ratio of (c) component / ((b) component + (c) component) is 0.01 / 1 to 1/1, and 60 to 100% by mass of (a) component is (a-1) dipropylene A monoalkyl ether having 4 to 8 carbon atoms in the alkyl group of glycol,
A liquid detergent composition for hard surfaces having a pH of 6 to 14 at 25 ° C.
R 1a (OR 2a ) l OH (a1)
[Wherein R 1a is an alkyl group having 4 to 8 carbon atoms, 1 is a number having 1 to 4 and R 2a is an alkylene group having 2 to 4 carbon atoms. ]
The composition according to claim 1, wherein the mass ratio of (a) component / ((b) component + (c) component) is 1/1 to 15/1.
The composition according to claim 1 or 2, wherein the component (b) is an alkyl or alkenylamine oxide represented by the following general formula (b1).

(Wherein R 1b represents a hydrocarbon group having 8 to 18 carbon atoms, R 2b and R 3b represent the same or different alkyl groups having 1 to 3 carbon atoms, and D represents a —NHC (═O) — group or —C (═O) NH— group, E represents an alkylene group having 1 to 5 carbon atoms, and m and n represent m = 0 and n = 0 or m = 1 and n = 1.)
The composition according to any one of claims 1 to 3, wherein the component (b) is an alkyl dimethylamine oxide having 8 to 18 carbon atoms in the alkyl group.
The composition according to any one of claims 1 to 4, comprising 0.05 to 15% by mass of the component (b).
The composition according to any one of claims 1 to 5, wherein the component (c) is an anionic surfactant excluding soap.
Component (c) is an alkylbenzene sulfonate, alkane sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester, α-olefin sulfonate, α-sulfo fatty acid methyl ester salt, polyoxyethylene alkyl ( Or an alkenyl) ether carboxylate or a polyoxyethyleneamidoalkyl (or alkenyl) ether carboxylate.
The component (c) is one or more amphoteric surfactants selected from betaines represented by the following general formulas (c1), (c2), (c3) and (c4). 8. The composition according to any one of to 7.

(Wherein R 1c represents a hydrocarbon group having 8 to 18 carbon atoms, R 2c and R 3c represent the same or different alkyl groups having 1 to 5 carbon atoms which may be substituted by a hydroxyl group, and R 4c Represents a hydrocarbon group having 7 to 17 carbon atoms, Y represents a hydrogen atom or a hydroxyl group, r, s, and t represent a number of 1 to 3, u represents a number of 1 to 5, and v represents 1 or more And w and x are numbers satisfying 0 ≦ w + x ≦ 4.)
The composition according to any one of claims 1 to 8, comprising 0.01 to 20% by mass of an alkanolamine and / or an alkali hydroxide as the component (d).
The composition according to any one of claims 1 to 9, wherein the component (a-1) is dipropylene glycol monobutyl ether.
The composition according to any one of claims 1 to 10, wherein the component (a) comprises the component (a-1).
The composition according to any one of claims 1 to 11, wherein the mass ratio of (c) component / ((b) component + (c) component) is 0.04 / 1 to 0.6 / 1.
The composition according to any one of claims 1 to 12, comprising 70 to 98% by mass of water.
The composition according to any one of claims 1 to 13, which has a pH of 7.5 to 14 at 25 ° C.
The composition according to any one of claims 1 to 14, which exists as a homogeneous liquid phase.
The composition according to any one of claims 1 to 15, which has a pH of 8 to 13 at 25 ° C.
The composition according to any one of claims 1 to 16, which can be applied as a kitchen cleaner.
A cleaning method in which the composition according to any one of claims 1 to 17 is applied to a hard surface on which oil stains are present for cleaning.