WO2018216731A1

WO2018216731A1 - Liquid detergent composition for hard surfaces

Info

Publication number: WO2018216731A1
Application number: PCT/JP2018/019832
Authority: WO
Inventors: 中島弘樹
Original assignee: 花王株式会社
Priority date: 2017-05-26
Filing date: 2018-05-23
Publication date: 2018-11-29
Also published as: TWI749229B; CN110506101A; TW201900859A; CN110506101B; MY193105A

Abstract

The present invention is a liquid detergent composition for hard surfaces, which contains: (a) a copolymer that comprises a specific constituent unit (a1) having a betaine group and a specific constituent unit (a2) having a cation group, with the molar ratio of the constituent unit (a1) to the constituent unit (a2), namely (constituent unit (a1))/(constituent unit (a2)) being from 30/70 to 99.9/0.1 (inclusive); (b) a cationic surfactant; and (c) one or more surfactants selected from among amphoteric surfactants, nonionic surfactants and anionic surfactants.

Description

Liquid detergent composition for hard surfaces

The present invention relates to a liquid cleaning composition for hard surfaces and a method for preventing the adhesion of dirt on hard surfaces.

BACKGROUND ART Living environment facilities surrounding us have various hard surfaces made of tiles, plastics, metals, etc., and these hard surfaces are exposed to an environment where various kinds of dirt adhere to in daily life. In particular, hard surfaces used as toilets, bathrooms, kitchens, etc. are also surfaces that people come into contact with on a daily basis, so that many stains remain and accumulate, and furthermore, they have properties that are difficult to remove. It has become.

For example, Japanese Patent Application Laid-Open No. 2010-1000086 discloses a method for cleaning or rinsing a hard surface in an aqueous medium or an aqueous alcohol medium containing at least one surfactant and at least one polybetaine (B). Wherein the polybetaine (B) has a total constant anionic charge and a total constant cation charge in the pH range of 1-14 (each individual betaine unit being the same number as the constant cation charge). A hard surface cleaning or rinsing composition exhibiting an absolute weight average molecular weight (Mw) of 5,000 to 3,000,000 g / mole.
In addition, US Patent Application Publication No. 2009/0197791 discloses a copolymer containing a unit A containing a betaine group and a cationic unit B.

SUMMARY OF THE INVENTION Japanese Patent Application Laid-Open No. 2010-1000086 and US Patent Application Publication No. 2009/0197791 are not sufficient in terms of satisfying foaming, sterilization performance, and antifouling properties. In particular, the present inventors have found that when a polymer having a betaine group and a cationic surfactant are used in combination, as described in JP-A 2010-1000086, in order to further improve foaming. It has been found that when other surfactants such as nonionic surfactants, amphoteric surfactants or anionic surfactants are used, the antifouling performance on hard surfaces decreases.

In addition, Japanese Patent Application Laid-Open No. 2010-1000086 and US Patent Application Publication No. 2009/0197791 satisfy scale removal cleaning power (hereinafter also simply referred to as cleaning power), sterilization performance, and antifouling properties. It is not enough in terms. In particular, the present inventors have found that when a polymer having a betaine group and a cationic surfactant are used in combination with a cationic surfactant as described in JP-A 2010-1000086, the detergency is further improved. It has been found that when a chelating agent is used, the antifouling performance on a hard surface is lowered.

The present invention relates to a liquid detergent composition for hard surfaces that maintains sterilization performance, is excellent in foaming, and has excellent antifouling performance, i.e., excellent antifouling performance.

The present invention relates to a liquid detergent composition for a hard surface that maintains sterilization performance, is excellent in detergency, and suppresses the adhesion of dirt to a hard surface, that is, is excellent in antifouling performance.

The present inventors use a polymer having a specific betaine group and a specific cationic group, a cationic surfactant, and a nonionic surfactant, an amphoteric surfactant or an anionic surfactant. It has been found that excellent effects can be obtained in all of antifouling performance, foaming (hereinafter also referred to as foaming property) and disinfection performance.

The present invention includes (a) a structural unit (a1) represented by the following formula (1) and a structural unit (a2) represented by the following formula (2), wherein the structural unit (a1) and the structural unit (a2) ) Is a molar ratio of the structural unit (a1) / the structural unit (a2) is from 30/70 to 99.9 / 0.1, (b) a cationic surfactant, and (c) amphoteric Provided is a hard surface liquid cleaning composition containing one or more surfactants selected from surfactants, nonionic surfactants and anionic surfactants (hereinafter referred to as component (c)).

[Where,
R ¹ to R ³ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ⁴ : an alkylene group having 1 to 4 carbon atoms, or —Y ¹ —OPO ₃ ^— —Y ² —
Y ¹ , Y ² : the same or different, alkylene group having 1 to 4 carbon atoms R ⁵ , R ⁶ : the same or different, hydrocarbon group having 1 to 4 carbon atoms X ¹ : O or NR ⁷ , R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X ² : a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R ¹⁷ SO ₃ ⁻ , or R ¹⁷ COO ^— . However, when R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, X ² is R ¹⁷ SO ₃ ⁻ , or R ¹⁷ COO ⁻ , R ¹⁷ is an alkylene group having 1 to 4 carbon atoms, and R ⁴ is When —Y ¹ —OPO ₃ ^— —Y ² —, X ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

[Where,
R ⁸ to R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms X ³ : O
R ^{11 is} an alkylene group having 1 to 4 carbon atoms X ^{4 is} N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ¹² to R ¹⁶ are the same or different and are a hydrogen atom or a carbon number 1 to 4 hydrocarbon groups, X ⁵ represents an anion. ]

In addition, the present inventors use a polymer having a specific betaine group and a specific cationic group, a cationic surfactant, and a chelating agent, so that all of the antifouling performance, detergency and sterilization performance can be obtained. It was found that an excellent effect can be obtained.

The present invention includes (a) a structural unit (a1) represented by the following formula (1) and a structural unit (a2) represented by the following formula (2), wherein the structural unit (a1) and the structural unit (a2) ) Is a molar ratio of the structural unit (a1) / the structural unit (a2) is 30/70 to 99.9 / 0.1 [hereinafter referred to as component (a)], (b) cationic It is related with the liquid detergent composition for hard surfaces containing surfactant [henceforth (b) component] and (d) chelating agent [henceforth (d) component].

Hereinafter, the hard surface liquid detergent composition of the present invention includes the above two hard surface liquid detergent compositions.

The present invention also relates to a method for preventing the adhesion of dirt on a hard surface, wherein the hard surface is treated with the liquid detergent composition for hard surface of the present invention.

According to the present invention, there is provided a liquid detergent composition for a hard surface that maintains sterilization performance, is excellent in foaming, and has excellent antifouling performance, that is, excellent antifouling performance.

Further, according to the present invention, there is provided a liquid detergent composition for a hard surface that maintains sterilization performance, is excellent in detergency, and suppresses the adhesion of dirt to a hard surface, that is, is excellent in antifouling performance.

MODE FOR CARRYING OUT THE INVENTION [Liquid detergent composition for hard surface]
In one aspect, the liquid detergent composition for hard surface of the present invention is a liquid detergent composition for hard surface containing the component (a), the component (b) and the component (c).
<(A) component>
The component (a) is a copolymer containing the structural unit (a1) represented by the formula (1) and the structural unit (a2) represented by the formula (2).
The structural unit (a1) represented by the formula (1) may be a structural unit derived from an unsaturated monomer having a betaine group. The structural unit (a2) represented by the formula (2) may be a structural unit derived from an unsaturated monomer having a cationic group.

[Weight average molecular weight of component (a)]
The weight average molecular weight of the component (a) is preferably 500 or more, more preferably 5000 or more, still more preferably 10,000 or more, and still more preferably 30,000 or more, from the viewpoint of enhancing the antifouling performance of the component (a). From the same viewpoint, it is preferably 200,000 or less, more preferably 150,000 or less, and still more preferably 100,000 or less. This weight average molecular weight can be measured by the method described in Examples.

[Molar ratio of structural unit (a1) to structural unit (a2)]
The molar ratio of the structural unit (a1) to the structural unit (a2) of the component (a) is 30/70 or more and 99.9 / 0 in terms of the antifouling performance, as the structural unit (a1) / the structural unit (a2). .1 or less. From the same viewpoint, the molar ratio of the structural unit (a1) / structural unit (a2) is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, and even more preferably 75 / 25 or more, still more preferably 90/10 or more, and from the viewpoint of enhancing the antifouling performance of the component (a), it is preferably 98/2 or less, more preferably 96/4 or less.

[Structural unit (a1)]
(Content of structural unit (a1))
The content of the structural unit (a1) in the component (a) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol%, from the viewpoint of enhancing the antifouling performance of the component (a). More preferably, it is 80 mol% or more, more preferably 90 mol% or more, and from the same viewpoint, it is preferably 99 mol% or less, more preferably 98 mol% or less, still more preferably 95 mol%. It is as follows.
Further, the content of the structural unit (a1) in the component (a) is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70%, from the viewpoint of improving the antifouling performance of the component (a). From the same viewpoint, it is preferably 99% by mass or less, more preferably 98% by mass or less, and still more preferably 95% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more. It is below mass%.

(Structure of structural unit (a1))
The structural unit (a1) of the component (a) is a structural unit represented by the following formula (1).

In the formula (1), R ¹ and R ² are each a hydrogen atom from the viewpoint of availability of unsaturated monomers, the viewpoint of polymerizability of the monomers, and the viewpoint of enhancing the antifouling performance of the component (a). Is preferred.
In the formula (1), R ³ is preferably a hydrogen atom or a methyl group from the viewpoint of availability of unsaturated monomers, the polymerizability of the monomers, and the viewpoint of enhancing the antifouling performance of the component (a). A methyl group is more preferable.
In the formula (1), X ¹ is preferably O from the viewpoint of availability of unsaturated monomers, the polymerizability of the monomers, and the antifouling performance of the component (a). From the same viewpoint, the alkylene group having 1 to ⁴ carbon atoms of R ⁴ is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
In formula (1), R ⁴ is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, from the viewpoint of enhancing the antifouling performance.
In Formula (1), Y ¹ and Y ² are each preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
In the formula (1), R ⁵ and R ⁶ are each methyl from the viewpoint of availability of the unsaturated monomer, the polymerizability of the monomer, and the antifouling performance of the component (a). Group or ethyl group is preferable, and methyl group is more preferable.
In the formula (1), X ² is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R ¹⁷ SO ₃ ⁻ , or R ¹⁷ COO ^— , and R ⁴ is an alkylene having 1 to 4 carbon atoms. X ² is R ¹⁷ SO ₃ ⁻ , or COO ^— , and when R ⁴ is —Y ¹ —OPO ₃ ^— —Y ² —, X ² is a hydrogen atom or a carbon atom having 1 to 4 carbon atoms. It is a hydrogen group. R ⁴ is ^-Y 1 -OPO ₃ ^- ^-Y ² ^- when, in view of enhancing the antifouling performance, ^{X 2} is preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group. When R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, X ² is preferably R ¹⁷ SO ₃ ^— from the same viewpoint.
R ¹⁷ is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms.

[Structural unit (a2)]
(Content of structural unit (a2))
The content of the structural unit (a2) in the component (a) is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 5 mol% or more, from the viewpoint of enhancing the antifouling performance. From the same viewpoint, it is preferably not more than 70 mol%, more preferably not more than 50 mol%, still more preferably not more than 30 mol%, still more preferably not more than 20 mol%, still more preferably not more than 10 mol%.
Further, the content of the structural unit (a2) in the component (a) is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more, from the viewpoint of enhancing the antifouling performance. From the viewpoint of improving the antifouling performance of the component (a), it is preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably. It is 10 mass% or less.

(Structure of structural unit (a2))
The structural unit (a2) of the component (a) is a structural unit represented by the following formula (2).

[Where,
R ⁸ to R ¹⁰ : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms X ³ : O or NH
R ^{11 is} an alkylene group having 1 to 4 carbon atoms X ^{4 is} N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ¹² to R ¹⁶ are the same or different and are a hydrogen atom or a carbon number 1 to 4 hydrocarbon groups, X ⁵ represents an anion. ]

In formula (2), R ⁸ and R ⁹ are each a hydrogen atom from the viewpoint of availability of unsaturated monomers, the viewpoint of polymerizability of monomers, and the viewpoint of enhancing the antifouling performance of component (a). Is preferred.
In Formula (2), R ¹⁰ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of the polymerizability of the monomer and the antifouling performance of the component (a).
In the formula (2), X ³ is preferably O from the viewpoint of the polymerizability of the monomer and the antifouling performance of the component (a).
In Formula (2), R ¹¹ is preferably a C 2 or C 3 alkylene group from the viewpoint of the polymerizability of the monomer and the antifouling performance of the component (a), and the C 2 alkylene group is preferably More preferred.
In the formula (2), X ⁴ is N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ from the viewpoint of enhancing the antifouling performance of the component (a) and from the viewpoint of easy quaternization reaction. N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ is preferable, and R ¹² , R ¹³ and R ¹⁴ are each preferably a methyl group or an ethyl group from the same viewpoint.
In the formula (2), R ¹⁵ and R ¹⁶ are preferably a methyl group or an ethyl group, and more preferably a methyl group, from the viewpoint of enhancing the antifouling performance of the component (a) and the ease of the quaternization reaction.
In the formula (2), X ⁵ is an anion, preferably a halogen ion or C ₂ H ₅ SO ₄ ^{—, and} more preferably C ₂ H ₅ SO ₄ ^— .

[Structural units other than structural unit (a1) and structural unit (a2)]
(A) A component may contain structural units other than a structural unit (a1) and a structural unit (a2) in the range which does not impair the effect of this invention. As the structural unit other than the structural unit (a1) and the structural unit (a2), a structural unit derived from an unsaturated monomer other than an unsaturated monomer having a sulfobetaine group is preferable, and hydrophobic unsaturated such as styrene. A structural unit derived from a monomer is more preferable.

The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 10 mol% or less, more preferably 5 mol% or less, more preferably from the viewpoint of antifouling properties. Is 1 mol% or less, more preferably 0.5 mol% or less, still more preferably 0.1 mol% or less. The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) may be 0 mol%.

The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably from the viewpoint of antifouling properties. Is 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less. The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) may be 0% by mass.

The total content of the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 90 mol% or more, more preferably 95 mol% or more, and still more preferably 99, from the viewpoint of antifouling properties. It is more than mol%, More preferably, it is 99.5 mol% or more, More preferably, it is 99.9 mol% or more. The total content of the structural unit (a1) and the structural unit (a2) in the component (a) may be 100 mol%.
The total content of the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 99% from the viewpoint of antifouling properties. It is more than mol%, More preferably, it is 99.5 mass% or more, More preferably, it is 99.9 mass% or more. The total content of the structural unit (a1) and the structural unit (a2) in the component (a) may be 100% by mass.

[Method for producing component (a)]
As the method for producing the component (a), any method may be employed, and specifically, the following methods (i) and (ii) may be mentioned. From the viewpoint of availability of raw materials and ease of production, the method (ii) is preferred.
(I) Method obtained by copolymerizing an unsaturated monomer having a betaine group and a cationic group (ii) After copolymerizing an unsaturated monomer having an amino group and a cationic group, Method obtained by classification

<(B) component>
The component (b) is a cationic surfactant. As the cationic surfactant, mono- or di-long alkyl quaternary ammonium salts are preferable. As the component (b), a cationic surfactant selected from a compound represented by the following general formula (b1) and a compound represented by the general formula (b2) is preferable.

[Wherein, at least one selected from R ^1b and R ^2b represents an alkyl group having 8 to 18 carbon atoms, an alkenyl group having 8 to 18 carbon atoms, or a hydroxyalkyl group having 8 to 18 carbon atoms, The remainder represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a polyoxyethylene group having an average addition mole number of 10 or less, and R ^3b and R ^4b are the same or different, Each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a polyoxyethylene group having an average addition mole number of 10 or less, and Y 2 ⁻ is a halogen atom or 1 to 5 carbon atoms. An anion residue of a sulfonate ester or a sulfate ester. ]

[Wherein, R ^5b represents an alkyl group having 8 to 18 carbon atoms, an alkenyl group having 8 to 18 carbon atoms, or a hydroxyalkyl group having 8 to 18 carbon atoms, and R ^6b and R ^7b are the same or Differently, each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a polyoxyethylene group having an average addition mole number of 10 or less, and R ^8b represents 1 to 3 carbon atoms. The following alkylene groups are shown. Z ^- represents a halogen atom or an anion residue of a sulfonate ester or sulfate ester having 1 to 5 carbon atoms. ]

In the case of a mono long chain alkyl type quaternary ammonium salt, in the general formula (b1), R ^1b is preferably an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 16 carbon atoms, R ^2b , R ^3b and R ^4b are the same or different and are each an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having an average addition mole number of 10 or less.
In the case of the di-long-chain alkyl type quaternary ammonium salt, in the general formula (b1), preferably, R ^1b and R ^2b are the same or different and are each an alkyl group or alkenyl group having 8 to 16 carbon atoms. Or R ^3b and R ^4b are the same or different and are each an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having an average addition mole number of 10 or less.

In the general formula (b2), R ^5b is preferably a linear alkyl group having 12 to 16 carbon atoms, R ^6b and R ^7b are each preferably a methyl group, R ^8b is preferably a methylene group, and Z ⁻ is Halogen ions, and further chloride ions (Cl ⁻ ) are preferred.

The component (b) is preferably a cationic surfactant selected from the compounds represented by the general formula (b2).

<(C) component>
The component (c) is one or more surfactants selected from amphoteric surfactants, nonionic surfactants and anionic surfactants. The component (c) is preferably one or more surfactants selected from amphoteric surfactants and nonionic surfactants from the viewpoint of blending stability.

[Amphoteric surfactant]
The amphoteric surfactant preferably contains one or more amphoteric surfactants selected from amine oxides, sulfobetaines and carbobetaines from the viewpoint of blending stability and foaming properties, and is selected from sulfobetaines and carbobetaines. It is more preferable to include one or more amphoteric surfactants, and it is more preferable to include carbobetaine. Two or more of these may be used.

In the amphoteric surfactant, the content of one or more amphoteric surfactants selected from amine oxide, sulfobetaine and carbobetaine is preferably 50% by mass or more, more preferably from the viewpoint of blending stability and foamability. Is 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass. It is as follows.
In the amphoteric surfactant, the content of one or more amphoteric surfactants selected from sulfobetaine and carbobetaine is preferably 50% by mass or more, more preferably from the viewpoint of blending stability and foamability. 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less. It is.

The sulfobetaine is preferably an N-alkyl-N, N-dimethyl having an alkyl group with a carbon number of 10 or more, preferably 18 or less, more preferably 14 or less, from the viewpoint of blending stability and foamability. -N-sulfopropylammonium sulfobetaine, N-alkyl-N having an alkyl group with carbon number of preferably 10 or more, and preferably 18 or less, more preferably 14 or less, from the viewpoint of blending stability and foamability , N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine, the number of carbon atoms of the alkanoyl group is preferably 10 or more, and preferably 18 or less, more preferably from the viewpoint of blending stability and foamability. 14 or less N-alkanoylaminopropyl-N, N-dimethyl-N-sulfopropylammonium sulfate N-alkanoylaminopropyl-N, N-dimethyl having a carbon number of betaine or alkanoyl group of preferably 10 or more, and preferably 18 or less, more preferably 14 or less, from the viewpoint of blending stability and foamability. N- (2-hydroxysulfopropyl) ammonium sulfobetaine may be mentioned.

The carbobetaine is preferably an N-alkyl-N, N-dimethyl having an alkyl group with a carbon number of 10 or more, preferably 18 or less, more preferably 14 or less, from the viewpoint of blending stability and foamability. Examples include —N-carboxymethylammonium betaine and a compound represented by the following general formula (I). From the viewpoint of blending stability and foamability, a compound represented by the following general formula (I) is preferable.

[Wherein, R ^1c represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, R ^2c represents a propylene group, and R ^3c and R ^4c each independently represents an alkyl group having 1 to 3 carbon atoms. Indicates. ]

In general formula (I), R ^1c is preferably an alkyl group or an alkenyl group of 9 or more, more preferably 11 or more, and preferably 15 or less, more preferably 13 or less, from the viewpoint of blending stability and foamability. A nonyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group.
In general formula (I), R ^3c and R ^4c are preferably methyl groups from the viewpoints of blending stability and foamability.
Examples of the compound represented by the general formula (I) include almond amidopropyl betaine, apricot amidopropyl betaine, avocado amidopropyl betaine, babasamidopropyl betaine, behenamidopropyl betaine, canola amidopropyl betaine, capryl / capramidopropyl betaine. , Cocamidopropyl betaine, coco / oleamidopropyl betaine, isostearamidepropyl betaine, lauramidopropylcarbobetaine, milkamidopropyl betaine, mincamidopropyl betaine, myristamidopropyl betaine, oleamidopropyl betaine, oliveamidopropyl betaine, Palmamamidopropyl betaine, palmitamidopropyl betaine, ricinoleic acid amidopropyl betaine, sesamidpropyl Tyne, soy amidopropyl betaine, stearamidopropyl betaine, tallow amidopropyl betaine, undecylenic acid amidopropyl betaine, and wheat germ amido propyl betaine and the like.
Among these, one or more selected from lauramidopropylcarbobetaine, myristamidopropylbetaine, oleamidopropylbetaine, and cocamidopropylbetaine are preferable from the viewpoint of blending stability and foamability. These are compounds in which R ^3c and R ^4c in general formula (I) are each a methyl group.

As the amine oxide, a compound of the following general formula (II) is suitable.

[Wherein, R ^5c represents a hydrocarbon group having 8 to 22 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and R ^6c and R ^7c each independently represent 1 to 3 carbon atoms. The following alkyl groups are shown. D represents an —NHC (═O) — group or a —C (═O) NH— group, and E represents an alkylene group having 1 to 5 carbon atoms. m and p represent m = 0 and p = 0 or m = 1 and p = 1. ]

In the above general formula (II), R ^5c is preferably an alkyl group having 10 to 18 carbon atoms, more preferably an alkyl group having 12 to 16 carbon atoms, from the viewpoint of blending stability and foamability. More preferably an alkyl group having 12 to 14 carbon atoms, and still more preferably an alkyl group having 12 carbon atoms. R ^6c and R ^7c are preferably a methyl group having 1 carbon atom from the viewpoint of blending stability.

As a preferable specific example of amine oxide,
(1) alkyl (8 to 22 carbon atoms) dialkyl (1 to 3 carbon atoms) amine oxide such as capryldimethylamine oxide, caprin dimethylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide,
(2) Fatty acids (8 to 22 carbon atoms) amidopropyl dialkyl (1 to 3 carbon atoms) amine oxides such as lauric acid amidopropyldimethylamine oxide, myristic acid amidopropyldimethylamine oxide, palmitic acid amidopropyldimethylamine oxide From the viewpoint of blending stability, (1) alkyl (8 to 22 carbon atoms) dialkyl (1 to 3 carbon atoms) amine oxide is more preferable.

[Nonionic surfactant]
Nonionic surfactants include (c1) monoalkyl glyceryl ether (hereinafter referred to as component (c1)), (c2) polyoxyalkylene monoalkyl or alkenyl ether (hereinafter referred to as “non-ionic surfactant”) from the viewpoint of blending stability and foaming properties. (Referred to as component (c2)), (c3) alkyl polyglycoside (glycoside type nonionic surfactant) (hereinafter referred to as component (c3)), (c4) sorbitan nonionic surfactant (hereinafter referred to as component (c4)) ], (C5) Aliphatic alkanolamide [hereinafter referred to as (c5) component], (c6) Fatty acid monoglyceride (hereinafter referred to as (c6) component), and (c7) Sucrose fatty acid ester (hereinafter referred to as (c7) component) One or more selected from the group consisting of these are preferred, and two or more of these may be used.

The nonionic surfactant preferably contains at least one selected from the component (c1), the component (c2), and the component (c3) from the viewpoint of blending stability and foamability, and includes the component (c3). It is even more preferable.
In the nonionic surfactant, the total content of the component (c1), the component (c2) and the component (c3) is preferably 50% by mass or more, and more preferably 70% by mass, from the viewpoint of blending stability and foamability. % Or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, still more preferably 95% by weight or more, still more preferably 99% by weight or more, and preferably 100% by weight or less. .
In addition, the content of the component (c3) in the nonionic surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, from the viewpoint of blending stability and foamability. More preferably, it is 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less.

Component (c1) The component (c1) is a monoalkyl glyceryl ether.
As the component (c1), specifically, a compound represented by the following general formula (c1) is preferable.
R ^11c —O— (Gly) _r —H (c1)
[Wherein, R ^11c represents an alkyl group having 6 to 18 carbon atoms, Gly represents a structural unit derived from glycerin, and preferably represents a residue obtained by removing one hydroxyl group and one hydrogen atom from glycerin; Represents a number from 1 to 4. ]

In the general formula (c1), R ^11c is preferably 6 or more carbon atoms, more preferably 7 or more carbon atoms, still more preferably 8 or more carbon atoms, and preferably carbon from the viewpoint of foamability and blending stability. It is an alkyl group having a carbon number of 18 or less, more preferably a carbon number of 12 or less, and even more preferably a carbon number of 10 or less, and straight chain alkyl groups such as hexyl group, heptyl group, octyl group, nonyl group, and decyl group can be used. However, in the present invention, a branched alkyl group is preferable from the viewpoint of compounding stability. Specific alkyl groups having a branched chain of R ^1c include a 2-ethylhexyl group, a sec-octyl group, an isononyl group, and A group selected from an isodecyl group is more preferable, a 2-ethylhexyl group or an isodecyl group is still more preferable, and a 2-ethylhexyl group is more preferable.

In general formula (c1), r is preferably 1 or more and preferably 2 or less. A compound in which r is 1 is more preferable. A more preferred compound is a compound in which R ^1c is a 2-ethylhexyl group and r is 1.
The structure represented by Gly is a structure represented by —CH ₂ CH (OH) CH ₂ — in which the 1-position and 3-position hydroxyl groups of glycerin are bonded, or the glycerin 1- and 2-position hydroxyl groups are bonded. It is a structure represented by —CH (CH ₂ OH) CH ₂ —, which varies depending on the catalyst and reaction conditions.

In order to obtain the compound of the general formula (c1), for example, an alkyl alcohol represented by R ^11c —OH is used as an alcohol having 6 to 10 carbon atoms, and an epoxy compound such as epihalohydrin or glycidol is reacted with an acid catalyst such as BF ₃ , Or the method of manufacturing by making it react using an aluminum catalyst can be used. For example, when 2-ethylhexanol is used, the obtained 2-ethylhexyl monoglyceryl ether is a mixture that can contain a plurality of products as described in JP-A-2001-49291.

Component (c2) The component (c2) is a polyoxyalkylene monoalkyl or alkenyl ether.
In the nonionic surfactant as the component (c2), the number of carbon atoms of the alkyl group or alkenyl group is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, from the viewpoint of blending stability and foamability. More preferably, it is 12 or more, and from the same viewpoint, it is preferably 22 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less.

In the nonionic surfactant of component (c2), the average number of added moles of alkylene oxide is preferably more than 0, more preferably 1 or more, still more preferably 3 or more, from the viewpoint of blending stability and foaming properties. From the same viewpoint, it is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, and still more preferably 10 or less.
The alkylene oxide is preferably at least one selected from ethylene oxide, propylene oxide, and butylene oxide, and more preferably at least one selected from ethylene oxide and propylene oxide, from the viewpoints of blending stability and foamability. It is.

As a preferred example of the nonionic surfactant as the component (c2), a nonionic surfactant represented by the following general formula (c2) can be exemplified.
R ^12c O [(C ₂ H ₄ O) ₁ / (C ₃ H ₆ O) _j ] H (c2)
[Wherein, R ^12c represents a hydrocarbon group having 6 to 22 carbon atoms. l and j represent the average number of moles added, l represents a number from 0 to 30 and j represents a number from 0 to 30. l and j are not 0 at the same time. “/” Indicates that the oxyethylene group and the oxypropylene group may be added either randomly or in a block regardless of the order. ]

The carbon number of R ^{12c in} the general formula (c2) is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and the same viewpoint from the viewpoints of blending stability and foamability. Therefore, it is preferably 18 or less, more preferably 16 or less, and still more preferably 14 or less.
R ^12c is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, from the viewpoint of blending stability and foaming property, and more preferably an alkyl group, and a secondary alkyl group from the viewpoint of blending stability and foaming property. is there. Here, the secondary alkyl group refers to an alkyl group in which the carbon atom of R ^12c bonded to O in R ^12c O in the general formula (c2) is a secondary carbon atom.
Specific examples of the alkyl group include various octyl groups (including 2-ethylhexyl group), various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups (lauryl group), various tridecyl groups, various tetradecyl groups, Examples include various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, and various octadecyl groups.
Examples of the alkenyl group include various octanyl groups, various nonanyl groups, various decanyl groups, various undecanyl groups, various dodecanyl groups, various tridecanyl groups, various tetradecanyl groups, various pentadecanyl groups, various hexadecanyl groups, various heptadecanyl groups, various octadecanyl groups (for example, Oleyl group, linole group). The “various” means various isomers including n-, sec-, tert-, and iso-.

The HLB value of the polyoxyalkylene monoalkyl or alkenyl ether which is the component (c2) and the nonionic surfactant represented by the general formula (c2) is preferably 5 or more from the viewpoint of blending stability and foamability. More preferably, it is 7 or more, and from the same viewpoint, it is preferably 19 or less, more preferably 15 or less, and still more preferably 13 or less.
Here, the HLB value is defined by the following Griffin equation.
HLB value = 20 × Mw / M
(Wherein, M is the molecular weight of the nonionic surfactant, and Mw is the molecular weight of the hydrophilic portion of the nonionic surfactant.)
In addition, in general formula (c2), a hydrophilic part is a total part of an oxyethylene group and an oxypropylene group.

(C3) Component The (c3) component is an alkyl polyglycoside (glycoside type nonionic surfactant).
The nonionic surfactant as the component (c3) is preferably a nonionic surfactant represented by the following general formula (c3).
R ^13c (OR ^14c ) _s G _t (c3)
[Wherein, R ^13c represents a linear or branched alkyl group having 8 to 18 carbon atoms, preferably 12 to 14 alkyl group, alkenyl group or alkylphenyl group, preferably an alkyl group, and R ^14c represents carbon number. 2 to 4 alkylene groups, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms. s represents the average number of moles added, and is a number from 0 to 5. t represents a number whose average value is 1 or more and 5 or less. ]

In the general formula (c3), R ^13c is a linear or branched alkyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 14 or less, from the viewpoint of blending stability and foamability. It is.
In general formula (c3), s is preferably 0 or more and 2 or less, more preferably 0, from the viewpoints of blending stability and foamability. t is preferably 1.1 or more, and preferably 1.5 or less, more preferably 1.4 or less, from the viewpoint of blending stability and foamability. Here, t is a value measured by proton NMR method.
In general formula (c3), G includes a residue derived from one or more monosaccharides selected from glucose and fructose from the viewpoint of availability and cost. Examples of G include a residue derived from one or more polysaccharides selected from maltose and sucrose. G is preferably a residue derived from a monosaccharide of glucose.

(C4) component to (c7) component (c4) sorbitan nonionic surfactant, (c5) aliphatic alkanolamide, (c6) fatty acid monoglyceride, and (c7) sucrose fatty acid ester each preferably have 8 carbon atoms. It has a linear or branched alkyl group having a carbon number of 12 or more and 14 or less, more preferably 18 or less.

[Anionic surfactant]
The anionic surfactant is preferably an anionic surfactant having a sulfate ester group, a phosphate ester group, a phosphonic acid group, a sulfonic acid group or a carboxy group.
The anionic surfactant has a hydrocarbon group. The hydrocarbon group possessed by the anionic surfactant preferably has 5 or more carbon atoms, more preferably 6 or more, still more preferably 7 or more, and still more preferably 8 or more, from the viewpoint of blending stability and foamability. More preferably, it is 10 or more, more preferably 12 or more, and preferably 21 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less. The hydrocarbon group is preferably a linear or branched alkyl group, an alkylene group or an aryl group.

The anionic surfactant includes (c8) a sulfosuccinic acid ester having a hydrocarbon group having 5 to 18 carbon atoms or a salt thereof (hereinafter referred to as (c8) component), and (c9) a carbon having 8 to 21 carbon atoms. An anionic surfactant having a hydrogen group and a sulfate ester group or a sulfonic acid group [excluding the component (c8)] (hereinafter referred to as the component (c9)), (c10) carbonization having 7 to 21 carbon atoms Anionic surfactant having a hydrogen group and a carboxy group (hereinafter referred to as component (c10)), and (c11) an anionic interface having a hydrocarbon group having 8 to 21 carbon atoms and a phosphate group One or more anionic surfactants selected from the group consisting of an activator [hereinafter referred to as component (c11)] are preferred, and two or more of them may be used.

The anionic surfactant preferably contains at least one selected from the group consisting of the component (c8) and the component (c9), and includes the component (c9) from the viewpoint of blending stability and foamability. More preferred.
Further, in the anionic surfactant, the content of the component (c9) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass from the viewpoints of blending stability and foamability. More preferably, it is 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less.
In addition, content (mass%) of each component in anionic surfactant is computed based on the quantity of sodium salt conversion.

The component (c9) used in the present invention is an anionic surfactant [except for the component (c8)] having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester group or a sulfonic acid group. .

The hydrocarbon group (c9) has a carbon number of 8 or more, preferably 10 or more, more preferably 12 or more, and 21 or less, preferably 18 or less, more preferably, from the viewpoint of blending stability and foamability. Is 14 or less, more preferably 12 or less. The hydrocarbon group (c9) is preferably an alkyl group or an aryl group.

As the anionic surfactant of component (c9), one or more selected from alkyl sulfates, polyoxyalkylene alkyl ether sulfates and alkane sulfonates are preferable.

The anionic surfactant having a sulfate ester group has a carbon number of 8 or more, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably 14 or less, from the viewpoint of blending stability and foamability. More preferred is an alkyl sulfate ester salt having a linear or branched alkyl group of 12 or less.
The anionic surfactant having a sulfate ester group and a polyoxyalkylene group has a carbon number of 8 or more, preferably 10 or more, and preferably 21 or less, preferably from the viewpoint of blending stability and foamability. 18 or less, more preferably 14 or less, and even more preferably 12 or less, a linear or branched alkyl group, and the average added mole number of an oxyalkylene group having 2 to 3 carbon atoms is preferably 0.1 or more, More preferably 0.3 or more, further preferably 0.4 or more, and preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, polyoxyalkylene alkyl ether sulfate ester salt having a polyoxyalkylene group Is preferred.
In addition, as the anionic surfactant having a sulfonic acid group, from the viewpoint of blending stability and foamability,
(1) an alkylbenzenesulfonate having an alkyl group having 6 to 15 carbon atoms, and (2) 8 or more carbon atoms, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably 14 or less, Preferably, one or more anionic surfactants selected from 12 or less alkane sulfonates are suitable.

As the salt of the anionic surfactant (c9), from an inorganic salt selected from sodium salt, ammonium salt, potassium salt, magnesium salt, etc., monoethanolammonium salt, diethanolammonium salt, triethanolammonium salt, morpholinium salt, etc. The selected organic ammonium salt is preferred.

As the component (c9), a compound represented by the following general formula (c9) is preferable from the viewpoint of blending stability and foamability.
R ^23c —O— (R ^24c O) _n —SO ₃ M ² (c9)
[Wherein, R ^23c is a linear or branched alkyl group having 8 to 21 carbon atoms, R ^24c is an ethylene group and / or propylene group, n is an average added mole number, and is 0 or more. The number is 6 or less. M ² is a hydrogen atom or a cation, preferably an inorganic or organic cation. ]

In the general formula (c9), R ^23c has a carbon number of 8 or more, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less, from the viewpoint of detergency. A chain or branched alkyl group, preferably a linear alkyl group. Specifically, R ^23c is preferably an alkyl group selected from an octyl group, a decyl group, a dodecyl group, a tridecyl group, and a tetradecyl group, and more preferably a dodecyl group.

In general formula (c9), n is preferably 0 or more, and preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, and still more preferably 1.5 or less, from the viewpoint of foamability. Is a number. N may be 0.
In the general formula (c9), when R ^24c is an ethylene group, n is preferably 0.1 or more, more preferably 0.5 or more, and preferably 6 or less, from the viewpoint of foamability. The number is preferably 3 or less.
In the general formula (c9), when R ^24c is a propylene group, n is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.4 from the viewpoint of foamability. The number is preferably 1.5 or less, more preferably 1.0 or less, and still more preferably 0.8 or less.
In the general formula (c9), when R ^24c is an ethylene group or a propylene group, n can be selected from the ranges described above for these groups.

In the general formula (c9), M ² is a hydrogen atom, or an inorganic cation such as sodium ion, ammonium ion, potassium ion, magnesium ion, monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, morpholinium ion. And an organic cation such as sodium ion, potassium ion, ammonium ion, and magnesium ion are preferable.

In formula ^{(c9), when R 23c} to obtain a compound containing a branched alkyl group as the alcohol represented by the raw material ^R 23c -OH, hydroformylating the number 8 to 14 of the 1-alkene carbon After condensing the alcohol obtained (contained from 15 mol% to 70 mol% of an alkyl group having a methyl group branched at the β-position with respect to the OH group) and an aldehyde having 4 to 8 carbon atoms, it is reduced. 3 obtained by hydroformylating a dimer of isobutene, which is obtained by the gel-type alcohol obtained (containing 100 mol% of a structure in which an alkyl group having 3 to 6 carbon atoms is branched at the β-position relative to the OH group). , 5,5-trimethylhexanol, a polybranched tridecanol obtained by hydroformylating a trimer of isobutene (branching rate is 100 mol%), petroleum, Examples thereof include synthetic alcohols having coal as a raw material (an alkyl group having a branching ratio of about 20 mol% to 100 mol%).

The component (c10) used in the present invention is an anionic surfactant having a hydrocarbon group having 7 to 21 carbon atoms and a carboxy group.
Specific examples include higher fatty acids or salts thereof, polyoxyethylene alkyl ether carboxylic acids or salts thereof, and N-acyl amino acids or salts thereof.

As the higher fatty acid or a salt thereof, one represented by the following general formula (c10-1) is preferable.
R ^25c -COOX ^1c (c10-1)
[Wherein, R ^25c represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, and X ^1c represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkanol ammonium, or a basic amino acid. ]
More specific examples of higher fatty acids or salts thereof include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, arachidic acid, behenic acid, and salts thereof. Of these, lauric acid, myristic acid, palmitic acid, and salts thereof are preferred.

The polyoxyethylene alkyl ether carboxylic acid or a salt thereof is preferably one represented by the following general formula (c10-2).
R ^26c —O— (CH ₂ CH ₂ O) _g COOX ^2c (c10-2)
[In the formula, R ^26c represents an alkyl group or alkenyl group having 7 or more carbon atoms, preferably 8 or more and 21 or less, g is an average addition mole number of ethylene oxide, and represents a number of 0.5 to 10; ^2c represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkanol ammonium or a basic amino acid. ]

In another aspect, the liquid detergent composition for hard surface of the present invention is a liquid detergent composition for hard surface containing the component (a), the component (b), and the component (d). Specific examples and preferred embodiments of the component (a) and the component (b) for the hard surface liquid detergent composition are as described above.

<(D) component>
The component (d) is a chelating agent. As the chelating agent, one or more compounds selected from aminocarboxylic acids, hydroxycarboxylic acids, hydroxyxyphosphonic acids, and salts thereof are preferable.
Aminocarboxylic acids and salts thereof include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid, diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), methylglycine diacetic acid 1 type (s) or 2 or more types chosen from (MGDA), aspartic acid diacetic acid (ASDA), glutamic acid diacetic acid (GLDA), and these salts are mentioned. The aminocarboxylic acid and its salt are preferably one or more selected from ethylenediaminetetraacetic acid and its salt, methylglycine diacetic acid and its salt, and L-glutamic acid diacetic acid and its salt.
As hydroxycarboxylic acid and its salt, the compound chosen from aliphatic hydroxycarboxylic acid and its salt is preferable. Examples of the hydroxycarboxylic acid and salts thereof include compounds selected from malic acid, citric acid and salts thereof.
Examples of hydroxyxyphosphonic acid and salts thereof include compounds selected from 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts thereof.
Examples of the salt of the chelating agent include alkali metal salts, ammonium salts, and amine salts. Alkali metal salts are preferable, and sodium salts or potassium salts are more preferable.
The chelating agent is preferably one or more compounds selected from aminocarboxylic acids, hydroxycarboxylic acids, and salts thereof, more preferably aminocarboxylic acids or salts thereof, and still more preferably ethylenediaminetetraacetic acid or salts thereof.

<Composition, optional components, etc.>
In the liquid detergent composition for hard surface of the present invention, the content of the component (a) is preferably 0.01% by mass or more, more preferably 0, from the viewpoint of hydrophilizing the hard surface and attaching a stain prevention effect. .05% by mass or more, more preferably 0.1% by mass or more, and from the viewpoint of blending stability, it is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and still more. Preferably it is 0.8 mass% or less, More preferably, it is 0.5 mass% or less, More preferably, it is 0.4 mass% or less.

Further, in the liquid detergent composition for hard surface of the present invention, the content of the component (b) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of sterilizing power. More preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and from the viewpoint of blending stability, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass. % Or less, more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.

In the liquid detergent composition for hard surface of the present invention, the mass ratio of (a) / (b) is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably, from the viewpoint of preventing soil adhesion. 0.1 or more, more preferably 0.15 or more, and from the viewpoint of blending stability, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, and still more preferably Is 1 or less. When the liquid detergent composition for hard surfaces of this invention contains (d) component, the said upper limit is preferable also from a viewpoint of disinfection performance.

Moreover, the liquid detergent composition for hard surfaces of the present invention containing the component (c) preferably has a content of the component (c) of 0.05% by mass or more, more preferably from the viewpoint of foamability. 0.1% by mass or more, more preferably 0.15% by mass or more, and from the viewpoint of economy (low cost), preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass. Hereinafter, it is more preferably 3% by mass or less.

When the component (c) contains an amphoteric surfactant, the content of the amphoteric surfactant in the liquid detergent composition for hard surface of the present invention containing the component (c) From the viewpoint of economy (low cost), preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and preferably 10% by mass or less, More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less.
When the component (c) contains a nonionic surfactant, the content of the nonionic surfactant in the liquid detergent composition for hard surface of the present invention containing the component (c) In view of the above, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and from the viewpoint of economy (low cost), preferably 10% by mass. Hereinafter, it is more preferably 8% by mass or less, further preferably 5% by mass or less, and still more preferably 3% by mass or less.
In addition, when the component (c) contains an anionic surfactant, the content of the anionic surfactant in the liquid detergent composition for hard surface of the present invention containing the component (c) is foaming property. From the viewpoint of, preferably from 0.05% by weight or more, more preferably from 0.1% by weight or more, still more preferably from 0.15% by weight or more, and from the viewpoint of economy (low cost) and blending stability, Is 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, and still more preferably 1% by mass or less.

In addition, the hard surface liquid detergent composition of the present invention containing the component (c) preferably has a mass ratio of (b) / (c) of 0.05 or more, more preferably from the viewpoint of sterilization performance. Is 0.1 or more, more preferably 0.15 or more, and from the viewpoint of foaming, it is preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, and still more preferably 10 or less.

Further, in the hard surface liquid detergent composition of the present invention containing the component (d), the content of the component (d) is preferably 0.01% by mass or more, more preferably 0, from the viewpoint of detergency. .05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and from the viewpoint of economy and blending stability, Preferably it is 10 mass% or less, More preferably, it is 9 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 4 mass% or less. is there. In addition, the mass of (d) component is an acid conversion value (it is the same also in other quantitative ratios with which the mass of (d) component is related).

Further, in the liquid detergent composition for hard surface of the present invention containing the component (d), the mass ratio of (b) / (d) is preferably 0.01 or more, more preferably from the viewpoint of sterilization performance. Is 0.03 or more, more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.15 or more, and preferably 10 or less, more preferably from the viewpoint of blending stability and detergency. Is 5 or less, more preferably 3 or less, still more preferably 1 or less, and still more preferably 0.8 or less.

(D) The liquid detergent composition for hard surfaces of this invention containing a component can contain surfactants other than (b) component. Examples of the surfactant include component (c), that is, one or more surfactants selected from amphoteric surfactants, nonionic surfactants, and anionic surfactants. The component (c) is preferably one or more surfactants selected from amphoteric surfactants and nonionic surfactants from the viewpoint of blending stability. Specific examples and preferred embodiments of the component (c) in this case are as described above. Moreover, in the liquid detergent composition for hard surfaces of this invention containing (d) component, the viewpoint used as the preferable reason of (c) component can add the viewpoint of detergency.

When the liquid detergent composition for hard surfaces of the present invention containing the component (d) contains the component (c), the content of the component (c) in the composition is preferably 0 from the viewpoint of foaming. 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and from the viewpoint of low cost, preferably 10% by mass or less, more preferably 8% by mass or less, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less.

Moreover, when the liquid detergent composition for hard surfaces of this invention containing (d) component contains an amphoteric surfactant, content of an amphoteric surfactant in this composition is from a foamable viewpoint. , Preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and from the viewpoint of economy (low cost), preferably 10% by mass or less, more Preferably it is 8 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less.
Moreover, when the liquid detergent composition for hard surfaces of this invention containing (d) component contains nonionic surfactant, content of nonionic surfactant in this composition is foaming property. From the viewpoint, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.15% by mass or more, and from the viewpoint of economy (low cost), preferably 10% by mass or less. More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less.
Moreover, when the liquid detergent composition for hard surfaces of this invention containing (d) component contains an anionic surfactant, content of an anionic surfactant in this composition is foaming property. From a viewpoint, Preferably it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, More preferably, it is 0.15 mass% or more, and from a viewpoint of economical efficiency (low cost) and compounding stability, Preferably It is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less.

The liquid detergent composition for hard surfaces of the present invention contains water. That is, the remainder other than the component (a), the component (b), the component (c) and / or the component (d), and the optional component is water.
In the liquid detergent composition for hard surface of the present invention, the water content is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and preferably 95% by mass or less. More preferably, it is 93 mass% or less.
As the water, it is preferable to use ion exchange water, sterilized ion exchange water, or the like.

The liquid detergent composition for hard surface of the present invention has a pH of 20 ° C. of preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 10 or less, more preferably 9 or less, Preferably it is 8 or less.

The hard surface liquid detergent composition of the present invention includes polyacrylic acid, polymethacrylic acid, polymaleic acid, poly-2-acrylamido-2-methylpropanesulfonic acid, poly-p--, as long as the object of the present invention is not impaired. Polyhydric carboxylic acids such as styrenesulfonic acid; lower alcohols such as ethyl alcohol and isopropyl alcohol; solvents such as diethylene glycol monobutyl ether; solubilizers such as toluene sulfonate, xylene sulfonate and urea; clay minerals, high water solubility Viscosity modifiers such as molecular compounds (excluding component (a)); water-insoluble abrasives such as calcite, silica, calcium phosphate, zeolite, calcium carbonate, polyethylene, nylon and polystyrene; humectants such as glycerin and sorbitol; cations Feel-improving agents such as modified cellulose (however, (a) Except); sodium carbonate, alkali builders such as sodium silicate; enzymes can be added dyes, perfumes, preservatives and antifungal agents.

[Prevention of dirt adhesion on hard surface]
The present invention relates to a method for preventing adhesion of dirt on a hard surface, wherein the hard surface is treated with the liquid detergent composition for hard surface of the present invention.

Hard surface is not particularly limited, glass, ceramic, porcelain, glazed, tile, ceramics; metals such as aluminum, stainless steel, brass; synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP; cotton And natural fibers such as silk and wool; solid hard surfaces such as synthetic fibers such as polyester, nylon and rayon. The fiber is preferably a fiber product having a shape and strength suitable for treatment with the hard surface liquid detergent composition of the present invention.
The hard surface to which the composition and the treatment method of the present invention can be applied is preferably a hydrophilic hard surface. Here, “hydrophilic” for a hard surface means that the static contact angle with respect to water is less than 70 °. In addition, this static contact angle can be measured by the method as described in an Example.
Suitable hard surfaces in the present invention include one or more hard surfaces selected from glass, ceramics, porcelain, plastics, stainless steel, and silicon wafers.

The subject of the present invention is an article having a hard surface, specifically a hard surface. Articles having a hard surface include toilet bowls, bathtubs, kitchen sinks, window glass, mirrors, faucets and the like.

In the method for preventing soil adhesion according to the present invention, the liquid detergent composition for hard surface according to the present invention comprises (a) component, (b) component, (c) component and / or (d) component in the above content. It is preferable to use a product.

The hard surface treatment with the hard surface liquid detergent composition of the present invention can be performed by bringing the hard surface liquid detergent composition of the present invention into contact with the hard surface. The method for contacting the hard surface liquid detergent composition of the present invention with the hard surface is not particularly limited. For example, the following methods (i) to (ii) can be mentioned.
(I) Method of immersing an article having a hard surface in the liquid detergent composition for hard surface of the present invention (ii) Method of spraying or applying the liquid detergent composition for hard surface of the present invention to a hard surface

In the method (i), the immersion time is preferably 0.5 minutes or more, more preferably 1 minute or more, and preferably 60 minutes or less from the viewpoint of enhancing the antifouling performance and economical efficiency. More preferably, it is 50 minutes or less.
In the method (ii), the method of spraying or coating the hard surface liquid detergent composition of the present invention on the hard surface can be appropriately selected according to the width (area) of the hard surface. The method of drying after spraying the liquid detergent composition for hard surfaces of this invention on a hard surface with a spray etc. is preferable. If necessary, rinse with water after spraying. Further, after spraying, it may be thinly applied using a sponge or the like. Alternatively, the liquid detergent composition for hard surface of the present invention may be directly applied to the hard surface by discharging it from a discharge container such as a squeeze bottle.
The amount of the liquid detergent composition for hard surface of the present invention sprayed or applied to the hard surface is, for example, preferably 0.01 mL or more and 1 mL or less, more preferably 0.01 mL or more and 0.1 mL or less per 10 cm ^2. .

The temperature of the liquid detergent composition for hard surface of the present invention for treating the hard surface is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, from the viewpoint of enhancing the antifouling performance and the ease of the processing method. Preferably it is 15 degreeC or more, Preferably it is 50 degrees C or less, More preferably, it is 40 degrees C or less, More preferably, it is 30 degrees C or less.

Further, from the viewpoint of imparting hydrophilicity to the hard surface and enhancing antifouling properties, the hard surface treated with the liquid detergent composition for hard surface of the present invention, preferably a hydrophilic hard surface, more preferably a glass surface, The static contact angle with respect to water is preferably 20 ° or less, more preferably 15 ° or less, still more preferably 10 ° or less, still more preferably 8 ° or less, and preferably 1 ° or more. By imparting hydrophilicity to the hard surface in this manner, the antifouling performance of the hard surface against a hydrophobic substance can be enhanced. The static contact angle of water on the glass surface can be determined by the method described in the examples.
Moreover, it is preferable that the hard surface processed with the liquid detergent composition for hard surfaces of this invention is processed uniformly from a viewpoint of improving antifouling performance etc. The uniformity of the surface treatment can be judged by visually observing the hard surface after the treatment.
Furthermore, when the hard surface is a toilet bowl, the liquid cleaning composition for hard surface of the present invention can be eluted in the cleaning water in the tank, and can be used as a method for continuously cleaning the toilet bowl. In this case, a certain amount can be dropped automatically or manually into the toilet tank.

<Aspect of the Present Invention>
Examples of the present invention are illustrated below. In these embodiments, the matters described in the liquid detergent composition for hard surface and the dirt adhesion preventing method of the present invention can be appropriately applied.

<1a>
(A) including the structural unit (a1) represented by the following formula (1) and the structural unit (a2) represented by the following formula (2), the molar ratio of the structural unit (a1) and the structural unit (a2) A copolymer in which structural unit (a1) / structural unit (a2) is 30/70 or more and 99.9 / 0.1 or less (hereinafter referred to as component (a)), (b) a cationic surfactant [ (Hereinafter referred to as component (b)), and (c) one or more surfactants selected from amphoteric surfactants, nonionic surfactants and anionic surfactants (hereinafter referred to as component (c)). , Liquid detergent composition for hard surfaces.

<2a>
The weight average molecular weight of the component (a) is preferably 500 or more, more preferably 5000 or more, still more preferably 10,000 or more, still more preferably 30,000 or more, and preferably 200,000 or less, more preferably 150,000 or less. The liquid detergent composition for hard surfaces according to <1a>, more preferably 100,000 or less.

<3a>
The molar ratio of the structural unit (a1) to the structural unit (a2) of the component (a) is 30/70 or more, preferably 50/50 or more, more preferably 55, in terms of the structural unit (a1) / structural unit (a2). / 45 or more, more preferably 60/40 or more, even more preferably 75/25 or more, even more preferably 90/10 or more, and 99.9 / 0.1 or less, preferably 98/2 or less, more preferably Is a liquid detergent composition for hard surfaces according to <1a> or <2a>, which is 96/4 or less.

<4a>
The content of the structural unit (a1) in the component (a) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, and even more. Preferably, it is 90 mol% or more, and preferably 99 mol% or less, more preferably 98 mol% or less, and still more preferably 95 mol% or less, for the hard surface according to any one of <1a> to <3a> Liquid detergent composition.

<5a>
The content of the structural unit (a2) in the component (a) is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 5 mol% or more, and preferably 70 mol% or less, more preferably Is at most 50 mol%, more preferably at most 30 mol%, further preferably at most 20 mol%, more preferably at most 10 mol%, the liquid cleaning for hard surfaces according to any one of <1a> to <4a> Agent composition.

<6a>
The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 10 mol% or less, more preferably 5 mol% or less, more preferably 1 mol% or less, The hard surface liquid detergent composition according to any one of <1a> to <5a>, preferably 0.5 mol% or less, more preferably 0.1 mol% or less, or 0 mol%. .

<7a>
The total content of the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and even more preferably. Is a liquid detergent composition for hard surfaces according to any one of <1a> to <6a>, which is 99.5 mol% or more, more preferably 99.9 mol% or more, or 100 mol%.

<8a>
The hard surface liquid detergent composition according to any one of <1a> to <7a>, wherein the component (b) is a cationic surfactant selected from mono- or di-long-chain alkyl quaternary ammonium salts .

<9a>
In any one of <1a> to <8a>, the component (b) is a cationic surfactant selected from a compound represented by the following general formula (b1) and a compound represented by the general formula (b2) The liquid detergent composition for hard surfaces as described.

[Wherein, at least one selected from R ^1b and R ^2b represents an alkyl group, alkenyl group or hydroxyalkyl group having 8 to 18 carbon atoms, and the remainder is an alkyl group having 1 to 3 carbon atoms, hydroxy An alkyl group or a polyoxyethylene group having an average number of added moles of 10 or less; R ^3b and R ^4b are the same or different and are each an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or an average number of added moles of 10; The following polyoxyethylene groups are shown, and Y ^- represents a halogen atom or an anion residue of a sulfonate ester or sulfate ester having 1 to 5 carbon atoms. ]

[Wherein, R ^5b represents an alkyl group, alkenyl group or hydroxyalkyl group having 8 to 18 carbon atoms, and R ^6b and R ^7b are the same or different and each represents an alkyl group having 1 to 3 carbon atoms. , A hydroxyalkyl group or a polyoxyethylene group having an average added mole number of 10 or less, and R ^8b represents an alkylene group having 1 to 3 carbon atoms. Z ^- represents a halogen atom or an anion residue of a sulfonate ester or sulfate ester having 1 to 5 carbon atoms. ]

<10a>
The liquid detergent composition for hard surface according to any one of <1a> to <9a>, wherein the component (c) is one or more surfactants selected from amphoteric surfactants and nonionic surfactants.

<11a>
The amphoteric surfactant is one or more amphoteric surfactants selected from amine oxide, sulfobetaine and carbobetaine, preferably one or more amphoteric surfactants selected from sulfobetaine and carbobetaine, The liquid detergent composition for hard surfaces according to any one of <1a> to <10a>, which is preferably carbobetaine.

<12a>
In the amphoteric surfactant, the content of one or more amphoteric surfactants selected from amine oxide, sulfobetaine and carbobetaine is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass. % Or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less. Any of <1a> to <11a> A liquid detergent composition for hard surfaces according to claim 1.

<13a>
In the amphoteric surfactant, the content of one or more amphoteric surfactants selected from sulfobetaine and carbobetaine is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more. More preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less, according to any one of <1a> to <12a> A liquid detergent composition for hard surfaces.

<14a>
Nonionic surfactants include (c1) monoalkyl glyceryl ether (hereinafter referred to as component (c1)), (c2) polyoxyalkylene monoalkyl or alkenyl ether (hereinafter referred to as component (c2)), (c3) alkyl poly Glycoside (glycoside type nonionic surfactant) [hereinafter referred to as component (c3)], (c4) sorbitan nonionic surfactant [hereinafter referred to as component (c4)], (c5) aliphatic alkanolamide [hereinafter referred to as component] (Referred to as component (c5)], (c6) fatty acid monoglyceride (hereinafter referred to as component (c6)), and (c7) sucrose fatty acid ester (hereinafter referred to as component (c7)). The liquid detergent composition for hard surfaces according to any one of <1a> to <13a>, which is a surfactant.

<15a>
The nonionic surfactant is at least one nonionic surfactant selected from the component (c1), the component (c2) and the component (c3), preferably the component (c3), described in <14a>. A liquid detergent composition for hard surfaces.

<16a>
In the nonionic surfactant, the content of the component (c3) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more. The liquid detergent composition for hard surfaces according to <14a> or <15a>, preferably 95% by mass or more, more preferably 99% by mass or more, and preferably 100% by mass or less.

<17a>
The hard surfactant according to any one of <1a> to <16a>, wherein the anionic surfactant is an anionic surfactant having a sulfate ester group, a phosphate ester group, a phosphonic acid group, a sulfonic acid group, or a carboxy group. Liquid detergent composition for surfaces.

<18a>
The anionic surfactant has a hydrocarbon group, and the hydrocarbon group preferably has 5 or more carbon atoms, more preferably 6 or more, still more preferably 7 or more, still more preferably 8 or more, and still more preferably. 10 or more, more preferably 12 or more, and preferably 21 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less. The hydrocarbon group is linear or branched. The liquid detergent composition for hard surface according to any one of <1a> to <17a>, which is an alkyl group, an alkylene group, or an aryl group.

<19a>
The anionic surfactant is (c8) a sulfosuccinic acid ester having a hydrocarbon group having 5 to 18 carbon atoms or a salt thereof (hereinafter referred to as (c8) component), (c9) a carbon having 8 to 21 carbon atoms. An anionic surfactant having a hydrogen group and a sulfate ester group or a sulfonic acid group [excluding the component (c8)] (hereinafter referred to as the component (c9)), (c10) carbonization having 7 to 21 carbon atoms Anionic surfactant having a hydrogen group and a carboxy group (hereinafter referred to as component (c10)), and (c11) an anionic interface having a hydrocarbon group having 8 to 21 carbon atoms and a phosphate group The liquid detergent composition for hard surfaces according to any one of <1a> to <18a>, which is one or more anionic surfactants selected from the group consisting of activators (hereinafter referred to as component (c11)) .

<20a>
The anionic surfactant is at least one anionic surfactant selected from the group consisting of component (c8) and component (c9), preferably at least one anionic interface selected from component (c9) The liquid detergent composition for hard surfaces according to <19a>, which is an activator.

<21a>
In the anionic surfactant, the content of the component (c9) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more. The liquid detergent composition for hard surfaces according to <19a> or <20a>, preferably 95% by mass or more, more preferably 99% by mass or more, and preferably 100% by mass or less.

<22a>
The content of component (a) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.4% by mass or less, <1a The liquid detergent composition for hard surfaces according to any one of> to <21a>.

<23a>
The content of the component (b) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and Preferably, it is 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, still more preferably 2% by mass or less, and still more preferably 1.5% by mass or less. <22a> The liquid cleaning composition for hard surfaces according to any one of the above.

<24a>
The content of the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and preferably 10% by mass or less, more preferably The liquid detergent composition for hard surface according to any one of <1a> to <23a>, which is 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

<25a>
The mass ratio of (a) / (b) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.15 or more, and preferably 5 or less. The hard surface liquid detergent composition according to any one of <1a> to <24a>, more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, and even more preferably 1 or less. .

<26a>
The mass ratio of (b) / (c) is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.15 or more, and preferably 30 or less, more preferably 25 or less, still more preferably The hard surface liquid detergent composition according to any one of <1a> to <25a>, wherein is 20 or less, more preferably 10 or less.

<27a>
The water content is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, and preferably 95% by weight or less, more preferably 93% by weight or less, <1a > The liquid detergent composition for hard surfaces according to any one of <26a>.

<28a>
The liquid detergent composition for hard surface according to any one of <1a> to <27a>, wherein the hard surface is a hydrophilic hard surface.

<29a>
The hard surface treated with the liquid detergent composition for hard surface, preferably a hydrophilic hard surface, more preferably the static contact angle with respect to water of the glass surface is preferably 20 ° or less, more preferably 15 ° or less, still more preferably. The liquid detergent composition for hard surfaces according to any one of <1a> to <28a>, which is 10 ° or less, more preferably 8 ° or less.

<30a>
<1a> to <29a> A method for preventing adhesion of dirt on a hard surface, wherein the hard surface is treated with the liquid detergent composition for hard surface according to any one of <1a> to <29a>.

<31a>
The method for preventing contamination of a hard surface according to <30a>, wherein the hard surface is a hydrophilic hard surface.

<32a>
Hard surface is glass, earthenware, porcelain, glazed, tile, ceramics; metals such as aluminum, stainless steel, brass; synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP; cotton, silk, wool, etc. <30a> or <31a>, which is a solid hard surface of a synthetic fiber such as polyester, nylon, or rayon.

<33a>
The hard surface according to any one of <30a> to <32a>, wherein the hard surface is one or more hard surfaces selected from glass, ceramic, porcelain, plastic, stainless steel and silicon wafer Method.

<34a>
Treating an article having a hard surface, and further an article having a hard surface selected from a toilet bowl, bathtub, kitchen sink, window glass, mirror, and faucet, on the hard surface according to any one of <30a> to <33a> Adhesion prevention method.

<35a>
The hard surface treated with the liquid detergent composition for hard surface, preferably a hydrophilic hard surface, more preferably the static contact angle with respect to water of the glass surface is preferably 20 ° or less, more preferably 15 ° or less, still more preferably. The method for preventing soil adhesion on a hard surface according to any one of <30a> to <34a>, wherein is 10 ° or less, more preferably 8 ° or less.

<36a>
Use of the composition according to any one of <1a> to <29a> as a liquid detergent for hard surfaces.

<1b>
(A) including the structural unit (a1) represented by the following formula (1) and the structural unit (a2) represented by the following formula (2), the molar ratio of the structural unit (a1) and the structural unit (a2) A copolymer in which structural unit (a1) / structural unit (a2) is 30/70 or more and 99.9 / 0.1 or less (hereinafter referred to as component (a)), (b) a cationic surfactant [ Hereinafter, the liquid detergent composition for hard surfaces containing (b) component] and (d) chelating agent (hereinafter referred to as (d) component).

<2b>
The weight average molecular weight of the component (a) is preferably 500 or more, more preferably 5000 or more, still more preferably 10,000 or more, still more preferably 30,000 or more, and preferably 200,000 or less, more preferably 150,000 or less. The liquid detergent composition for hard surfaces according to <1b>, more preferably 100,000 or less.

<3b>
The molar ratio of the structural unit (a1) to the structural unit (a2) of the component (a) is 30/70 or more, preferably 50/50 or more, more preferably 55, in terms of the structural unit (a1) / structural unit (a2). / 45 or more, more preferably 60/40 or more, even more preferably 75/25 or more, even more preferably 90/10 or more, and 99.9 / 0.1 or less, preferably 98/2 or less, more preferably Is a liquid detergent composition for hard surfaces according to <1b> or <2b>, which is 96/4 or less.

<4b>
The content of the structural unit (a1) in the component (a) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, and even more. Preferably, it is 90 mol% or more, and preferably 99 mol% or less, more preferably 98 mol% or less, still more preferably 95 mol% or less, for a hard surface according to any one of <1b> to <3b> Liquid detergent composition.

<5b>
The content of the structural unit (a2) in the component (a) is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 5 mol% or more, and preferably 70 mol% or less, more preferably Is 50 mol% or less, more preferably 30 mol% or less, more preferably 20 mol% or less, more preferably 10 mol% or less, and the liquid cleaning for hard surfaces according to any one of <1b> to <4b> Agent composition.

<6b>
The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 10 mol% or less, more preferably 5 mol% or less, more preferably 1 mol% or less, The hard surface liquid detergent composition according to any one of <1b> to <5b>, preferably 0.5 mol% or less, more preferably 0.1 mol% or less, or 0 mol%. .

<7b>
The total content of the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and even more preferably. Is a liquid detergent composition for hard surfaces according to any one of <1b> to <6b>, which is 99.5 mol% or more, more preferably 99.9 mol% or more, or 100 mol%.

<8b>
(B) The hard surface liquid detergent composition according to any one of <1b> to <7b>, wherein the component is a mono- or di-long alkyl quaternary ammonium salt.

<9b>
The component (b) is a cationic surfactant selected from the compound represented by the following general formula (b1) and the compound represented by the general formula (b2), and any one of <1b> to <8b> The liquid detergent composition for hard surfaces as described.

<10b>
(D) The hard surface according to any one of <1b> to <9b>, wherein the component is one or more compounds selected from aminocarboxylic acids, hydroxycarboxylic acids, hydroxyphosphonic acids, and salts thereof Liquid detergent composition.

<11b>
The component (d) is one or more compounds selected from aminocarboxylic acids, hydroxycarboxylic acids, and salts thereof, preferably aminocarboxylic acids or salts thereof, more preferably ethylenediaminetetraacetic acid or salts thereof. <1b> to <10b>, The liquid detergent composition for hard surfaces according to any one of <1b> to <10b>.

<12b>
The content of component (a) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less, and still more preferably 0.4% by mass or less, <1b > The liquid detergent composition for hard surfaces according to any one of <11b>.

<13b>
The content of the component (b) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and , Preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, still more preferably 1.5% by mass or less, and still more preferably 1% by mass. % Of the liquid detergent composition for hard surfaces according to any one of <1b> to <12b>.

<14b>
(D) Content of component becomes like this. Preferably it is 0.01 mass% or more, More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, More preferably, it is 0.2 mass% or more, more More preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 9% by mass or less, still more preferably 8% by mass or less, still more preferably 6% by mass or less, and still more preferably 5% by mass. % Of the liquid detergent composition for hard surfaces according to any one of <1b> to <13b>, more preferably 4% by mass or less.

<15b>
The mass ratio of (a) / (b) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.15 or more, and preferably 5 or less. More preferably, it is 4 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1 or less, the liquid detergent composition for hard surfaces according to any one of <1b> to <14b> .

<16b>
The mass ratio of (b) / (d) is 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.15 or more, Preferably, it is 10 or less, more preferably 5 or less, still more preferably 3 or less, even more preferably 1 or less, and still more preferably 0.8 or less, according to any one of <1b> to <15b>. Liquid detergent composition for hard surfaces.

<17b>
The liquid detergent composition for hard surfaces according to any one of <1b> to <16b>, which contains a surfactant other than the component (b) [hereinafter referred to as the component (c)].

<18b>
The component (c) is one or more surfactants selected from amphoteric surfactants, nonionic surfactants and anionic surfactants, preferably one selected from amphoteric surfactants and nonionic surfactants The liquid detergent composition for hard surfaces according to <17b>, which is the above surfactant.

<19b>
The amphoteric surfactant is at least one amphoteric surfactant selected from amine oxide, sulfobetaine and carbobetaine, preferably at least one amphoteric surfactant selected from sulfobetaine and carbobetaine. Liquid detergent composition for hard surfaces as described in 18b>.

<20b>
Nonionic surfactant is (c1) monoalkyl glyceryl ether, (c2) polyoxyalkylene monoalkyl or alkenyl ether, (c3) alkyl polyglycoside (glycoside type nonionic surfactant), (c4) sorbitan nonionic <18b> or <19b> which is at least one nonionic surfactant selected from the group consisting of a surfactant, (c5) aliphatic alkanolamide, (c6) fatty acid monoglyceride, and (c7) sucrose fatty acid ester The liquid detergent composition for hard surfaces described in 1.

<21b>
The anionic surfactant is (c8) a sulfosuccinic acid ester or a salt thereof having a hydrocarbon group having 5 to 18 carbon atoms, (c9) a hydrocarbon group having 8 to 21 carbon atoms, a sulfate group or a sulfone. An anionic surfactant having an acid group (excluding (c8)), (c10) an anionic surfactant having a hydrocarbon group having 7 to 21 carbon atoms and a carboxy group, and (c11) <18b> to <20b>, which is one or more anionic surfactants selected from the group consisting of an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a phosphate ester group The liquid detergent composition for hard surfaces in any one.

<22b>
The content of the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and preferably 10% by mass or less, more preferably The liquid detergent composition for hard surfaces according to any one of <17b> to <21b>, which is 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

<23b>
The water content is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, and preferably 95% by weight or less, more preferably 93% by weight or less, <1b > The liquid detergent composition for hard surfaces according to any one of <22b>.

<24b>
The liquid detergent composition for hard surface according to any one of <1b> to <23b>, wherein the hard surface is a hydrophilic hard surface.

<25b>
<1b> to <24b> A method for preventing adhesion of dirt on a hard surface, comprising treating the hard surface with the liquid detergent composition for hard surface according to any one of <1b> to <24b>.

<26b>
The method for preventing soil adhesion on a hard surface according to <25b>, wherein the hard surface is a hydrophilic hard surface.

<27b>
Hard surface is glass, earthenware, porcelain, glazed, tile, ceramics; metals such as aluminum, stainless steel, brass; synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP; cotton, silk, wool, etc. <25b> or <26b>, which is a solid hard surface of a synthetic fiber such as polyester, nylon, or rayon.

<28b>
Antifouling of hard surface according to any one of <25b> to <27b>, wherein the hard surface is one or more hard surfaces selected from glass, earthenware, porcelain, plastic, stainless steel and silicon wafer Method.

<29b>
Treating an article having a hard surface, and further an article having a hard surface selected from a toilet bowl, a bathtub, a kitchen sink, a window glass, a mirror, and a faucet, on the hard surface according to any one of <25b> to <28b> Adhesion prevention method.

<30b>
The hard surface treated with the liquid detergent composition for hard surface, preferably a hydrophilic hard surface, more preferably the static contact angle with respect to water of the glass surface is preferably 20 ° or less, more preferably 15 ° or less, still more preferably. Is a method for preventing adhesion of dirt on a hard surface according to any one of <25b> to <29b>, which is 10 ° or less, more preferably 8 ° or less, and preferably 1 ° or more.

<31b>
Use of the composition according to any one of <1b> to <24b> as a liquid detergent for hard surfaces.

Example Production Example 1 [Production of Copolymer A1]
(Process 1)
126.30 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a four-necked flask with an internal volume of 1000 mL, and the mixture was heated to 78 ° C. and refluxed. Here, 181.12 g of 2- (dimethylamino) ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 2- (dimethylamino) ethyl diethylsulfate methacrylate (manufactured by Kao Corporation / 90% aqueous solution) 23. A solution in which 60 g and 53.20 g of ethanol are mixed, and 5.83 g of 2,2′-azobis (2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) and 10.00 g of ethanol are mixed. Were added dropwise over 2 hours. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.

(Process 2)
94.70 g of the obtained polymer solution, 3.15 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) and 150.00 g of water were added to a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 50 ° C. did. Thereto, 38.70 g of 1,3-propane sultone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour to carry out the reaction. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain an aqueous solution containing the copolymer A1.

In the copolymer A1, the structural unit (a1) has the following structure in the formula (1), the structural unit (a2) has the following structure in the formula (2), and the structural unit (a1) / The molar ratio of the structural unit (a2) is 95/5.
The structural unit ^{^{^{_{(a1): R 1 = R}}}} 2 = H, R 3 = CH 3, R 4 = C 2 H 4, R 5 = R 6 = CH 3, X 1 = O, X 2 = R 17 SO 3 - , R ¹⁷ = C ₃ H ₆
Structural unit (a2): R ⁸ = R ⁹ = H, R ¹⁰ = CH ₃ , X ³ = O, R ¹¹ = C ₂ H ₄ , X ⁴ = N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ , R ¹² = ^{_{^{_{R 13 = CH 3, R 14}}}} = C 2 H 5, X 5 = C 2 H 5 SO 4 -
Further, the copolymer A1 had a weight average molecular weight of 63,000.

Production Example 2 [Production of Copolymer A2]
(Process 1)
In a four-necked flask with an internal volume of 1000 mL, 37.95 g of ethanol was placed, heated to 78 ° C. and refluxed. A solution prepared by mixing 122.94 g of 2- (dimethylamino) ethyl methacrylate, 30.06 g of 2- (dimethylamino) ethyl diethylsulfate and 28.88 g of ethanol with 2,2′-azobis (2 -Methylbutyronitrile) A solution in which 1.67 g and 3.90 g of ethanol were mixed was dropped separately over 2 hours for polymerization. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.
(Process 2)
270.77 g of the obtained polymer solution, 6.56 g of sodium bicarbonate, and 308.91 g of water were placed in a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 50 ° C. Thereto, 102.21 g of 1,3-propane sultone was added dropwise over 1 hour to carry out the reaction. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain an aqueous polymer solution containing the copolymer A2.

In the copolymer A2, the structural units (a1) and (a2) are the same as the copolymer A1, and the molar ratio of the structural unit (a1) / the structural unit (a2) is 90/10.
Further, the copolymer A2 had a weight average molecular weight of 69000.

Production Example 3 [Production of Copolymer A3]
(Process 1)
94.46 g of ethanol was placed in a four-necked flask having an internal volume of 1000 mL, and the mixture was heated to 78 ° C. and refluxed. A solution prepared by mixing 267.52 g of 2- (dimethylamino) ethyl methacrylate, 147.20 g of 2- (dimethylamino) ethyldiethyl sulfate, and 78.29 g of ethanol with 2,2′-azobis (2 -Methylbutyronitrile) A solution in which 4.09 g and 9.54 g of ethanol were mixed was dropped separately over 2 hours for polymerization. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.
(Process 2)
In a four-necked flask with an internal volume of 1000 mL, 307.82 g of the obtained polymer solution, 7.15 g of sodium hydrogen carbonate, and 394.56 g of water were placed, and the temperature was raised to 50 ° C. Thereto was reacted 111.20 g of 1,3-propane sultone dropwise over 1 hour. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain a polymer aqueous solution containing the copolymer A3.

In the copolymer A3, the structural units (a1) and (a2) are the same as the copolymer A1, and the molar ratio of the structural unit (a1) / the structural unit (a2) is 80/20.
Further, the copolymer A3 had a weight average molecular weight of 78,000.

Production Example 4 [Production of Copolymer A4]
(Process 1)
33.27 g of ethanol was placed in a four-necked flask with an internal volume of 1000 mL, and the mixture was heated to 78 ° C. and refluxed. A solution prepared by mixing 81.13 g of 2- (dimethylamino) ethyl methacrylate, 76.52 g of 2- (dimethylamino) ethyl diethylsulfate and 29.76 g of ethanol with 2,2′-azobis (2 -Methylbutyronitrile) A solution in which 1.42 g and 3.31 g of ethanol were mixed was dropped separately over 2 hours for polymerization. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.
(Process 2)
270.77 g of the obtained polymer solution, 4.34 g of sodium bicarbonate, and 285.67 g of water were placed in a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 50 ° C. Thereto, 67.45 g of 1,3-propane sultone was added dropwise over 1 hour to carry out the reaction. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain a polymer aqueous solution containing a copolymer.

In the copolymer A4, the structural units (a1) and (a2) are the same as the copolymer A1, and the molar ratio of the structural unit (a1) / the structural unit (a2) is 70/30.
In addition, the copolymer A4 had a weight average molecular weight of 81,000.

Production Example 5 [Production of Polymer A′1]
(Process 1)
53.23 g of ethanol was placed in a four-necked flask having an internal volume of 500 mL, and the mixture was heated to 78 ° C. and refluxed. A solution prepared by mixing 150.00 g of 2- (dimethylamino) ethyl methacrylate and 16.60 g of ethanol, 0.92 g of 2,2′-azobis (2-methylbutyronitrile), and 10.00 g of ethanol are mixed there. The resulting solutions were separately dropped over 2 hours to polymerize. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.
(Process 2)
75.76 g of the obtained polymer solution, 3.47 g of sodium hydrogen carbonate, and 150.00 g of water were placed in a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 50 ° C. Thereto, 42.73 g of 1,3-propane sultone was added dropwise over 1 hour to carry out the reaction. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain a polymer aqueous solution containing the polymer A′1.

The polymer A′1 was a polymer containing only the same structural unit (a1) as the copolymer A1 as a structural unit (the structural unit (a1) was 100 mol%).
Further, the polymer A′1 had a weight average molecular weight of 40000.

The weight average molecular weights of the copolymers A1 to A4 were measured by gel permeation chromatography (pullulan) under the following conditions.
Column: Two TSKgel α-M (manufactured by Tosoh Corporation) were connected in series.
Column temperature: 40 ° C
Eluent: 0.15 mol Na ₂ SO ₄ /1% CH ₃ COOH / water Flow rate: 1.0 ml / min Detector: Differential refractometer

Further, the weight average molecular weight of the polymer A′1 was measured by SLS (static light scattering method). That is, using a light scattering photometer “DLS-7000” (manufactured by Otsuka Electronics Co., Ltd.), static light scattering was measured under the following conditions to calculate Zimm-plot. Further, the refractive index increment necessary for calculating the molecular weight was measured using a differential refractometer “DRM3000” (manufactured by Otsuka Electronics Co., Ltd.).
Wavelength: 632.8 nm (helium-neon laser)
Scattering angle: measured at intervals of 10 ° from 30 ° to 150 °.
Temperature: 25 ° C
Solvent: trifluoroethanol

Examples 1a to 17a and Comparative Examples 1a to 8a
Using the following blending components, hard surface liquid detergent compositions shown in Tables 1 and 2 were prepared, and the following items were evaluated. The results are shown in Tables 1 and 2. In the table, the (a) / (b) mass ratio is shown with the component (a ′) as the component (a) for convenience.
In addition, the mass% of the mixing | blending component in Table 1, 2 is a numerical value based on all effective parts. Moreover, the anionic surfactant of (c) component has shown the mass% based on the quantity as a sodium salt.
The pH was adjusted with a small amount of sodium hydroxide and hydrochloric acid.

<Blending ingredients>
(A) Components / copolymers A1 to A4 were used.
Component (a ′) (Comparative component of component (a))
-Polymer A'1 was used.
(B) Component / cationic surfactant: alkyldimethylbenzylammonium chloride: alkyl group having 8 carbon atoms (product name “Sanisol 08”, manufactured by Kao Corporation)
Component (c) Nonionic surfactant: alkyl polyglycoside: alkyl (carbon number 12-16) polyglucose (average degree of sugar condensation 1-2) (product name “AG124”, manufactured by Kao Corporation)
・ Amphoteric surfactant: Lauramidopropylcarbobetaine (Product name “Amphithol 20AB”, manufactured by Kao Corporation)
Anionic surfactant: sodium polyoxyethylene alkyl ether sulfate, alkyl group having 12 to 16 carbon atoms, ethylene oxide average added mole number 4.0 (product name “ES-4K”, manufactured by Kao Corporation)

<Contact angle>
1 mL of the liquid detergent composition for hard surface was applied to a glass plate (Matsunami Glass Industry Co., Ltd., shape 76 mm × 26 mm × 1 mm) and allowed to stand for 5 minutes, and then 25 ° C. tap water (flow rate 50 mL / second) ) For 20 seconds. The static contact angle with respect to the ion-exchanged water of the glass plate subjected to the above treatment was measured in a measurement chamber that was temperature-controlled at 25 ° C. and 40% RH. For measurement, a fully automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd. was used, and 20 μl of ion-exchanged water droplets were deposited on the treated surface and contacted 10 times at 1-second intervals after 3 seconds of deposition. The angle was measured and the average value was recorded as data. In addition, the static contact angle of the glass plate before a process was 25 degrees. The lower the contact angle, that is, the smaller the static contact angle of the glass plate before processing, the more hydrophilic it is.

<Anti-fouling property (anti-fouling property)>
A glass plate (Matsunami Glass Industry Co., Ltd., shape: 76 mm × 26 mm × 1 mm) is coated with 1 mL of the hard surface liquid detergent composition on one side and allowed to stand for 5 minutes, and then 25 ° C. tap water (flow rate 50 mL) / Second) was used for the following evaluation.
450 ml of water and 50 ml of a model oil solution (model oil: oleic acid, pigment: Sudan III (0.1 part by mass with respect to 100 parts by mass of oleic acid)) are mixed in a 500 ml beaker having a diameter of 10 cm, and the lower layer is water. The liquid which the upper layer isolate | separated into two layers of oil was prepared.
The glass plate was passed through the upper layer and immersed in the lower layer for 10 seconds so that the entire plate was immersed, and then pulled up.
Then, after drying the glass plate after soaking, take a picture of the glass plate, image it (using ImageJ) to measure the residual area of the oil on the glass plate, and based on the processing area of the glass plate, The residual ratio was calculated (first time). Thereafter, using the glass plate as it was, the operation of again dipping for 10 seconds was performed, and the residual ratio was calculated by the same method (second time). Residual rate (%) was calculated based on how much oil was coated on the surface (degree of coating), where the treated area of the glass was 100.

<Bubbling>
The liquid detergent composition for hard surface is filled in a trigger type spray container (toilet magic phosphorus deodorizing and cleaning spray, manufactured by Kao Corporation), and 10 in a 200 mL graduated cylinder (inner diameter 40 mm) in the wide foam mode of the container. Sprayed twice. The mass of the 200 mL graduated cylinder after spraying was measured using a 4-digit balance, and the difference from the mass of the graduated cylinder before spraying was defined as the foam application amount (g) (a). The volume (mL) of foam in the graduated cylinder after spraying was visually read (b). The foam specific volume was calculated by the following formula. The results are shown in Tables 1 and 2.
Foam specific volume (mL / g) = (b) / (a)
It shows that it is excellent in foaming, so that foam specific volume is large.

<Sterilization power>
Staphylococcus aureus (strain NBRC12732) was scraped after culturing twice at 37 ° C./24 hours on a nutrient agar medium (prepared according to the Nutrient Agar reagent manufactured by Difco). Suspended and dispersed in a medium (Difco's Nutrient Broth reagent prepared at 1/2 concentration of Noh), and the bacterial concentration was adjusted to 2.5 to 13 × 10 6 using 1/2 neutral liquid medium. Prepared to ⁸ cfu / mL, mixed with an equal volume of 3% by weight bovine serum albumin aqueous solution to obtain a test bacterial solution. A stainless steel disc having a diameter of 20 mm, a thickness of 1 mm, and a surface grade 2B is placed on a glass petri dish having an inner diameter of 75 mm, and 10 μL of the above-mentioned test bacterial solution is placed on the disc surface using a micropipette (Gilson, trade name Pipetteman). ) Inoculated and spread. After leaving the glass petri dish under the condition of 25 ± 1 ° C. without confirming the drying of the bacterial solution, the liquid detergent composition for hard surface was immediately washed with water adjusted to a hardness of 4 ° dH with 100 ° C. The diluted solution was allowed to adhere. Attachment of a liquid obtained by diluting a liquid detergent composition for a hard surface 100 times with water adjusted to a hardness of 4 ° dH is performed using a micropipette (Gilson, trade name Pipetteman) and a stainless steel disk surface 3 having a diameter of 20 mm. against .14cm ^2, (corresponding to 0.32 g / 100 cm ²⁾ inoculating the solution 10μL of the diluted hard surface liquid detergent composition 100-fold in water to adjust the hardness to 4 ° dH to and spread went. After 5 minutes of adhesion, add a certain amount of LP water dilution (prepared by Nissui Pharmaceutical Co., Ltd. according to the Noboru), taking care not to run off the adhered composition, and remove the composition. Bacterial performance was inactivated and the bacterial concentration in the LP water dilution was counted by the pour culture method. Control operation with the same operation (inoculated and spread 10 μL on the surface of the disc by inoculation with the micropipette and put into the LP diluent 5 minutes after inoculation) using physiological saline instead of the composition As a rule, the logarithmic difference in the number of bacteria with the control operation in the LP diluted solution was calculated and used as an index of the sterilization performance according to the following criteria.
* Evaluation criteria for sterilization power A: Logarithmic difference in the number of bacteria is 2 or more B: Logarithmic difference in the number of bacteria is less than 2

<Compounding stability>
The appearance immediately after the preparation of the hard surface liquid detergent composition was visually observed at a liquid temperature of 20 ° C. and evaluated according to the following criteria.
* Evaluation criteria of compounding stability A: Dissolved uniformly.
B: Slightly cloudy.
C: It is clearly cloudy.

Examples 1b to 9b and Comparative Examples 1b to 4b
Using the following blending components, the hard surface liquid detergent composition shown in Table 3 was prepared, and the following items were evaluated. The results are shown in Table 3. Note that the mass% of the blended components in Table 3 are all numerical values based on the effective component. In the table, the (a) / (b) mass ratio is shown with the component (a ′) as the component (a) for convenience. Moreover, the mass ratio of (b) / (d) showed the value computed based on the mass% of the acid conversion of (d) component.
The pH was adjusted with a small amount of sodium hydroxide or hydrochloric acid.

<Blending ingredients>
Component (a) The copolymer A1 of Production Example 1 and the copolymer A4 of Production Example 4 were used.
Component (a ′) (Comparative component of component (a))
-Polymer A'1 of the said manufacture example 5 was used.
(B) Component / cationic surfactant: alkyldimethylbenzylammonium chloride: alkyl group having 8 carbon atoms (product name “Sanisol 08”, manufactured by Kao Corporation)
Component (d): EDTA: ethylenediaminetetraacetic acid, tetrasodium salt (the numbers in the table are mass% as sodium salts, and the numbers in parentheses are mass% in terms of acid)
Other components / nonionic surfactant: alkyl polyglycoside: alkyl (carbon number 12-16) polyglucose (average sugar condensation degree 1-2) (product name “AG124”, manufactured by Kao Corporation)
・ Amphoteric surfactant: Lauramidopropylcarbobetaine (Product name “Amphithol 20AB”, manufactured by Kao Corporation)

<Contact angle>
The static contact angle was measured by the same method as in Example 1a and the like.

<Anti-fouling property (anti-fouling property)>
A glass plate (Matsunami Glass Industry Co., Ltd., shape: 76 mm × 26 mm × 1 mm) is coated with 1 mL of the hard surface liquid detergent composition on one side and allowed to stand for 5 minutes, and then 25 ° C. tap water (flow rate 50 mL) / Second) was used for the following evaluation.
450 ml of water and 50 ml of a model oil solution (model oil: oleic acid, pigment: Sudan III (0.1 part by mass with respect to 100 parts by mass of oleic acid)) are mixed in a 500 ml beaker having a diameter of 10 cm, and the lower layer is water. The liquid which the upper layer isolate | separated into two layers of oil was prepared.
The glass plate was passed through the upper layer and immersed in the lower layer for 10 seconds so that the entire plate was immersed, and then pulled up.
Then, after drying the glass plate after soaking, take a picture of the glass plate, image it (using ImageJ) to measure the residual area of the oil on the glass plate, and based on the processing area of the glass plate, The residual ratio of was calculated. Residual rate (%) was calculated based on how much oil was coated on the surface (degree of coating), where the treated area of the glass was 100. The antifouling property was evaluated according to the following criteria based on the residual rate.
* Evaluation standard of antifouling property A: Residual rate is less than 10% B: Residual rate is 10% or more

<Detergency (scale removal)>
As a soil model, 2 ml of a 0.5% calcium dihydrogen phosphate aqueous solution was uniformly applied to a black ceramic board (10 cm × 10 cm tile) and dried at 120 ° C. for 30 minutes. This was repeated 10 times to make a model contaminated plate, which was used for the detergency test.
The composition was dripped (0.3 ml) on the model-contaminated plate fixed horizontally, left for 1 minute, and then washed with a cotton swab 10 times. Images were obtained with the same shooting conditions such as brightness for the uncoated soiled ceramic plate, the uncleaned ceramic plate after washing (model contamination plate), and the cleaned ceramic plate. The gray scale of each ceramic plate was measured from the image. The cleaning rate of the ceramic plate was calculated by comparing the state of the ceramic plate after cleaning with the cleaning rate of 0% for the ceramic plate before washing the soil, and the cleaning rate of 100% for the uncoated soiled ceramic plate. Note that the image processing software ImageJ1.47v was used for the gray scale measurement.

<Sterilization power>
The sterilizing power was evaluated by the same method as in Example 1a and the like.

<Compounding stability>
The blending stability was evaluated in the same manner as in Example 1a and the like.

<Bubbling>
The liquid detergent composition for hard surface is filled in a trigger type spray container (toilet magic phosphorus deodorizing and cleaning spray, manufactured by Kao Corporation), and 10 in a 200 mL graduated cylinder (inner diameter 40 mm) in the wide foam mode of the container. Sprayed twice. The mass of the 200 mL graduated cylinder after spraying was measured using a 4-digit balance, and the difference from the mass of the graduated cylinder before spraying was defined as the foam application amount (g) (a). The volume (mL) of foam in the graduated cylinder after spraying was visually read (b). The foam specific volume was calculated by the following formula. The results are shown in Table 3.
Foam specific volume (mL / g) = (b) / (a)
It shows that it is excellent in foaming, so that foam specific volume is large. The foaming performance was evaluated from the foam specific volume according to the following criteria.
* Evaluation criteria for foaming performance A: Foam specific volume of 10 mL / g or more B: Foam specific volume of 5 mL / g or more and less than 10 mL / g C: Foam specific volume of less than 5 mL / g

Claims

(A) including the structural unit (a1) represented by the following formula (1) and the structural unit (a2) represented by the following formula (2), the molar ratio of the structural unit (a1) and the structural unit (a2) A copolymer in which structural unit (a1) / structural unit (a2) is 30/70 or more and 99.9 / 0.1 or less (hereinafter referred to as component (a)), (b) a cationic surfactant [ (Hereinafter referred to as component (b)), and (c) one or more surfactants selected from amphoteric surfactants, nonionic surfactants and anionic surfactants (hereinafter referred to as component (c)). , Liquid detergent composition for hard surfaces.

[Where,
R 1 to R 3 : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R 4 : an alkylene group having 1 to 4 carbon atoms, or —Y 1 —OPO 3 — —Y 2 —
Y 1 , Y 2 : the same or different, alkylene group having 1 to 4 carbon atoms R 5 , R 6 : the same or different, hydrocarbon group having 1 to 4 carbon atoms X 1 : O or NR 7 , R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X 2 : a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R 17 SO 3 − , or R 17 COO — . However, when R 4 is an alkylene group having 1 to 4 carbon atoms, X 2 is R 17 SO 3 − , or R 17 COO − , R 17 is an alkylene group having 1 to 4 carbon atoms, and R 4 is When —Y 1 —OPO 3 — —Y 2 —, X 2 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

[Where,
R 8 to R 10 : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms X 3 : O
R 11 is an alkylene group having 1 to 4 carbon atoms X 4 is N + R 12 R 13 R 14 X 5 or NR 15 R 16 , and R 12 to R 16 are the same or different and are a hydrogen atom or a carbon number 1 to 4 hydrocarbon groups, X 5 represents an anion. ]
The liquid detergent composition for hard surfaces according to claim 1, wherein the mass ratio of (b) / (c) is 0.05 or more and 30 or less.
(A) including the structural unit (a1) represented by the following formula (1) and the structural unit (a2) represented by the following formula (2), the molar ratio of the structural unit (a1) and the structural unit (a2) A copolymer in which structural unit (a1) / structural unit (a2) is 30/70 or more and 99.9 / 0.1 or less (hereinafter referred to as component (a)), (b) a cationic surfactant [ Hereinafter, the liquid detergent composition for hard surfaces containing (b) component] and (d) chelating agent (hereinafter referred to as (d) component).

[Where,
R 1 to R 3 : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R 4 : an alkylene group having 1 to 4 carbon atoms, or —Y 1 —OPO 3 — —Y 2 —
Y 1 , Y 2 : the same or different, alkylene group having 1 to 4 carbon atoms R 5 , R 6 : the same or different, hydrocarbon group having 1 to 4 carbon atoms X 1 : O or NR 7 , R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X 2 : a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R 17 SO 3 − , or R 17 COO — . However, when R 4 is an alkylene group having 1 to 4 carbon atoms, X 2 is R 17 SO 3 − , or R 17 COO − , R 17 is an alkylene group having 1 to 4 carbon atoms, and R 4 is When —Y 1 —OPO 3 — —Y 2 —, X 2 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

[Where,
R 8 to R 10 : the same or different, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms X 3 : O
R 11 is an alkylene group having 1 to 4 carbon atoms X 4 is N + R 12 R 13 R 14 X 5 or NR 15 R 16 , and R 12 to R 16 are the same or different and are a hydrogen atom or a carbon number 1 to 4 hydrocarbon groups, X 5 represents an anion. ]
The liquid detergent composition for hard surfaces according to claim 3, wherein the mass ratio of (b) / (d) is 0.01 or more and 10 or less.
The liquid detergent composition for hard surface according to any one of claims 1 to 4, wherein the content of the component (a) is 0.01% by mass or more and 3% by mass or less.
The liquid detergent composition for hard surface according to any one of claims 1 to 5, wherein a mass ratio of (a) / (b) is 0.01 or more and 5 or less.
The liquid detergent composition for a hard surface according to any one of claims 1 to 6, wherein the hard surface is a hydrophilic hard surface.
A method for preventing adhesion of dirt on a hard surface, wherein the hard surface is treated with the liquid detergent composition for hard surface according to any one of claims 1 to 7.