JP2018199769A - Liquid detergent composition for hard surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition for a hard surface, which maintains a sterilizing performance, has excellent detergency, suppresses adhesion of stains to a hard surface, that is, has excellent antifouling performance. A specific structural unit (a1) having a betaine group and a specific structural unit (a2) having a cation group are included, and the molar ratio of the structural unit (a1) to the structural unit (a2). Hard containing a copolymer having a structural unit (a1) / structural unit (a2) of 30/70 or more and 99.9 / 0.1 or less, (b) a cationic surfactant, and (c) a chelating agent. Surface liquid detergent composition. [Selection diagram] None

Description

  The present invention relates to a liquid detergent composition for hard surfaces and a method for preventing soil adhesion on hard surfaces.

  The living environment equipment that surrounds us has various hard surfaces made of tile, plastic, metal, etc., and these hard surfaces are exposed to an environment where various kinds of dirt adhere 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, Patent Document 1 discloses a composition 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 anion charge and a constant total cation charge within the pH range of 1-14 (each individual betaine unit being the same number of constant anions as the constant cation charge). Hard surface cleaning or rinsing compositions are disclosed that exhibit an absolute weight average molecular weight (Mw) of 5,000 to 3,000,000 g / mole (assuming charge).
Patent Document 2 discloses a copolymer containing a unit A containing a betaine group and a cationic unit B.

JP 2010-1000086 A US Patent Application Publication No. 2009/0197791

  Patent Documents 1 and 2 are not sufficient in satisfying the scale removal cleaning power (hereinafter also simply referred to as cleaning power), sterilization performance, and antifouling properties. In particular, the present inventors have added a chelating agent in order to further improve detergency when used in combination with a polymer having a betaine group and a cationic surfactant as described in Patent Document 1. It has been found that when 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 and is excellent in detergency, and is excellent in suppressing adhesion of dirt to a hard surface, that is, excellent in antifouling performance.

  By using a polymer having a specific betaine group and a specific cationic group, a cationic surfactant, and a chelating agent, the present inventors have excellent antifouling performance, detergency and sterilization performance. It was found that the effect was 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 The present invention relates to a hard surface liquid detergent composition comprising a surfactant (hereinafter referred to as component (b)) and (c) a chelating agent (hereinafter referred to as component (c)).

[Where,
R ¹ to R ^3: same or different, a hydrogen atom or C 1 or 2 alkyl radicals R ^4: 1 to 4 alkylene group having a carbon number, 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, the number of hydrogen atom or a C 1 or 2 alkyl groups ^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 have a hydrogen atom or carbon number 1 to 4 hydrocarbon groups, X ⁵ represents an anion. ]

  The present invention also relates to a method for preventing adhesion of a hard surface by treating a hard surface with the above-described 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 detergency, and is excellent in suppressing adhesion of dirt to a hard surface, that is, excellent in antifouling performance.

[Liquid detergent composition for hard surface]
<(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).

[Where,
R ¹ to R ^3: same or different, a hydrogen atom or C 1 or 2 alkyl radicals R ^4: 1 to 4 alkylene group having a carbon number, 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. ]

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 and ethyl group are preferable, and methyl group is more preferable.
In 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. when group, ^{X 2} is ^R 17 SO ₃ ^-, or COO ^- and is, ^{R 4} is ^-Y 1 -OPO ₃ ^{- -Y 2 -} when, ^{X 2} is carbon hydrogen atom or 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. From the same viewpoint, when R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, X ² is preferably R ¹⁷ SO ₃ ^— .
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 same viewpoint, it is preferably 70% by mass or less, preferably 50% by mass or less, preferably 30% by mass or less, preferably 20% by mass or less, preferably 10% by 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, the number of hydrogen atom or a C 1 or 2 alkyl groups ^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 have a hydrogen atom or 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 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 preferred, 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, more preferably a methyl group, from the viewpoint of enhancing the antifouling performance of the component (a) and the ease of quaternization reaction.
In 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 1 mol% or less, Preferably it is 0.5 mol% or less, More preferably, it is 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, 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; It showed the following polyoxyethylene group, Y ^- represents an anion residue of a halogen atom, or a number of 1 to 5 sulfonic acid ester or sulfuric ester carbon. ]

[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. ]

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.

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

<(C) component>
(C) A component 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 (DPTA), 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 0.05% from the viewpoint of imparting antifouling performance to the hard surface. % Or more, more preferably 0.1% by weight or more, and from the viewpoint of blending stability, preferably 3% by weight or less, more preferably 2% by weight or less, still more preferably 1% by weight or less, and still more preferably 0. 0.8 mass% or less, more preferably 0.5 mass% or less, and still more preferably 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, still more preferably 1.5% by mass or less, and still more preferably 1% by mass or less.

  In the hard surface liquid detergent composition of the present invention, the content of the component (c) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of detergency. Preferably 0.1% by weight or more, more preferably 0.2% by weight or more, still more preferably 0.5% by weight or more, and from the viewpoint of economy and blending stability, preferably 10% by weight 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. In addition, the mass of (c) component is an acid conversion value (it is the same also in other quantitative ratios with which the mass of (c) component is related).

  In the liquid detergent composition for hard surface of the present invention, the mass ratio (a) / (b) is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably from the viewpoint of antifouling properties. From the viewpoint of 0.1 or more and sterilization performance, it is 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 1 or less.

  In the liquid detergent composition for hard surface of the present invention, the mass ratio of (b) / (c) is preferably 0.01 or more, more preferably 0.03 or more, from the viewpoint of sterilization performance. Preferably it is 0.05 or more, more preferably 0.1 or more, still more preferably 0.15 or more, and from the viewpoint of blending stability and detergency, it is preferably 10 or less, more preferably 5 or less, still more preferably It is 3 or less, more preferably 1 or less, and still more preferably 0.8 or less.

  The liquid detergent composition for hard surfaces of the present invention can contain a surfactant other than the component (b) [hereinafter referred to as the component (d)]. Examples of the component (d) include one or more surfactants selected from amphoteric surfactants, nonionic surfactants, and anionic surfactants. The component (d) 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 includes one or more amphoteric surfactants selected from amine oxides, sulfobetaines and carbobetaines from the viewpoint of detergency and foamability, 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 detergency 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.
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%, from the viewpoint of detergency and foamability. % 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. is there.

  As sulfobetaine, from the viewpoint of detergency, the alkyl group preferably has 10 or more, preferably 18 or less, more preferably 14 or less N-alkyl-N, N-dimethyl-N-sulfopropylammonium sulfone. N-alkyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) in which the number of carbon atoms of the betaine or alkyl group is preferably 10 or more, preferably 18 or less, more preferably 14 or less, from the viewpoint of detergency. N-alkanoylaminopropyl-N, N-dimethyl-N-sulfopropylammonium having a carbon number of ammonium sulfobetaine or alkanoyl group of preferably 10 or more, preferably 18 or less, more preferably 14 or less from the viewpoint of detergency. The number of carbon atoms of the sulfobetaine or alkanoyl group is preferably 1 from the viewpoint of detergency. Or more, preferably 18 or less, more preferably 14 or less of N- alkanoylamino propyl -N, include N- dimethyl-N-(2-hydroxy-sulfopropyl) ammonium sulfobetaine.

  The carbobetaine is preferably an N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine in which the carbon number of the alkyl group is preferably 10 or more, preferably 18 or less, more preferably 14 or less, from the viewpoint of detergency. Or a compound represented by the following general formula (I), and a compound represented by the following general formula (I) is preferred from the viewpoint of detergency.

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

In general formula (I), R ^1d 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. A nonyl group, a decyl group, or an undecyl group. Group, dodecyl group and tridecyl group are preferred.
In general formula (I), R ^3d and R ^4d are preferably methyl groups.
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, at least one selected from lauramidopropyl carbobetaine, myristamidopropyl betaine, oleamidopropyl betaine, and cocamidopropyl betaine is preferable. These are compounds in which R ^3d and R ^4d in the general formula (I) are each a methyl group.

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

[Wherein, R ^5d 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 ^6d and R ^7d each independently represent 1 to 3 carbon atoms. The following alkyl groups are shown. D represents a —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 general formula (II), R ^5d is preferably an alkyl group having 10 to 18 carbon atoms, more preferably an alkyl group having 12 to 16 carbon atoms, and more preferably from the viewpoint of detergency. It is an alkyl group having 12 to 14 carbon atoms, and more preferably an alkyl group having 12 carbon atoms. R ^6d and R ^7d are preferably a methyl group having 1 carbon atom from the viewpoint of detergency.

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 detergency, (1) alkyl (8 to 22 carbon atoms) dialkyl (1 to 3 carbon atoms) amine oxide is more preferable.

[Nonionic surfactant]
Nonionic surfactants include (d1) monoalkyl glyceryl ether (hereinafter referred to as component (d1)), (d2) polyoxyalkylene monoalkyl or alkenyl ether (hereinafter referred to as (non-ionic surfactant) from the viewpoint of detergency and foamability. d2) component], (d3) alkylpolyglycoside (glycoside type nonionic surfactant) [hereinafter referred to as component (d3)], (d4) sorbitan nonionic surfactant (hereinafter referred to as component (d4)) (D5) aliphatic alkanolamide (hereinafter referred to as component (d5)), (d6) fatty acid monoglyceride (hereinafter referred to as component (d6)), and (d7) sucrose fatty acid ester (hereinafter referred to as component (d7)). 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 (d1), the component (d2), and the component (d3) from the viewpoints of detergency and foamability, and includes the component (d3). Is even more preferable.
In the nonionic surfactant, the total content of the component (d1), the component (d2) and the component (d3) is preferably 50% by mass or more, more preferably 70% by mass, from the viewpoints of detergency and foamability. More preferably, it is 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.
In addition, the content of the component (d3) in the nonionic surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, from the viewpoints of detergency and foamability. Still more preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is 99 mass% or more, Preferably it is 100 mass% or less.

The component (d1) is a monoalkyl glyceryl ether.
As the component (d1), specifically, a compound represented by the following general formula (d1) is preferable.
R ^11d —O— (Gly) _r —H (d1)
[Wherein, R ^11d 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 (d1), R ^11d is preferably 6 or more carbon atoms, more preferably 7 or more carbon atoms, still more preferably 8 or more carbon atoms, and preferably 18 or less carbon atoms, from the viewpoint of detergency. Preferably, it is an alkyl group having 12 or less carbon atoms, more preferably 10 or less carbon atoms, and straight chain alkyl groups such as hexyl group, heptyl group, octyl group, nonyl group and decyl group can be used. From the viewpoint of detergency, an alkyl group having a branched chain is preferable, and a specific alkyl group having a branched chain of R ^1d is a group selected from a 2-ethylhexyl group, a sec-octyl group, an isononyl group, and an isodecyl group. Is more preferable, 2-ethylhexyl group or isodecyl group is still more preferable, and 2-ethylhexyl group is particularly preferable.

In the general formula (d1), r is preferably 1 or more and preferably 2 or less. A compound in which r is 1 is more preferable. Particularly preferred compounds are those in which R ^1d 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 first and third hydroxyl groups of glycerin are bonded, or the first and second hydroxyl groups of glycerin are bonded. It is a structure represented by —CH (CH ₂ OH) CH ₂ —, which varies depending on the catalyst and reaction conditions.

The component (d2) is polyoxyalkylene monoalkyl or alkenyl ether.
In the nonionic surfactant of component (d2), 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, and still more preferably 12 from the viewpoint of detergency. 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 (d2), the average added mole number of alkylene oxide is preferably more than 0, more preferably 1 or more, still more preferably 3 or more, and the same viewpoint from the viewpoint of detergency. , Preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 10 or less.
From the viewpoint of detergency, the alkylene oxide is preferably at least one selected from ethylene oxide, propylene oxide, and butylene oxide, more preferably at least one selected from ethylene oxide and propylene oxide.

As a preferred example of the nonionic surfactant as the component (d2), a nonionic surfactant represented by the following general formula (d2) can be given.
R ^12d O [(C ₂ H ₄ O) ₁ / (C ₃ H ₆ O) _j ] H (d2)
[Wherein, R ^12d 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. ]

From the viewpoint of detergency, the HLB value of the polyoxyalkylene monoalkyl or alkenyl ether as component (d2) and the nonionic surfactant represented by formula (d2) is preferably 5 or more, more preferably 7 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 (d2), a hydrophilic part is a total part of an oxyethylene group and an oxypropylene group.

The component (d3) is an alkyl polyglycoside (glycoside type nonionic surfactant).
The nonionic surfactant as the component (d3) is preferably a nonionic surfactant represented by the following general formula (d3).
R ^13d (OR ^14d ) _s G _t (d3)
[Wherein, R ^13d 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 ^14d represents a carbon number. 2 to 4 alkylene groups, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms. s shows an average added mole number, and is a number of 0 or more and 5 or less. t represents a number whose average value is 1 or more and 5 or less. ]

In the general formula (d3), R ^13d 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 detergency.
In general formula (d3), s is preferably 0 or more and 2 or less, more preferably 0, from the viewpoint of detergency. From the viewpoint of detergency, t is preferably 1.1 or more, and preferably 1.5 or less, more preferably 1.4 or less. Here, t is a value measured by proton NMR method.
In general formula (d3), 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.

[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.
From the viewpoint of detergency, 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, 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, a linear or branched alkyl group, alkylene group or aryl group Is preferred.

  The anionic surfactant includes (d8) a sulfosuccinic acid ester having a hydrocarbon group having 5 to 18 carbon atoms or a salt thereof (hereinafter referred to as (d8) component), and (d9) 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 (d8)] (hereinafter referred to as the component (d9)), (d10) carbonization having 8 to 21 carbon atoms Anionic surfactant having a hydrogen group and a carboxy group (hereinafter referred to as (d10) component), and (d11) an anionic interface having a hydrocarbon group having 8 to 21 carbon atoms and a phosphoric acid ester group One or more anionic surfactants selected from the group consisting of an activator [hereinafter referred to as component (d11)] are preferred, and two or more of them may be used.

From the viewpoint of detergency and foamability, the anionic surfactant preferably includes one or more selected from the group consisting of the component (d8) and the component (d9), and more preferably includes the component (d9). preferable.
In the anionic surfactant, the content of the component (d9) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more, from the viewpoints of detergency 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.
In addition, content (mass%) of each component in anionic surfactant is computed based on the quantity of sodium salt conversion.

  The component (d9) used in the present invention is an anionic surfactant [except for the component (d8)] having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester group or a sulfonic acid group. .

  The hydrocarbon group of component (d9) 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 14 or less, from the viewpoint of detergency. Preferably it is 12 or less. The hydrocarbon group as the component (d9) is preferably an alkyl group or an aryl group.

  The anionic surfactant (d9) is preferably at least one selected from alkyl sulfates, polyoxyalkylene alkyl ether sulfates and alkane sulfonates.

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, and still more preferably 12 from the viewpoint of detergency. The following alkyl sulfate esters having a linear or branched alkyl group are preferred.
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 21 or less, preferably 18 or less, more preferably from the viewpoint of detergency. Has a linear or branched alkyl group of 14 or less, more preferably 12 or less, and the average added mole number of the oxyalkylene group having 2 or more and 3 or less carbon atoms is preferably 0.1 or more, more preferably 0.8. Polyoxyalkylene alkyl ether sulfates having a polyoxyalkylene group of 3 or more, more preferably 0.4 or more, and preferably 6 or less, more preferably 5 or less, and still more preferably 4 or less are suitable.
In addition, as the anionic surfactant having a sulfonic acid group, from the viewpoint of detergency,
(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.

  (D9) As the salt of the anionic surfactant of the component, from an inorganic salt selected from sodium salt, ammonium salt, potassium salt, magnesium salt and the like, monoethanolammonium salt, diethanolammonium salt, triethanolammonium salt, morpholinium salt and the like The selected organic ammonium salt is preferred.

The component (d10) used in the present invention is an anionic surfactant having a hydrocarbon group having 8 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 a higher fatty acid or its salt, what is represented by the following general formula (d10-1) is preferable.
R ^25d -COOX ^1d (d10-1)
[Wherein, R ^25d represents an alkyl group or alkenyl group having 8 to 21 carbon atoms, and X ^1d 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.

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

In addition, when the hard surface liquid detergent composition of the present invention contains an amphoteric surfactant, the content of the amphoteric surfactant in the liquid detergent composition for hard surface of the present invention is a foaming viewpoint. 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.
In addition, when the hard surface liquid detergent composition of the present invention contains a nonionic surfactant, the content of the nonionic surfactant in the liquid detergent composition for hard surface of the present invention is foaming property. 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.
Further, when the hard surface liquid detergent composition of the present invention contains an anionic surfactant, the content of the anionic surfactant in the liquid detergent composition for hard surface of the present invention 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.

The liquid detergent composition for hard surfaces of the present invention contains water. That is, the remainder other than the components (a) to (c) 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.

  In the liquid detergent composition for hard surfaces of the present invention, 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 improver such as modified cellulose (however, component (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, in particular a hard surface. Articles having a hard surface include toilet bowls, bathtubs, kitchen sinks, window glass, mirrors, faucets and the like.

  In the dirt adhesion preventing method of the present invention, it is preferable to use the liquid detergent composition for hard surface of the present invention containing the components (a) to (c) in the above-mentioned content.

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) may 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 the antifouling performance, the static contact angle with respect to water of the glass surface treated with the liquid detergent composition for hard surface of the present invention is preferably 20 °. In the following, it is more preferably 15 ° or less, further preferably 10 ° or less, still more preferably 8 ° or less, and preferably 1 ° or more. By imparting hydrophilicity in this way, the antifouling performance of the hard surface can be enhanced from the hydrophobic substance. 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.

<1>
(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 (c) chelating agent (hereinafter referred to as component (c)).

[Where,
R ¹ to R ^3: same or different, a hydrogen atom or C 1 or 2 alkyl radicals R ^4: 1 to 4 alkylene group having a carbon number, 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, the number of hydrogen atom or a C 1 or 2 alkyl groups ^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 have a hydrogen atom or carbon number 1 to 4 hydrocarbon groups, X ⁵ represents an anion. ]

<2>
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. More preferably, the liquid detergent composition for hard surfaces according to <1>, which is 100,000 or less.

<3>
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 96/4 or less, The liquid detergent composition for hard surfaces as described in <1> or <2>.

<4>
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 for 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 a hard surface according to any one of <1> to <3> Liquid detergent composition.

<5>
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, and even more preferably 10 mol% or less. The liquid cleaning for hard surfaces according to any one of <1> to <4> Agent composition.

<6>
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 liquid detergent composition for hard surfaces according to any one of <1> to <5>, preferably 0.5 mol% or less, more preferably 0.1 mol% or less, or 0 mol%. .

<7>
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 <1> to <6>, which is 99.5 mol% or more, more preferably 99.9 mol% or more, or 100 mol%.

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

<9>
In any one of <1> to <8>, 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; It showed the following polyoxyethylene group, Y ^- represents an anion residue of a halogen atom, or a number of 1 to 5 sulfonic acid ester or sulfuric ester carbon. ]

[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. ]

<10>
(C) The hard surface according to any one of <1> to <9>, wherein the component is at least one compound selected from aminocarboxylic acids, hydroxycarboxylic acids, hydroxyxphosphonic acids, and salts thereof. Liquid detergent composition.

<11>
Component (c) 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. <1>-<10> The liquid detergent composition for hard surfaces in any one of.

<12>
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% or less, more preferably 1% or less, even more preferably 0.8% or less, even more preferably 0.5% or less, and still more preferably 0.4% or less, <1 The liquid detergent composition for hard surfaces according to any one of> to <11>.

<13>
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 <1> to <12>.

<14>
(C) 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 <1> to <14>, more preferably 4% by mass or less.

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

<16>
The mass ratio of (b) / (c) 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, And preferably 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 <1> to <15>. Liquid detergent composition for hard surfaces.

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

<18>
The component (d) 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 <17>, which is the above surfactant.

<19>
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. 18> The liquid detergent composition for hard surfaces as described in 18>.

<20>
Nonionic surfactant is (d1) monoalkyl glyceryl ether, (d2) polyoxyalkylene monoalkyl or alkenyl ether, (d3) alkyl polyglycoside (glycoside type nonionic surfactant), (d4) sorbitan nonionic <18> or <19> which is one or more nonionic surfactants selected from the group consisting of surfactants, (d5) aliphatic alkanolamides, (d6) fatty acid monoglycerides, and (d7) sucrose fatty acid esters The liquid detergent composition for hard surfaces described in 1.

<21>
The anionic surfactant is (d8) a sulfosuccinic acid ester or a salt thereof having a hydrocarbon group having 5 to 18 carbon atoms, (d9) a hydrocarbon group having 8 to 21 carbon atoms, a sulfate group or a sulfone. An anionic surfactant having an acid group (excluding the component (d8)), (d10) an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a carboxy group, and (d11 <18> to <20>, 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 phosphoric acid ester group. The liquid detergent composition for hard surfaces in any one of.

<22>
The content of the component (d) 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 <17> to <21>, which is 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

<23>
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, <1 > -22 The liquid detergent composition for hard surfaces in any one of <22>.

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

<25>
<1>-<24> The dirt adhesion prevention method of a hard surface which processes a hard surface with the liquid cleaning composition for hard surfaces in any one of.

<26>
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. <25> The method for preventing soiling of a hard surface according to <25>, which is a solid hard surface such as a synthetic fiber such as polyester, nylon, or rayon.

<27>
<25> or <26> The method for preventing contamination of a hard surface according to <25> or <26>, wherein the hard surface is one or more hard surfaces selected from glass, ceramics, porcelain, plastics, stainless steel, and silicon wafers.

<28>
An article having a hard surface, and further treating an article having a hard surface selected from a toilet bowl, a bathtub, a kitchen sink, a window glass, a mirror, and a faucet, according to any one of <25> to <27> Adhesion prevention method.

<29>
The static contact angle with respect to water of the glass surface treated with the liquid detergent composition for hard surface is preferably 20 ° or less, more preferably 15 ° or less, still more preferably 10 ° or less, still more preferably 8 ° or less, And the dirt adhesion prevention method of the hard surface in any one of <25>-<28> which is preferably 1 degree or more.

<30>
Use of the composition according to any one of <1> to <24> as a liquid detergent for hard surfaces.

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, 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)
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, and 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. 1,3-propane sultone 67.45g was dripped there over 1 hour, and reaction was performed. 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.
Further, the copolymer A2 had a weight average molecular weight of 81,000.

Production Example 3 [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 was reacted by dropping 42.73 g of 1,3-propane sultone 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 polymer A′1.

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

In addition, the weight average molecular weights of the copolymers A1 to A2 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 1-9 and Comparative Examples 1-4
Using the following blending components, the hard surface liquid detergent composition shown in Table 1 was prepared, and the following items were evaluated. The results are shown in Table 1. In addition, all the mass% of the mixing | blending component in Table 1 is a numerical value based on an effective part. 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) / (c) showed the value computed based on the mass% of the acid conversion of (c) component.
The pH was adjusted with a small amount of sodium hydroxide or hydrochloric acid.

<Blending ingredients>
(A) Component and copolymer A1-A2 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)
(C) Component / 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 to 16) polyglucose (average sugar condensation degree 1 to 2) (product name “AG124”, manufactured by Kao Corporation)
・ Amphoteric surfactant: Lauramidopropylcarbobetaine (Product name “Amphithol 20AB”, 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 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>
Staphylococcus aureus (strain NBRC12732) was scraped after culturing twice at 37 ° C./24 hours on a nutrient agar medium (prepared according to NucleentAgar reagent manufactured by Difco) as a half-nutrient liquid medium. Suspended and dispersed in Difco (Nuturient Broth reagent prepared at 1/2 concentration of Noh), and the bacterial concentration was adjusted to 2.5 to 13 × 10 ⁸ using 1/2 neutral liquid medium. Prepared to cfu / mL and mixed with an equal volume of 3% by weight bovine serum albumin aqueous solution to prepare 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 fungus solution, the liquid detergent composition for hard surface was immediately washed with water adjusted to a hardness of 4 ° dH. A solution diluted 100 times was attached. The surface of a stainless steel disk having a diameter of 20 mm is attached to a liquid obtained by diluting a liquid detergent composition for a hard surface 100 times with water whose hardness is adjusted to 4 ° dH with a micropipette (Gilson, trade name Pipetteman). the 3.14cm hard surface liquid detergent compositions for ^two were inoculated with liquid 10μL diluted 100-fold with water to adjust the hardness to 4 ° dH (equivalent to 0.32 g / 100 cm ^2), spreadable I 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 for blending stability A: Dissolve uniformly B: Slightly cloudy C: Clearly cloudy

<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 1.
Foam specific volume (mL / g) = (b) / (a)
It shows that it is excellent in foaming, so that foam specific volume is large. From the foam specific volume, foaming performance was evaluated 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 (6)

(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 (c) chelating agent (hereinafter referred to as component (c)).

[Where,
R ¹ to R ^3: same or different, a hydrogen atom or C 1 or 2 alkyl radicals R ^4: 1 to 4 alkylene group having a carbon number, 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, the number of hydrogen atom or a C 1 or 2 alkyl groups ^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 have a hydrogen atom or 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 content of component (a) is 0.01% by mass or more and 3% by mass or less.   The liquid detergent composition for hard surfaces according to claim 1 or 2, wherein a mass ratio of (a) / (b) is 0.01 or more and 5 or less.   The liquid cleaning composition for hard surfaces according to any one of claims 1 to 3, wherein a mass ratio of (b) / (c) is 0.01 or more and 10 or less.   The liquid cleaning composition for hard surfaces according to any one of claims 1 to 4, 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 5.