CN110506101B - Liquid detergent composition for hard surface - Google Patents

Abstract

The present invention provides a liquid detergent composition for hard surfaces, comprising: (a) a copolymer which comprises a specific structural unit (a1) having a betaine group and a specific structural unit (a2) having a cationic group, and in which the molar ratio of the structural unit (a1) to the structural unit (a2) in the structural unit (a 1)/the structural unit (a2) is 30/70 or more and 99.9/0.1 or less; (b) a cationic surfactant; and (c) at least one surfactant selected from the group consisting of amphoteric surfactants, nonionic surfactants, and anionic surfactants.

Description

Liquid detergent composition for hard surface

Technical Field

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

Background

In the equipment surrounding our living environment, there are various hard surfaces made of ceramic tiles, plastic, metal, etc., which are exposed to environments where various dirt adheres in a living scene. Among them, hard surfaces used in toilets, bathrooms, kitchens, and the like are also surfaces that people come into contact with on a daily basis, and therefore have properties that they are likely to remain, accumulate a large amount of dirt, and are difficult to clean and remove.

For example, Japanese patent application laid-open No. 2010-100861 discloses a composition for cleaning or rinsing hard surfaces, which contains at least 1 surfactant and at least 1 polybetaine (B) having a constant total anionic charge and a constant total cationic charge (each betaine unit having a constant cationic charge and the same number of constant anionic charges) in a pH range of 1 to 14 and exhibiting an absolute weight average molecular weight (Mw) of 5,000 to 3,000,000 g/mole, and which is used for cleaning or rinsing hard surfaces in an aqueous medium or an aqueous alcoholic medium.

U.S. patent application publication No. 2009/0197791 discloses a copolymer containing a unit a containing a betaine group and a cationic unit B.

Disclosure of Invention

It is difficult to say that the specifications of Japanese patent application laid-open No. 2010-100861 and U.S. patent application laid-open No. 2009/0197791 are sufficient in terms of satisfying foaming ability, sterilizing performance, and antifouling property. In particular, the inventors found that: when a polymer having a betaine group as described in Japanese patent application laid-open No. 2010-100861 is used in combination with a cationic surfactant, if another surfactant, for example, a nonionic surfactant, an amphoteric surfactant or an anionic surfactant, is further used in order to improve foaming ability, the antifouling performance against a hard surface is lowered.

Further, it is difficult to say that the specifications of Japanese patent application laid-open No. 2010-100861 and U.S. patent application laid-open No. 2009/0197791 are sufficient in terms of satisfying the scale removal cleaning force (hereinafter, simply referred to as cleaning force), the sterilization performance, and the antifouling property. In particular, the inventors found that: when a polymer having a betaine group as described in Japanese patent application laid-open No. 2010-100861 is used in combination with a cationic surfactant, if a chelating agent is further used to improve the cleaning power, the stain-proofing performance on the hard surface is lowered.

The present invention relates to a liquid detergent composition for hard surfaces, which can maintain antibacterial performance, has excellent foamability, and is excellent in stain-proofing performance, i.e., inhibition of adhesion of stains to hard surfaces and the like.

The present invention relates to a liquid detergent composition for hard surfaces, which can maintain antibacterial performance, has excellent detergency, and has excellent antifouling performance, i.e., inhibition of adhesion of dirt to hard surfaces.

The inventor finds that: by using a polymer having a specific betaine group and a specific cationic group, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or an anionic surfactant, excellent effects in all of antifouling performance, foamability (hereinafter also referred to as foamability), and bacteria-removing performance can be obtained.

The present invention provides a liquid detergent composition for hard surfaces, comprising: (a) a copolymer which comprises a structural unit (a1) represented by the following formula (1) and a structural unit (a2) represented by the following formula (2) and in which the molar ratio of the structural unit (a1) to the structural unit (a2), that is, the structural unit (a 1)/the structural unit (a2), is 30/70 or more and 99.9/0.1 or less; (b) a cationic surfactant; and (c) at least one surfactant selected from amphoteric surfactants, nonionic surfactants and anionic surfactants [ hereinafter referred to as component (c) ].

[ in the formula,

R¹～R³the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

R⁴is an alkylene group having 1 to 4 carbon atoms, or-Y¹-OPO₃ ^--Y²-，

Y¹、Y²The same or different alkylene groups having 1 to 4 carbon atoms,

R⁵、R⁶the same or different hydrocarbon groups having 1 to 4 carbon atoms,

X¹is O or NR⁷，R⁷A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

X²represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R¹⁷SO₃ ^-Or R¹⁷COO^-Wherein, in R⁴When the alkylene group has 1 to 4 carbon atoms, X²Is R¹⁷SO₃ ^-Or R¹⁷COO^-，R¹⁷An alkylene group having 1 to 4 carbon atoms; at R⁴is-Y¹-OPO₃ ^--Y²When is, X²Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

[ in the formula,

R⁸～R¹⁰the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

X³is a compound of the formula (I) O,

R¹¹an alkylene group having 1 to 4 carbon atoms,

X⁴is N⁺R¹²R¹³R¹⁴X⁵Or NR¹⁵R¹⁶，R¹²～R¹⁶The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X⁵Represents an anion.]

Further, the present inventors found that: by using a polymer having a specific betaine group and a specific cationic group, a cationic surfactant, and a chelating agent, excellent effects in all of antifouling performance, detergency, and antibacterial performance can be obtained.

The present invention relates to a liquid detergent composition for hard surfaces, comprising: (a) a copolymer [ hereinafter referred to as component (a) ] comprising a structural unit (a1) represented by formula (1) and a structural unit (a2) represented by formula (2) and having a molar ratio of the structural unit (a1) to the structural unit (a2), that is, the structural unit (a 1)/the structural unit (a2), of 30/70 or more and 99.9/0.1 or less; (b) a cationic surfactant [ hereinafter referred to as component (b) ]; and (d) a chelating agent [ hereinafter referred to as component (d) ].

[ in the formula,

R¹～R³the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

R⁴is an alkylene group having 1 to 4 carbon atoms, or-Y¹-OPO₃ ^--Y²-，

Y¹、Y²The same or different alkylene groups having 1 to 4 carbon atoms,

R⁵、R⁶the same or different hydrocarbon groups having 1 to 4 carbon atoms,

X¹is O or NR⁷，R⁷A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

X²represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R¹⁷SO₃ ^-Or R¹⁷COO^-Wherein, in R⁴When the alkylene group has 1 to 4 carbon atoms, X²Is R¹⁷SO₃ ^-Or R¹⁷COO^-，R¹⁷An alkylene group having 1 to 4 carbon atoms; at R⁴is-Y¹-OPO₃ ^--Y²When is, X²Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

[ in the formula,

R⁸～R¹⁰the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

X³is a compound of the formula (I) O,

R¹¹alkylene having 1 to 4 carbon atomsThe base group is a group of a compound,

X⁴is N⁺R¹²R¹³R¹⁴X⁵Or NR¹⁵R¹⁶，R¹²～R¹⁶The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X⁵Represents an anion]

Hereinafter, the case of the liquid detergent composition for hard surface of the present invention is referred to as "including the 2 types of liquid detergent compositions for hard surface" described above.

The present invention also relates to a method for preventing the adhesion of dirt to a hard surface, which comprises treating the hard surface with the liquid detergent composition for hard surface of the present invention.

The present invention provides a liquid detergent composition for hard surfaces, which can maintain antibacterial performance, has excellent foamability, and is excellent in stain-proofing performance, i.e., inhibition of adhesion of stains to hard surfaces.

Further, the present invention provides a liquid detergent composition for hard surfaces, which can maintain antibacterial performance, has excellent detergency, and has excellent antifouling performance, i.e., inhibition of adhesion of dirt to hard surfaces.

Detailed Description

[ liquid detergent composition for hard surface ]

In one aspect, the liquid detergent composition for hard surfaces of the present invention is a liquid detergent composition for hard surfaces, which contains a component (a), a component (b), and a component (c).

< component (a) >

(a) Component (c) is a copolymer comprising a structural unit (a1) represented by the above formula (1) and a structural unit (a2) represented by the above formula (2).

The structural unit (a1) represented by the above formula (1) may be a structural unit derived from an unsaturated monomer having a betaine group. The structural unit (a2) represented by the above 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, further preferably 1 ten thousand or more, and further preferably 3 ten thousand or more from the viewpoint of improving the antifouling property of the component (a), and is preferably 20 ten thousand or less, more preferably 15 ten thousand or less, and further preferably 10 ten thousand or less from the same viewpoint. The weight average molecular weight can be measured by the method described in examples.

[ molar ratio of the structural unit (a1) to the structural unit (a2) ]

From the viewpoint of antifouling performance, the molar ratio of the structural unit (a1) to the structural unit (a2) of the component (a) is 30/70 or more and 99.9/0.1 or less in terms of the structural unit (a 1)/the structural unit (a 2). From the same viewpoint, the molar ratio of the structural unit (a 1)/the structural unit (a2) is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, still more preferably 75/25 or more, still more preferably 90/10 or more, and from the viewpoint of improving the antifouling property of the component (a), it is preferably 98/2 or less, and more preferably 96/4 or less.

[ structural Unit (a1) ]

(content of structural Unit (a 1))

The content of the constitutional unit (a1) in the component (a) is preferably 30 mol% or more, more preferably 50 mol% or more, further preferably 70 mol% or more, further preferably 80 mol% or more, further preferably 90 mol% or more, and from the same viewpoint, preferably 99 mol% or less, more preferably 98 mol% or less, further preferably 95 mol% or less, from the viewpoint of improving the antifouling property of the component (a).

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, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and from the same viewpoint, is preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 95% by mass or less, from the viewpoint of improving the antifouling performance of the component (a).

(constitution of structural Unit (a 1))

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

[ in the formula,

R¹～R³the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

R⁴is an alkylene group having 1 to 4 carbon atoms, or-Y¹-OPO₃ ^--Y²-，

Y¹、Y²The same or different alkylene groups having 1 to 4 carbon atoms,

R⁵、R⁶the same or different hydrocarbon groups having 1 to 4 carbon atoms,

X¹is O or NR⁷，R⁷A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

X²represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R¹⁷SO₃ ^-Or R¹⁷COO^-Wherein, in R⁴When the alkylene group has 1 to 4 carbon atoms, X²Is R¹⁷SO₃ ^-Or R¹⁷COO^-，R¹⁷An alkylene group having 1 to 4 carbon atoms; at R⁴is-Y¹-OPO₃ ^--Y²When is, X²Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.]

In the formula (1), R is R from the viewpoint of availability of the unsaturated monomer, the viewpoint of polymerizability of the monomer, and the viewpoint of improvement of the stain-proofing property of the component (a)¹And R²Each is preferably a hydrogen atom.

In the formula (1), R is R from the viewpoint of availability of the unsaturated monomer, the viewpoint of polymerizability of the monomer, and the viewpoint of improvement of the stain-proofing property of the component (a)³Preferably a hydrogen atom or a methyl group, more preferably a methyl group.

In-situ type(1) In (a), X is X from the viewpoint of the availability of the unsaturated monomer, the polymerizability of the monomer, and the viewpoint of the improvement of the stain-proofing property of the component (a)¹Preferably O. From the same viewpoint, R⁴The alkylene group having 1 to 4 carbon atoms in (b) is 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 is R from the viewpoint of improving antifouling property⁴Preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.

In formula (1), Y¹、Y²Each of them is 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 is R from the viewpoint of availability of the unsaturated monomer, the viewpoint of polymerizability of the monomer, and the viewpoint of improvement of the stain-proofing property of the component (a)⁵、R⁶Methyl or ethyl, respectively, is preferred, and methyl is more preferred.

In the formula (1), X²Is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R¹⁷SO₃ ^-Or R¹⁷COO^-But in R⁴When the alkylene group has 1 to 4 carbon atoms, X²Is R¹⁷SO₃ ^-Or COO^-At R⁴is-Y¹-OPO₃ ^--Y²When is, X²Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. At R⁴is-Y¹-OPO₃ ^--Y²When, from the viewpoint of improving antifouling property, X²The hydrocarbon group having 1 to 4 carbon atoms is preferable, and the methyl group is more preferable. At R⁴When the alkylene group has 1 to 4 carbon atoms, X is a group represented by the formula²Preferably R¹⁷SO₃ ^-。

And R is¹⁷Preferably 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 (a 2))

The content of the structural unit (a2) in the component (a) is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 5 mol% or more from the viewpoint of improving antifouling performance, and is also preferably 70 mol% or less, more preferably 50 mol% or less, even more preferably 30 mol% or less, even more preferably 20 mol% or less, and even more preferably 10 mol% or less from the same viewpoint.

The content of the constitutional unit (a2) in the component (a) is preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 5 mass% or more from the viewpoint of improving the antifouling property, and is preferably 70 mass% or less, more preferably 50 mass% or less, even more preferably 30 mass% or less, even more preferably 20 mass% or less, and even more preferably 10 mass% or less from the viewpoint of improving the antifouling property of the component (a).

(constitution of structural Unit (a 2))

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

[ in the formula,

R⁸～R¹⁰the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

X³is O or NH, and is a compound of the formula,

R¹¹an alkylene group having 1 to 4 carbon atoms,

X⁴is N⁺R¹²R¹³R¹⁴X⁵Or NR¹⁵R¹⁶，R¹²～R¹⁶The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X⁵Represents an anion.]

In the formula (2), the unsaturated monomer is obtained from the viewpoint of the availability of the unsaturated monomer, the polymerizability of the monomer, and the antifouling property of the component (a) is improvedIn a word, R⁸And R⁹Each is preferably a hydrogen atom.

In the formula (2), R is R in view of polymerizability of the monomer and in view of improvement of antifouling property of the component (a)¹⁰Preferably a hydrogen atom or a methyl group, more preferably a methyl group.

In the formula (2), X is X in view of polymerizability of the monomer and in view of improvement of antifouling property of the component (a)³Preferably O.

In the formula (2), R is R in view of polymerizability of the monomer and in view of improvement of antifouling property of the component (a)¹¹The alkylene group having 2 or 3 carbon atoms is preferable, and the alkylene group having 2 carbon atoms is more preferable.

In the formula (2), X is X from the viewpoint of improving the antifouling property of the component (a) and the viewpoint of easiness of the quaternary amination reaction⁴Is N⁺R¹²R¹³R¹⁴X⁵Or NR¹⁵R¹⁶Is preferably N⁺R¹²R¹³R¹⁴X⁵From the same viewpoint, R¹²、R¹³、R¹⁴Methyl or ethyl is preferred, respectively.

In the formula (2), R is R from the viewpoint of improving the antifouling property of the component (a) and the viewpoint of easiness of the quaternary amination reaction¹⁵、R¹⁶Preferably methyl or ethyl, more preferably methyl.

In the formula (2), X⁵Is an anion, preferably a halide or C₂H₅SO₄ ^-More preferably C₂H₅SO₄ ^-。

[ structural units other than the structural unit (a1) and the structural unit (a2) ]

(a) Component (c) may contain a structural unit other than the structural unit (a1) and the structural unit (a2) within a range not impairing the effects of the present invention. The structural units other than the structural unit (a1) and the structural unit (a2) are preferably structural units derived from unsaturated monomers other than the sulfobetaine-containing unsaturated monomer, and more preferably structural units derived from hydrophobic unsaturated monomers such as styrene.

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, even more preferably 0.5 mol% or less, and even more preferably 0.1 mol% or less, from the viewpoint of stain-proofing properties. (a) 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, further preferably 1% by mass or less, further preferably 0.5% by mass or less, further more preferably 0.1% by mass or less, from the viewpoint of antifouling property. (a) 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, even more preferably 99 mol% or more, even more preferably 99.5 mol% or more, and even more preferably 99.9 mol% or more, from the viewpoint of antifouling property. (a) 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, even more preferably 99% by mole or more, even more preferably 99.5% by mass or more, and even more preferably 99.9% by mass or more, from the viewpoint of antifouling property. (a) The total content of the structural unit (a1) and the structural unit (a2) in the component (a) may be 100% by mass.

[ (A) Process for producing component ]

As a method for producing the component (a), any method can be used, and specific examples thereof include the following methods (i) and (ii). The method (ii) is preferable from the viewpoint of availability of raw materials and ease of production.

(i) Method for copolymerizing unsaturated monomers having betaine group and cationic group

(ii) A method comprising copolymerizing an unsaturated monomer having an amino group and a cationic group, and quaternizing the resultant copolymer with a betaine aminating agent

< component (b) >

(b) The component is cationic surfactant. The cationic surfactant is preferably a mono-or di-long alkyl quaternary ammonium salt. The component (b) is preferably a cationic surfactant selected from the group consisting of a compound represented by the following general formula (b1) and a compound represented by the following general formula (b 2).

[ wherein, R is selected from^1bAnd R^2bAt least one of the above groups 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 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, R^3bAnd R^4bThe 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^-Represents a halogen atom, or an anionic residue of a sulfonic acid ester or sulfuric acid ester having 1 to 5 carbon atoms.]

[ in the formula, R^5bRepresents 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, R^6b、R^7bThe 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, R^8bRepresents an alkylene group having 1 to 3 carbon atoms; z^-Represents a halogen atom, or an anionic residue of a sulfonic acid ester or sulfuric acid ester having 1 to 5 carbon atoms.]

In the case of a mono-long alkyl-type quaternary ammonium salt, in the general formula (b1), R is preferably^1bIs an alkyl, alkenyl or hydroxyalkyl group having 8 to 16 carbon atoms, R^2b、R^3bAnd R^4bThe alkyl group and the hydroxyalkyl group each have 1 to 3 carbon atoms or a polyoxyethylene group having an average molar number of addition of 10 or less.

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

In the general formula (b2), R^5bPreferably a linear alkyl group having 12 to 16 carbon atoms, R^6b、R^7bAre each preferably methyl, R^8bPreferably methylene, Z^-Is a halogen ion, and is more preferably a chloride ion (Cl)^-)。

(b) The component (b) is preferably a cationic surfactant selected from the compounds represented by the general formula (b 2).

< component (c) >

(c) The component (A) is at least one surfactant selected from amphoteric surfactant, nonionic surfactant and anionic surfactant. From the viewpoint of the blending stability, the component (c) is preferably at least one surfactant selected from amphoteric surfactants and nonionic surfactants.

[ amphoteric surfactant ]

The amphoteric surfactant is preferably an amphoteric surfactant containing 1 or more selected from the group consisting of amine oxide, sulfobetaine, and carboxybetaine, more preferably an amphoteric surfactant containing 1 or more selected from the group consisting of sulfobetaine and carboxybetaine, and even more preferably an amphoteric surfactant containing carboxybetaine, from the viewpoint of blending stability and foaming properties. These may be used in 2 or more.

In the amphoteric surfactant, the content of 1 or more amphoteric surfactants selected from the group consisting of amine oxide, sulfobetaine, and carboxybetaine is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 99% by mass or more, and preferably 100% by mass or less, from the viewpoint of blending stability and foaming properties.

In the amphoteric surfactant, the content of 1 or more amphoteric surfactants selected from sulfobetaines and carboxybetaines is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 99% by mass or more, and preferably 100% by mass or less, from the viewpoint of blending stability and foaming properties.

As sulfobetaines, mention may be made of: from the viewpoint of blending stability and foaming properties, the number of carbon atoms of the alkyl group is preferably 10 or more, and preferably 18 or less, and more preferably 14 or less, N-alkyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine; from the viewpoint of blending stability and foaming properties, the number of carbon atoms of the alkyl group is preferably 10 or more, and preferably 18 or less, and more preferably 14 or less, N-alkyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine; from the viewpoint of blending stability and foamability, the number of carbon atoms of the alkanoyl group is preferably 10 or more, and preferably 18 or less, and more preferably 14 or less, N-alkanoylaminopropyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine; from the viewpoint of blending stability and foaming properties, the number of carbon atoms of the alkanoyl group is preferably 10 or more, and preferably 18 or less, and more preferably 14 or less, N-alkanoylaminopropyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine.

As carboxybetaines, mention may be made of: from the viewpoint of blending stability and foaming properties, N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine in which the number of carbon atoms in the alkyl group is preferably 10 or more, and preferably 18 or less, and more preferably 14 or less; or a compound represented by the following general formula (I); from the viewpoint of blending stability and foaming properties, compounds represented by the following general formula (I) are preferable.

[ in the formula, R^1cRepresents an alkyl or alkenyl group having 7 to 21 carbon atoms, R^2cRepresents propylene, R^3cAnd R^4cEach independently represents an alkyl group having 1 to 3 carbon atoms.]

In the general formula (I), R is R from the viewpoint of compounding stability and foaming property^1cIs preferably 9 or more, more preferably 11 or more, and preferably 15 or less, more preferably 13 or less, and is preferably nonyl, decyl, undecyl, dodecyl, tridecyl.

In the general formula (I), R is R from the viewpoint of compounding stability and foaming property^3cAnd R^4cPreferably methyl.

Examples of the compound represented by the general formula (I) include: almond oil amidopropyl betaine, wild apricot amidopropyl betaine, pyrus oil amidopropyl betaine, babassu amidopropyl betaine, behenamidopropyl betaine, rapeseed amidopropyl betaine, decanoyl/capamidopropyl betaine, cocamidopropyl betaine, coco/oleamidopropyl betaine, isostearamidopropyl betaine, lauramidopropyl carboxybetaine, cow amidopropyl betaine, mink amidopropyl betaine, myristamidopropyl betaine, oleamidopropyl betaine, olive amidopropyl betaine, palmitamidopropyl betaine, ricinoleic amidopropyl betaine, sesame amidopropyl betaine, soybean amidopropyl betaine, stearamidopropyl betaine, tallowamidopropyl betaine, undecylenamidopropyl betaine, undecylenic amidopropyl betaine, and mixtures thereof, And wheat germ oleamide propyl betaine.

Of these, from the viewpoint of blending stability and foaming property, 1 or more selected from lauramidopropyl carboxybetaine, myristamamidopropyl betaine, oleamidopropyl betaine, and cocamidopropyl betaine are preferable. These are R in the formula (I)^3cAnd R^4cEach methyl group.

The amine oxide is preferably a compound represented by the following general formula (II).

[ in the formula, R^5cRepresents a hydrocarbon group having 8 to 22 carbon atoms, preferably represents an alkyl group or an alkenyl group, more preferably represents an alkyl group, and R^6cAnd R^7cEach independently represents an alkyl group having 1 to 3 carbon atoms; d represents an-NHC (═ O) -group or-C (═ O) NH-group, and E represents an alkylene group having 1 or more and 5 or less carbon atoms; m and p represent m ═ 0 and p ═ 0 or m ═ 1 and p ═ 1.]

In the above general formula (II), R is R from the viewpoint of compounding stability and foaming property^5cThe alkyl group is preferably an alkyl group having 10 to 18 carbon atoms, more preferably an alkyl group having 12 to 16 carbon atoms, still more preferably an alkyl group having 12 to 14 carbon atoms, and yet more preferably an alkyl group having 12 carbon atoms. From the viewpoint of stability of blending, R^6cAnd R^7cThe methyl group having 1 carbon atom is preferred.

Preferred specific examples of the amine oxide include:

(1) alkyl (C8-22) dialkyl (C1-3) amine oxides such as decanoyl dimethyl amine oxide, decyl dimethyl amine oxide, lauryl dimethyl amine oxide, and myristyl dimethyl amine oxide,

(2) An amidopropyldialkyl (carbon number 1 or more and 3 or less) amine oxide of a fatty acid (carbon number 8 or more and 22 or less) such as lauramidopropyldimethylamine oxide, myristamidopropyldimethylamine oxide, palmitamidopropyldimethylamine oxide, and the like, and from the viewpoint of the blending stability, (1) an alkyl (carbon number 8 or more and 22 or less) dialkyl (carbon number 1 or more and 3 or less) amine oxide is more preferable.

[ nonionic surfactant ]

From the viewpoint of the blending stability and foaming properties, the nonionic surfactant is preferably at least one selected from the group consisting of (c1) monoalkyl glyceryl ether [ hereinafter referred to as (c1) component ], (c2) polyoxyalkylene monoalkyl or alkenyl ether [ hereinafter referred to as (c2) component ], (c3) alkyl polyglycoside (glycoside-type nonionic surfactant) [ hereinafter referred to as (c3) component ], (c4) sorbitan-based nonionic surfactant [ hereinafter referred to as (c4) component ], (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 ], and 2 or more of these may be used.

From the viewpoint of the blending stability and the foamability, the nonionic surfactant preferably contains 1 or more selected from the group consisting of the component (c1), the component (c2) and the component (c3), and more preferably contains the component (c 3).

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, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 99% by mass or more, and preferably 100% by mass or less, from the viewpoint of blending stability and foamability.

In the nonionic surfactant, the content of the component (c3) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 99% by mass or more, and preferably 100% by mass or less, from the viewpoint of blending stability and foamability.

(c1) Composition (I)

(c1) The component is monoalkyl glyceryl ether.

Specifically, the component (c1) is preferably a compound represented by the following general formula (c 1).

R^11c-O-(Gly)_r-H(c1)

[ in the formula, R^11cRepresents an alkyl group having 6 to 18 carbon atoms, Gly represents a structural unit derived from glycerol, preferably a residue obtained by removing 1 hydroxyl group and 1 hydrogen atom from glycerol, and r represents a number of 1 to 4.]

In the general formula (c1), R is R from the viewpoint of foamability and compounding stability^11cIn the present invention, a straight-chain alkyl group such as a hexyl group, heptyl group, octyl group, nonyl group, decyl group or the like is used so that the alkyl group is preferably an alkyl group having 6 or more carbon atoms, more preferably 7 or more carbon atoms, even more preferably 8 or more carbon atoms, and preferably 18 or less carbon atoms, more preferably 12 or less carbon atoms, even more preferably 10 or less carbon atoms, and in view of blending stability, an alkyl group having a branch is preferable as R in the present invention^1cThe branched alkyl group of (2) is more preferably a group selected from the group consisting of 2-ethylhexyl group, sec-octyl group, isononyl group and isodecyl group, further preferably a 2-ethylhexyl group or isodecyl group, and still more preferably a 2-ethylhexyl group.

In the general formula (c1), r is preferably 1 or more, and preferably 2 or less. More preferably, r is 1. More preferred compounds are R^1cA compound which is 2-ethylhexyl and r is 1.

Gly has a structure of-CH in which the hydroxyl groups at positions 1 and 3 of glycerol are bonded₂CH(OH)CH₂-CH (CH) having a structure represented by the formula, or a structure in which hydroxyl groups at 1-position and 2-position of glycerol are bonded₂OH)CH₂The structure represented, depending on the catalyst or the reaction conditions.

To obtain the compound of formula (c1), for example, the following method can be used: using BF₃Isoacid catalyst, or aluminum catalyst, using R^11cAn alkyl alcohol represented by-OH is produced by reacting an alcohol having 6 to 10 carbon atoms with an epoxy compound such as an epihalohydrin or glycidyl alcohol. For example, in the case of using 2-ethylhexanol, the obtained 2-ethylhexyl monoglyceryl ether is a mixture containing a plurality of products as described in Japanese patent laid-open No. 2001-49291.

(c2) Composition (I)

(c2) The component is polyoxyalkylene monoalkyl or alkenyl ether.

In the nonionic surfactant of component (c2), the number of carbon atoms of the alkyl group or alkenyl group is preferably 6 or more, more preferably 8 or more, further preferably 10 or more, further more preferably 12 or more, and from the same viewpoint, preferably 22 or less, more preferably 18 or less, further preferably 16 or less, further more preferably 14 or less, from the viewpoint of blending stability and foamability.

In the nonionic surfactant of the component (c2), the average molar number of addition of the alkylene oxide is preferably more than 0, more preferably 1 or more, and even more preferably 3 or more from the viewpoint of blending stability and foamability, and is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less from the same viewpoint.

From the viewpoint of the blending stability and the foaming property, the alkylene oxide is preferably 1 or more selected from ethylene oxide, propylene oxide, and butylene oxide, and more preferably 1 or more selected from ethylene oxide and propylene oxide.

Preferred examples of the nonionic surfactant as the component (c2) include nonionic surfactants represented by the following general formula (c 2).

R^12cO[(C₂H₄O)_l/(C₃H₆O)_j]H(c2)

[ in the formula, R^12cA hydrocarbon group having 6 to 22 carbon atoms; l and j represent average addition mole numbers, l represents a number of 0 to 30 inclusive, j represents a number of 0 to 30 inclusive, and there is no case where l and j are both 0; "/" indicates that: the addition of the oxyethylene group and oxypropylene group may be random or block regardless of the order.]

From the viewpoint of blending stability and foaming property, R in the general formula (c2)^12cIs preferably 8 or more, more preferably 10 or more, and even more preferably 12 or more, and from the same viewpoint, is preferably 18 or less, and more preferably16 or less, and more preferably 14 or less.

From the viewpoint of compounding stability and foamability, R^12cPreferably an alkyl group or an alkenyl group, more preferably an alkyl group, and from the viewpoint of compounding stability and foaming properties, a secondary alkyl group. Here, the secondary alkyl group means R in the general formula (c2)^12cR bonded to O in O^12cThe carbon atom (b) is an alkyl group having a secondary carbon atom.

Specific examples of the alkyl group include: various octyl groups (including 2-ethylhexyl), various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups (lauryl groups), various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, and various octadecyl groups.

As the alkenyl group, there may be mentioned: various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, various hexadecenyl groups, various heptadecenyl groups, and various octadecenyl groups (e.g., oleyl groups, linoleyl groups). The term "various" means various normal, secondary, tertiary and iso isomers.

From the viewpoint of blending stability and foaming properties, the HLB value of the polyoxyalkylene monoalkyl or alkenyl ether as the component (c2) and the nonionic surfactant represented by the general formula (c2) is preferably 5 or more, more preferably 7 or more, and from the same viewpoint, is preferably 19 or less, more preferably 15 or less, and further preferably 13 or less.

Here, the HLB value is defined by Griffin's formula shown below.

HLB value 20 XMw/M

(wherein M is the molecular weight of the nonionic surfactant and Mw is the molecular weight of the hydrophilic moiety of the nonionic surfactant.)

In the general formula (c2), the hydrophilic moiety means the total of oxyethylene groups and oxypropylene groups.

(c3) Composition (I)

(c3) The component is alkyl polyglycoside (glucoside type nonionic surfactant).

(c3) The nonionic surfactant of component (a) is preferably a nonionic surfactant represented by the following general formula (c 3).

R^13c(OR^14c)_sG_t(c3)

[ in the formula, R^13cRepresents a linear or branched alkyl, alkenyl or alkylphenyl group having 8 to 18 carbon atoms, preferably 12 to 14 carbon atoms, preferably an alkyl group, R^14cAn alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms; s represents an average molar number of addition and is a number of 0 to 5; t represents a number of 1 to 5 in average.]

In the general formula (c3), R is R from the viewpoint of compounding stability and foamability^13cIs a linear or branched alkyl group having 8 or more, preferably 10 or more, carbon atoms and 18 or less, preferably 14 or less.

In the general formula (c3), s is preferably 0 or more and 2 or less, and more preferably 0, from the viewpoint of blending stability and foamability. From the viewpoint of blending stability and foamability, t is preferably 1.1 or more, and preferably 1.5 or less, and more preferably 1.4 or less. Further, t is a value measured by proton NMR.

In the general formula (c3), G is a residue derived from 1 or more monosaccharides selected from glucose and fructose in terms of their availability and cost. Examples of G include residues derived from 1 or more polysaccharides selected from maltose and sucrose. G is preferably a residue of a monosaccharide derived from glucose.

(c4) Components (a) to (c7)

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

[ anionic surfactant ]

The anionic surfactant is preferably an anionic surfactant having a sulfate group, a phosphate group, a phosphonic acid group, a sulfonic acid group, or a carboxyl group.

The anionic surfactant has a hydrocarbon group. The hydrocarbon group of the anionic surfactant has preferably 5 or more carbon atoms, more preferably 6 or more, even more preferably 7 or more, even more preferably 8 or more, even more preferably 10 or more, even more preferably 12 or more, and preferably 21 or less, more preferably 18 or less, even more preferably 16 or less, and even more preferably 14 or less, from the viewpoint of blending stability and foaming properties. The hydrocarbyl group is preferably a linear or branched alkyl, alkylene or aryl group.

The anionic surfactant is preferably 1 or more anionic surfactants selected from the group consisting of (c8) sulfosuccinates or salts thereof having a hydrocarbon group having 5 to 18 carbon atoms [ hereinafter referred to as (c8) component ], (c9) anionic surfactants having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate group or a sulfonic acid group [ wherein the (c8) component is excluded ] [ hereinafter referred to as (c9) component ], (c10) anionic surfactants having a hydrocarbon group having 7 to 21 carbon atoms and a carboxyl group [ hereinafter referred to as (c10) component ], and (c11) anionic surfactants having a hydrocarbon group having 8 to 21 carbon atoms and a phosphate group [ hereinafter referred to as (c11) component ], and 2 or more of these may be used.

From the viewpoint of blending stability and foaming properties, the anionic surfactant preferably contains 1 or more selected from the group consisting of the component (c8) and the component (c9), and more preferably contains the component (c 9).

In the anionic surfactant, the content of the component (c9) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 99% by mass or more, and preferably 100% by mass or less, from the viewpoint of blending stability and foamability.

The content (mass%) of each component in the anionic surfactant was calculated based on the amount in terms of sodium salt.

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

The hydrocarbon group of the component (c9) has 8 or more, preferably 10 or more, more preferably 12 or more carbon atoms, and 21 or less, preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less carbon atoms from the viewpoint of blending stability and foaming properties. (c9) The hydrocarbyl group of component (a) is preferably an alkyl or aryl group.

The anionic surfactant as component (c9) is preferably at least 1 selected from alkyl sulfate, polyoxyalkylene alkyl ether sulfate and alkane sulfonate.

The anionic surfactant having a sulfate group is preferably an alkyl sulfate salt having a linear or branched alkyl group having 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 carbon atoms, from the viewpoint of blending stability and foaming properties.

The anionic surfactant having a sulfate group and a polyoxyalkylene group has a linear or branched alkyl group having 8 or more, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less carbon atoms, and preferably has a polyoxyalkylene alkyl ether sulfate salt having a polyoxyalkylene group having 2 to 3 carbon atoms, wherein the average molar number of addition of the oxyalkylene group is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less carbon atoms, from the viewpoint of blending stability and foaming properties.

The anionic surfactant having a sulfonic acid group is preferably selected from the group consisting of anionic surfactants, and nonionic surfactants from the viewpoint of blending stability and foaming properties

(1) An alkylbenzenesulfonate having an alkyl group having 6 to 15 carbon atoms, and

(2) alkanesulfonic acid salts having 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 carbon atoms

1 or more kinds of anionic surfactants.

The salt of the anionic surfactant as component (c9) is preferably an inorganic salt selected from sodium salt, ammonium salt, potassium salt, magnesium salt and the like, or an organic ammonium salt selected from monoethanolammonium salt, diethanolammonium salt, triethanolammonium salt, morpholinium salt and the like.

The component (c9) is preferably a compound represented by the following general formula (c9) from the viewpoints of blending stability and foaming properties.

R^23c-O-(R^24cO)_n-SO₃M²(c9)

[ in the formula, R^23cIs a linear or branched alkyl group having 8 to 21 carbon atoms, R^24cIs an ethylene group and/or a propylene group, and n is an average molar number of addition and is a number of 0 to 6; m²Is a hydrogen atom or a cation, preferably an inorganic or organic cation.]

In the general formula (c9), R is R from the viewpoint of detergency^23cThe alkyl group is a linear or branched alkyl group having 8 or more, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably 14 or less, and further preferably 12 or less carbon atoms, and is preferably a linear alkyl group. In particular, R^23cPreferably an alkyl group selected from the group consisting of octyl, decyl, dodecyl, tridecyl, and tetradecyl, and more preferably dodecyl.

In the general formula (c9), n is a number of preferably 0 or more, and preferably 6 or less, more preferably 4 or less, even more preferably 3 or less, and even more preferably 1.5 or less, from the viewpoint of foaming properties. Further, n may be 0.

In the general formula (c9), in R^24cIn the case of ethylene, n is a number of preferably 0.1 or more, more preferably 0.5 or more, and preferably 6 or less, more preferably 3 or less, from the viewpoint of foaming properties.

In the general formula (c9), R is^24cIn the case of propylene, n is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.4 or more, and also preferably 1.5 or less, more preferably 1.0 or less from the viewpoint of foamabilityMore preferably 0.8 or less.

In the general formula (c9), R is^24cIn the case of ethylene and propylene, n may be selected from the above ranges for these groups, respectively.

In the general formula (c9), for M²Examples thereof include: hydrogen atom, or inorganic cations such as sodium ion, ammonium ion, potassium ion, and magnesium ion, organic cations such as monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, and morpholinium ion, and inorganic cations selected from sodium ion, potassium ion, ammonium ion, and magnesium ion are preferred.

In the general formula (c9), R is obtained^23cIn the case of a compound containing a branched alkyl group, with respect to R as a raw material^23cAlcohols represented by-OH, there may be mentioned: an alcohol obtained by hydroformylating a 1-olefin having 8 to 14 carbon atoms (including an alkyl group having a methyl group branched at the β -position with respect to the OH group, in an amount of 15 to 70 mol%), a gibbet type alcohol obtained by condensing an aldehyde having 4 to 8 carbon atoms (including an alkyl group having 3 to 6 carbon atoms and branched at the β -position with respect to the OH group, in an amount of 100 mol%), 3,5, 5-trimethylhexanol obtained by hydroformylating a dimer of isobutylene, a polybranched tridecanol (having a branching ratio of 100 mol%) obtained by hydroformylating a trimer of isobutylene, and a synthetic alcohol (having an alkyl group having a branching ratio of about 20 to 100 mol%) using petroleum and coal as a raw material.

The component (c10) used in the present invention is an anionic surfactant having a hydrocarbon group having 7 to 21 carbon atoms and a carboxyl group.

Specific examples thereof include: higher fatty acids or salts thereof, polyoxyethylene alkyl ether carboxylic acids or salts thereof, and N-acylamino acids or salts thereof.

The higher fatty acid or a salt thereof is preferably a compound represented by the following general formula (c 10-1).

R^25c-COOX^1c(c10-1)

[ in the formula, R^25cRepresents an alkyl or alkenyl group having 7 to 21 carbon atoms, X^1cTo representHydrogen atom, alkali metal, alkaline earth metal, ammonium, alkanol ammonium or basic amino acid.]

More specifically, the higher fatty acid or a salt thereof includes: lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, arachidic acid, behenic acid, and salts thereof. Among these, lauric acid, myristic acid, palmitic acid, and salts thereof are preferable.

The polyoxyethylene alkyl ether carboxylic acid or a salt thereof is preferably a compound represented by the following general formula (c 10-2).

R^26c-O-(CH₂CH₂O)_gCOOX^2c(c10-2)

[ in the formula, R^26cRepresents an alkyl group or alkenyl group having 7 or more carbon atoms, preferably 8 or more and 21 or less carbon atoms, g is an average molar number of addition of ethylene oxide and represents a number of 0.5 or more and 10 or less, X^2cRepresents 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 surfaces of the present invention is a liquid detergent composition for hard surfaces, which contains the component (a), the component (b), and the component (d). Specific examples and preferred embodiments of the component (a) and the component (b) in the liquid detergent composition for hard surfaces are as described above.

< ingredient (d) >

(d) The component is chelating agent. The chelating agent is preferably at least 1 compound selected from the group consisting of aminocarboxylic acids, hydroxycarboxylic acids, hydroxyphosphonic acids, and salts thereof.

Examples of aminocarboxylic acids and salts thereof include: selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid, diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), methylglycinediacetic acid (MGDA), aspartic acid diacetic acid (ASDA), glutamic acid diacetic acid (GLDA), and 1 or 2 or more of these salts. The aminocarboxylic acid and the salt thereof are preferably 1 or 2 or more selected from ethylenediaminetetraacetic acid and the salt thereof, methylglycinediacetic acid and the salt thereof, and L-glutamic diacetic acid and the salt thereof.

The hydroxycarboxylic acid and its salt are preferably compounds selected from aliphatic hydroxycarboxylic acids and their salts. Examples of hydroxycarboxylic acids and salts thereof include: a compound selected from malic acid, citric acid and salts thereof.

Examples of hydroxyphosphonic acids and their salts are: a compound selected from 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP) and salts thereof.

As the salt of the chelating agent, there can be exemplified: alkali metal salts, ammonium salts, amine salts, and the like. Preferably an alkali metal salt, more preferably a sodium or potassium salt.

The chelating agent is preferably 1 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 surfaces of the present invention, the content of the component (a) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of the effect of hydrophilizing hard surfaces to prevent adhesion of dirt, and is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less, and even more preferably 0.4% by mass or less, from the viewpoint of blending stability.

In the liquid detergent composition for hard surfaces 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, further preferably 0.1% by mass or more, further preferably 0.2% by mass or more, from the viewpoint of sterilizing power, and is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, further more preferably 2% by mass or less, further more preferably 1.5% by mass or less, from the viewpoint of blending stability.

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

In the liquid detergent composition for hard surfaces of the present invention containing component (c), the content of component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more from the viewpoint of foaming properties, and is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less from the viewpoint of economy (low cost).

When the component (c) contains an amphoteric surfactant, the content of the amphoteric surfactant in the liquid detergent composition for hard surfaces of the present invention containing the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more from the viewpoint of foaming properties, and is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less from the viewpoint of economical efficiency (low cost).

When the component (c) contains a nonionic surfactant, the content of the nonionic surfactant in the liquid detergent composition for hard surfaces of the present invention containing the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more from the viewpoint of foaming properties, and is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less from the viewpoint of economical efficiency (low cost).

When the component (c) contains an anionic surfactant, the content of the anionic surfactant in the liquid detergent composition for hard surfaces of the present invention containing the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more from the viewpoint of foaming properties, and is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 1% by mass or less from the viewpoints of economy (low cost) and stability of mixing.

In the liquid detergent composition for hard surfaces of the present invention containing the component (c), the mass ratio of (b)/(c) is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.15 or more from the viewpoint of antibacterial performance, and is preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, and even more preferably 10 or less from the viewpoint of foaming ability.

In the liquid detergent composition for hard surfaces of the present invention containing component (d), the content of component (d) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, from the viewpoint of detergency, and is preferably 10% by mass or less, more preferably 9% by mass or less, even more preferably 8% by mass or less, even more preferably 6% by mass or less, even more preferably 5% by mass or less, even more preferably 4% by mass or less, from the viewpoint of economical efficiency and stability of blending. The mass of the component (d) is an acid equivalent (the same applies to other quantitative ratios relating to the mass of the component (d)).

In the liquid detergent composition for hard surfaces of the present invention containing the component (d), the mass ratio of (b)/(d) is preferably 0.01 or more, more preferably 0.03 or more, further preferably 0.05 or more, further preferably 0.1 or more, further preferably 0.15 or more, from the viewpoint of antibacterial performance, and is preferably 10 or less, more preferably 5 or less, further preferably 3 or less, further preferably 1 or less, further preferably 0.8 or less, from the viewpoint of blending stability and cleaning power.

The liquid detergent composition for hard surfaces of the present invention containing component (d) may contain a surfactant other than component (b). Examples of the surfactant include: (c) component (c), namely, at least one surfactant selected from amphoteric surfactants, nonionic surfactants and anionic surfactants. From the viewpoint of the blending stability, the component (c) is preferably at least one surfactant selected from amphoteric surfactants and nonionic surfactants. In this case, specific examples and preferred embodiments of the component (c) are as described above. In the liquid detergent composition for hard surfaces of the present invention containing component (d), the reason why component (c) is preferable can be considered to add a cleaning power.

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 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more from the viewpoint of foaming ability, and is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less from the viewpoint of low cost.

When the liquid detergent composition for hard surfaces of the present invention containing the component (d) contains an amphoteric surfactant, the content of the amphoteric surfactant in the composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more from the viewpoint of foaming properties, and is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less from the viewpoint of economy (low cost).

In the case where the liquid detergent composition for hard surfaces of the present invention containing the component (d) contains a nonionic surfactant, the content of the nonionic surfactant in the composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more from the viewpoint of foaming properties, and is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less from the viewpoint of economy (low cost).

In the case where the liquid detergent composition for hard surfaces of the present invention containing the component (d) contains an anionic surfactant, the content of the anionic surfactant in the composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more from the viewpoint of foaming properties, and is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 1% by mass or less from the viewpoints of economy (low cost) and stability of incorporation.

The liquid detergent composition for hard surfaces of the present invention contains water. That is, the component (a), the component (b), the component (c) and/or the component (d), and the remainder other than the optional components are water.

In the liquid detergent composition for hard surfaces of the present invention, the content of water is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and preferably 95% by mass or less, more preferably 93% by mass or less.

The water is preferably ion-exchanged water, sterilized ion-exchanged water, or the like.

The liquid detergent composition for hard surfaces of the present invention has a pH at 20 ℃ of preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more, and preferably 10 or less, more preferably 9 or less, and even more preferably 8 or less.

To the liquid detergent composition for hard surfaces of the present invention, the following may be added within a range not hindering the object of the present invention: polycarboxylic acids such as polyacrylic acid, polymethacrylic acid, polymaleic acid, poly-2-acrylamido-2-methylpropanesulfonic acid, and poly-p-styrenesulfonic acid; lower alcohols such as ethanol and isopropyl alcohol, and solvents such as diethylene glycol monobutyl ether; solubilizing agents such as tosylate, xylenesulfonate, and urea; viscosity modifiers such as clay minerals and water-soluble high molecular compounds (except for the component (a)); water-insoluble abrasives such as calcite, silica, calcium phosphate, zeolite, calcium carbonate, polyethylene, nylon, and polystyrene; humectants such as glycerin and sorbitol; a touch feeling improver such as cationized cellulose (except for the component (a)); alkaline auxiliaries such as sodium carbonate and sodium silicate; enzymes, pigments, perfumes, antiseptics and mildewcides, and the like.

[ method for preventing adhesion of dirt to hard surface ]

The present invention relates to a method for preventing the adhesion of dirt to a hard surface by treating the hard surface with the liquid detergent composition for hard surface of the present invention.

The hard surface is not particularly limited, and there may be mentioned: glass, pottery, porcelain, enamel, ceramic tile, ceramic; metals such as aluminum, stainless steel, and brass; synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP and the like; natural fibers such as cotton, silk, wool, and the like; and synthetic fibers such as polyester, nylon, and rayon. The fibers are preferably fibers having a shape or strength suitable for treatment with the liquid detergent composition for hard surfaces 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, "hydrophilicity" with respect to a hard surface means a static contact angle with water of less than 70 °. The static contact angle can be measured by the method described in examples.

As the hard surface preferable in the present invention, there are listed: 1 or more than 2 hard surfaces selected from glass, pottery, magnet, plastic, stainless steel and silicon wafer.

The present invention is directed to a hard surface, specifically an article having a hard surface. Examples of the article having a hard surface include: toilets, bathtubs, kitchen sinks, window glass, mirrors, faucets, etc.

In the method for preventing adhesion of stains according to the present invention, it is preferable to use the liquid detergent composition for hard surfaces of the present invention containing the component (a), the component (b), and the component (c) and/or the component (d) in the above-mentioned contents.

The treatment of a hard surface with the liquid detergent composition for hard surface of the present invention can be performed by bringing the liquid detergent composition for hard surface of the present invention into contact with a hard surface. The method of contacting the liquid detergent composition for hard surfaces of the present invention with hard surfaces is not particularly limited. Examples thereof include the following methods (i) to (ii).

(i) Method for immersing article having hard surface in liquid detergent composition for hard surface of the present invention

(ii) Method for spraying or coating a liquid detergent composition for hard surfaces of the present invention on 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, more preferably 50 minutes or less, from the viewpoint of improving antifouling performance and from the viewpoint of economy.

In the method (ii), the method of spraying or applying the liquid detergent composition for hard surfaces of the present invention to a hard surface may be appropriately selected depending on the width (area) of the hard surface and the like. The following method is preferred: the liquid detergent composition for hard surfaces of the present invention is sprayed on a hard surface with a sprayer or the like, and then dried. If desired, rinsing with water can also be carried out after spraying. Further, the coating may be thinly spread using a sponge or the like after spraying. Alternatively, the liquid detergent composition for hard surfaces of the present invention may be discharged from a discharge container such as a squeeze bottle to the hard surface and directly applied.

The amount of the liquid detergent composition for hard surface of the present invention sprayed or coated on a hard surface is, for example, per 10cm²Preferably 0.01mL or more and 1mL or less, and more preferably 0.01mL or more and 0.1mL or less.

The temperature of the liquid detergent composition for hard surfaces of the present invention for treating hard surfaces is preferably 5 ℃ or more, more preferably 10 ℃ or more, further preferably 15 ℃ or more, and preferably 50 ℃ or less, more preferably 40 ℃ or less, further preferably 30 ℃ or less, from the viewpoint of improving antifouling performance and from the viewpoint of easiness of the treatment method.

In addition, from the viewpoint of imparting hydrophilicity to a hard surface to improve antifouling properties, the static contact angle of a hard surface, preferably a hydrophilic hard surface, more preferably a glass surface, treated with the liquid detergent composition for hard surfaces of the present invention with respect to water is preferably 20 ° or less, more preferably 15 ° or less, further preferably 10 ° or less, further more preferably 8 ° or less, and preferably 1 ° or more. By imparting hydrophilicity to the hard surface in this way, the stain-proofing performance of the hard surface against hydrophobic substances can be improved. The static contact angle of the glass surface to water can be determined by the method described in examples.

In addition, from the viewpoint of improving antifouling performance and the like, the hard surface treated with the liquid detergent composition for hard surface of the present invention is preferably uniformly treated. The uniformity of the surface treatment can be judged by visually observing the treated hard surface.

Further, when the hard surface is a toilet bowl, the following method may be used: the liquid detergent composition for hard surfaces of the present invention is eluted into the cleaning water in the tank to continuously clean the dirt of the toilet bowl. In this case, a certain amount may be dropped into the toilet tank automatically or manually.

Mode for the invention

The following exemplifies the embodiments of the present invention. In these embodiments, the matters described in the liquid detergent composition for hard surfaces and the method for preventing adhesion of dirt of the present invention can be suitably applied.

＜1a＞

A liquid detergent composition for hard surfaces, comprising: (a) a copolymer [ hereinafter referred to as component (a) ] comprising a structural unit (a1) represented by formula (1) and a structural unit (a2) represented by formula (2) and having a molar ratio of the structural unit (a1) to the structural unit (a2), that is, the structural unit (a 1)/the structural unit (a2), of 30/70 or more and 99.9/0.1 or less; (b) a cationic surfactant [ hereinafter referred to as component (b) ]; and (c) at least one surfactant selected from amphoteric surfactants, nonionic surfactants and anionic surfactants [ hereinafter referred to as component (c) ],

[ in the formula,

R¹～R³the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

R⁴is an alkylene group having 1 to 4 carbon atoms, or-Y¹-OPO₃ ^--Y²-，

Y¹、Y²The same or different alkylene groups having 1 to 4 carbon atoms,

R⁵、R⁶the same or different hydrocarbon groups having 1 to 4 carbon atoms,

X¹is O or NR⁷，R⁷A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

X²represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R¹⁷SO₃ ^-Or R¹⁷COO^-Wherein, in R⁴When the alkylene group has 1 to 4 carbon atoms, X²Is R¹⁷SO₃ ^-Or R¹⁷COO^-，R¹⁷An alkylene group having 1 to 4 carbon atoms; at R⁴is-Y¹-OPO₃ ^--Y²When is, X²A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,]

[ in the formula,

R⁸～R¹⁰the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

X³is a compound of the formula (I) O,

R¹¹an alkylene group having 1 to 4 carbon atoms,

X⁴is N⁺R¹²R¹³R¹⁴X⁵Or NR¹⁵R¹⁶，R¹²～R¹⁶The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X⁵Represents an anion.]

＜2a＞

The liquid detergent composition for hard surfaces according to < 1a >, wherein the weight average molecular weight of the component (a) is preferably 500 or more, more preferably 5000 or more, further preferably 1 ten thousand or more, further preferably 3 ten thousand or more, and preferably 20 ten thousand or less, more preferably 15 ten thousand or less, further preferably 10 ten thousand or less.

＜3a＞

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

＜4a＞

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

＜5a＞

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

＜6a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 5a >, wherein the content of the structural unit (a1) and the structural unit other than 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, even more preferably 0.5 mol% or less, even more preferably 0.1 mol% or less, or 0 mol%.

＜7a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 6a >, wherein 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, even more preferably 99 mol% or more, even more preferably 99.5 mol% or more, even more preferably 99.9 mol% or more, or 100 mol%.

＜8a＞

The liquid detergent composition for hard surfaces 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＞

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

[ wherein, R is selected from^1bAnd R^2bAt least one of the above groups represents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 18 carbon atoms, and the others represent an alkyl group, a hydroxyalkyl group or a polyoxyethylene group having 10 or less average molar numbers of addition, wherein R represents^3bAnd R^4bThe same or different, each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a poly having an average molar number of addition of 10 or lessOxyethylene radical, Y^-Represents a halogen atom, or an anionic residue of a sulfonic acid ester or sulfuric acid ester having 1 to 5 carbon atoms,]

[ in the formula, R^5bRepresents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 18 carbon atoms, R^6b、R^7bThe same or different, each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a polyoxyethylene group having an average molar number of addition of 10 or less, R^8bRepresents an alkylene group having 1 to 3 carbon atoms; z^-Represents a halogen atom, or an anionic residue of a sulfonic acid ester or sulfuric acid ester having 1 to 5 carbon atoms.]

＜10a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 9a >, wherein the component (c) is at least one surfactant selected from amphoteric surfactants and nonionic surfactants.

＜11a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 10a >, wherein the amphoteric surfactant is at least 1 surfactant selected from the group consisting of amine oxides, sulfobetaines and carboxybetaines, preferably at least 1 surfactant selected from the group consisting of sulfobetaines and carboxybetaines, and more preferably carboxybetaines.

＜12a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 11a >, wherein the content of 1 or more amphoteric surfactants selected from the group consisting of amine oxide, sulfobetaine, and carboxybetaine among the amphoteric surfactants is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 99% by mass or more, and preferably 100% by mass or less.

＜13a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 12a >, wherein the content of 1 or more amphoteric surfactants selected from sulfobetaines and carboxybetaines among the amphoteric surfactants is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 99% by mass or more, and preferably 100% by mass or less.

＜14a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 13a >, wherein the nonionic surfactant is at least one nonionic surfactant selected from the group consisting of (c1) monoalkyl glyceryl ether [ hereinafter referred to as (c1) component ], (c2) polyoxyalkylene monoalkyl or alkenyl ether [ hereinafter referred to as (c2) component ], (c3) alkylpolyglycoside (glycoside type nonionic surfactant) [ hereinafter referred to as (c3) component ], (c4) sorbitan type nonionic surfactant [ hereinafter referred to as (c4) component ], (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 ].

＜15a＞

The liquid detergent composition for hard surfaces according to < 14a >, wherein the nonionic surfactant is at least 1 nonionic surfactant selected from the group consisting of component (c1), component (c2) and component (c3), preferably component (c 3).

＜16a＞

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

＜17a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 16a >, wherein the anionic surfactant is an anionic surfactant having a sulfate group, a phosphate group, a phosphonate group, a sulfonate group or a carboxyl group.

＜18a＞

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

＜19a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 18a >, wherein the anionic surfactant is at least 1 anionic surfactant selected from the group consisting of (c8) sulfosuccinates having a hydrocarbon group of 5 to 18 carbon atoms or less or salts thereof [ hereinafter referred to as (c8) component ], (c9) anionic surfactants having a hydrocarbon group of 8 to 21 carbon atoms and sulfate or sulfonic acid groups [ wherein (c8) component is excluded ] [ hereinafter referred to as (c9) component ], (c10) anionic surfactants having a hydrocarbon group of 7 to 21 carbon atoms and a carboxyl group [ hereinafter referred to as (c10) component ], and (c11) anionic surfactants having a hydrocarbon group of 8 to 21 carbon atoms and a phosphate group [ hereinafter referred to as (c11) component ].

＜20a＞

The liquid detergent composition for hard surfaces according to < 19a >, wherein the anionic surfactant is at least 1 selected from the group consisting of component (c8) and component (c9), preferably at least 1 selected from the group consisting of component (c 9).

＜21a＞

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

＜22a＞

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

＜23a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 22a >, wherein the content of the component (b) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, further preferably 2% by mass or less, further preferably 1.5% by mass or less.

＜24a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 23a >, wherein 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 8% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less.

＜25a＞

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

＜26a＞

The liquid detergent composition for hard surfaces according to any one of < 1a > to < 25a >, wherein 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, further preferably 20 or less, further preferably 10 or less.

＜27a＞

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

＜28a＞

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

＜29a＞

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

＜30a＞

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

＜31a＞

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

＜32a＞

The method for preventing adhesion of dirt to a hard surface according to < 30a > or < 31a >, wherein the hard surface is: glass, pottery, porcelain, enamel, ceramic tile, ceramic; metals such as aluminum, stainless steel, and brass; synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP and the like; natural fibers such as cotton, silk, wool, and the like; and synthetic fibers such as polyester, nylon, and rayon.

＜33a＞

The method for preventing the adhesion of dirt to a hard surface according to any one of < 30a > to < 32a >, wherein the hard surface is 1 or 2 or more hard surfaces selected from the group consisting of glass, ceramics, magnets, plastics, stainless steel and silicon wafers.

＜34a＞

The method for preventing adhesion of dirt to a hard surface according to any one of < 30a > to < 33a >, wherein an article having a hard surface, 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 is treated.

＜35a＞

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

＜36a＞

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

＜1b＞

A liquid detergent composition for hard surfaces, comprising: (a) a copolymer [ hereinafter referred to as component (a) ] comprising a structural unit (a1) represented by formula (1) and a structural unit (a2) represented by formula (2) and having a molar ratio of the structural unit (a1) to the structural unit (a2), that is, the structural unit (a 1)/the structural unit (a2), of 30/70 or more and 99.9/0.1 or less; (b) a cationic surfactant [ hereinafter referred to as component (b) ]; and (d) a chelating agent [ hereinafter referred to as component (d) ],

[ in the formula,

R¹～R³the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

R⁴is an alkylene group having 1 to 4 carbon atoms, or-Y¹-OPO₃ ^--Y²-，

Y¹、Y²The same or different alkylene groups having 1 to 4 carbon atoms,

R⁵、R⁶the same or different hydrocarbon groups having 1 to 4 carbon atoms,

X¹is O or NR⁷，R⁷A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

X²represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R¹⁷SO₃ ^-Or R¹⁷COO^-Wherein, in R⁴When the alkylene group has 1 to 4 carbon atoms, X²Is R¹⁷SO₃ ^-Or R¹⁷COO^-，R¹⁷An alkylene group having 1 to 4 carbon atoms; at R⁴is-Y¹-OPO₃ ^--Y²When is, X²A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,]

[ in the formula,

R⁸～R¹⁰the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

X³is a compound of the formula (I) O,

R¹¹an alkylene group having 1 to 4 carbon atoms,

X⁴is N⁺R¹²R¹³R¹⁴X⁵Or NR¹⁵R¹⁶，R¹²～R¹⁶The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X⁵Represents an anion.]

＜2b＞

The liquid detergent composition for hard surfaces according to < 1b >, wherein the weight average molecular weight of the component (a) is preferably 500 or more, more preferably 5000 or more, further preferably 1 ten thousand or more, further preferably 3 ten thousand or more, and preferably 20 ten thousand or less, more preferably 15 ten thousand or less, further preferably 10 ten thousand or less.

＜3b＞

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

＜4b＞

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

＜5b＞

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

＜6b＞

The liquid detergent composition for hard surfaces according to any one of < 1b > to < 5b >, wherein the content of the structural unit (a1) and the structural unit other than 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, even more preferably 0.5 mol% or less, even more preferably 0.1 mol% or less, or 0 mol%.

＜7b＞

The liquid detergent composition for hard surfaces according to any one of < 1b > to < 6b >, wherein 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, even more preferably 99 mol% or more, even more preferably 99.5 mol% or more, even more preferably 99.9 mol% or more, or 100 mol%.

＜8b＞

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

＜9b＞

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

[ wherein, R is selected from^1bAnd R^2bAt least one of the above groups represents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 18 carbon atoms, and the others represent an alkyl group, a hydroxyalkyl group or a polyoxyethylene group having 10 or less average molar numbers of addition, wherein R represents^3bAnd R^4bThe same or different, each represents 1 to 3 carbon atomsAlkyl groups, hydroxyalkyl groups or polyoxyethylene groups having an average addition mole number of 10 or less, Y^-Represents a halogen atom, or an anionic residue of a sulfonic acid ester or sulfuric acid ester having 1 to 5 carbon atoms,]

[ in the formula, R^5bRepresents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 18 carbon atoms, R^6b、R^7bThe same or different, each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a polyoxyethylene group having an average molar number of addition of 10 or less, R^8bRepresents an alkylene group having 1 to 3 carbon atoms; z^-Represents a halogen atom, or an anionic residue of a sulfonic acid ester or sulfuric acid ester having 1 to 5 carbon atoms.]

＜10b＞

The liquid detergent composition for hard surfaces according to any one of < 1b > to < 9b >, wherein the component (d) is at least 1 compound selected from the group consisting of aminocarboxylic acids, hydroxycarboxylic acids, hydroxyphosphonic acids, and salts thereof.

＜11b＞

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

＜12b＞

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

＜13b＞

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

＜14b＞

The liquid detergent composition for hard surfaces according to any one of < 1b > to < 13b >, wherein the content of the component (d) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, further preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, further preferably 6% by mass or less, further preferably 5% by mass or less, further preferably 4% by mass or less.

＜15b＞

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

＜16b＞

The liquid detergent composition for hard surfaces according to any one of < 1b > to < 15b >, wherein 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, and preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, still more preferably 1 or less, and still more preferably 0.8 or less.

＜17b＞

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

＜18b＞

The liquid detergent composition for hard surfaces according to < 17b >, wherein the component (c) is at least one surfactant selected from the group consisting of amphoteric surfactants, nonionic surfactants and anionic surfactants, preferably at least one surfactant selected from the group consisting of amphoteric surfactants and nonionic surfactants.

＜19b＞

The liquid detergent composition for hard surfaces according to < 18b >, wherein the amphoteric surfactant is at least 1 surfactant selected from the group consisting of amine oxide, sulfobetaine and carboxybetaine, and preferably at least 1 surfactant selected from the group consisting of sulfobetaine and carboxybetaine.

＜20b＞

The liquid detergent composition for hard surfaces according to < 18b > or < 19b >, wherein the nonionic surfactant is at least 1 nonionic surfactant selected from the group consisting of (c1) monoalkyl glyceryl ethers, (c2) polyoxyalkylene monoalkyl or alkenyl ethers, (c3) alkyl polyglycosides (glycoside type nonionic surfactants), (c4) sorbitan type nonionic surfactants, (c5) aliphatic alkanolamides, (c6) fatty acid monoglycerides, and (c7) sucrose fatty acid esters.

＜21b＞

The liquid detergent composition for hard surfaces according to any one of < 18b > to < 20b >, wherein the anionic surfactant is at least 1 anionic surfactant selected from the group consisting of (c8) sulfosuccinates having a hydrocarbon group of 5 to 18 carbon atoms or salts thereof, (c9) anionic surfactants having a hydrocarbon group of 8 to 21 carbon atoms and sulfate or sulfonate groups [ with the proviso that (c8) is excluded ], (c10) anionic surfactants having a hydrocarbon group of 7 to 21 carbon atoms and a carboxyl group, and (c11) anionic surfactants having a hydrocarbon group of 8 to 21 carbon atoms and a phosphate group.

＜22b＞

The liquid detergent composition for hard surfaces according to any one of < 17b > to < 21b >, wherein 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 8% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less.

＜23b＞

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

＜24b＞

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

＜25b＞

A method for preventing the adhesion of dirt to a hard surface, wherein the hard surface is treated with the liquid detergent composition for hard surface according to any one of < 1b > to < 24b >.

＜26b＞

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

＜27b＞

The method for preventing adhesion of dirt to a hard surface according to < 25b > or < 26b >, wherein the hard surface is: glass, pottery, porcelain, enamel, ceramic tile, ceramic; metals such as aluminum, stainless steel, and brass; synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP and the like; natural fibers such as cotton, silk, wool, and the like; and synthetic fibers such as polyester, nylon, and rayon.

＜28b＞

The method for preventing the adhesion of dirt to a hard surface according to any one of < 25b > to < 27b >, wherein the hard surface is 1 or 2 or more hard surfaces selected from the group consisting of glass, ceramics, magnets, plastics, stainless steel and silicon wafers.

＜29b＞

The method for preventing adhesion of dirt to a hard surface according to any one of < 25b > to < 28b >, wherein an article having a hard surface, 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 is treated.

＜30b＞

The method for preventing the adhesion of dirt to a hard surface according to any one of < 25b > to < 29b >, wherein the static contact angle of the hard surface, preferably a hydrophilic hard surface, more preferably a glass surface, treated with the liquid detergent composition for a hard surface against water is preferably 20 ° or less, more preferably 15 ° or less, further preferably 10 ° or less, further 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 cleaner for hard surfaces.

Examples

Production example 1[ production of copolymer A1 ]

(step 1)

126.30g of ethanol (manufactured by Wako pure chemical industries, Ltd.) was put into a four-necked flask having an internal volume of 1000mL, and the mixture was heated to 78 ℃ and refluxed. Separately, 181.12g of 2- (dimethylamino) ethyl methacrylate (manufactured by Wako pure chemical industries, Ltd.), 23.60g of 2- (dimethylamino) ethyldiethylsulfate methacrylate (manufactured by Kao corporation/90% aqueous solution) and 53.20g of ethanol, and 5.83g of 2,2' -azobis (2-methylbutyronitrile) (manufactured by Wako pure chemical industries, Ltd.) and 10.00g of ethanol were added dropwise over 2 hours. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.

(step 2)

94.70g of the obtained polymer solution, 3.15g of sodium bicarbonate (manufactured by Wako pure chemical industries, Ltd.) and 150.00g of water were added to a four-necked flask having an internal volume of 1000mL, and the temperature was raised to 50 ℃. 38.70g of 1, 3-propane sultone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise over 1 hour to carry out a reaction. After aging for 3 hours, the resulting mixture was heated at 90 ℃ under 20kPa for 2 hours under reduced pressure to distill off ethanol, thereby obtaining an aqueous solution containing copolymer A1.

In the copolymer a1, the structural unit (a1) has the following structure in formula (1), the structural unit (a2) has the following structure in formula (2), and the molar ratio of the structural unit (a 1)/the structural unit (a2) is 95/5.

Structural unit (a 1): r¹＝R²＝H、R³＝CH₃、R⁴＝C₂H₄、R⁵＝R⁶＝CH₃、X¹＝O、X²＝R¹⁷SO₃ ^-、R¹⁷＝C₃H₆

Structural unit (a 2): r⁸＝R⁹＝H、R¹⁰＝CH₃、X³＝O、R¹¹＝C₂H₄、X⁴＝N⁺R¹²R¹³R¹⁴X⁵、R¹²＝R¹³＝CH₃、R¹⁴＝C₂H₅、X⁵＝C₂H₅SO₄ ^-

The weight-average molecular weight of copolymer a1 was 63000.

Production example 2[ production of copolymer A2 ]

(step 1)

37.95g of ethanol was put into a four-necked flask having an internal volume of 1000mL, and the mixture was refluxed by raising the temperature to 78 ℃. Separately, a solution of 122.94g of 2- (dimethylamino) ethyl methacrylate, 30.06g of 2- (dimethylamino) ethyldiethylsulfate methacrylate and 28.88g of ethanol, and a solution of 1.67g of 2,2' -azobis (2-methylbutyronitrile) and 3.90g of ethanol were added dropwise over 2 hours to polymerize. After aging for 4 hours, the mixture was cooled to obtain a polymer solution. (step 2)

Into a four-necked flask having an internal volume of 1000mL were added 230.77g of the obtained polymer solution, 6.56g of sodium hydrogencarbonate and 308.91g of water, and the temperature was raised to 50 ℃. 102.21g of 1, 3-propane sultone was added dropwise thereto over 1 hour to effect a reaction. After aging for 3 hours, the resulting mixture was heated at 90 ℃ under 20kPa for 2 hours under reduced pressure to distill off ethanol, thereby obtaining an aqueous polymer solution containing copolymer A2.

In the copolymer a2, the structural units (a1) and (a2) were the same as in the copolymer a1, and the molar ratio of the structural unit (a 1)/the structural unit (a2) was 90/10.

The weight-average molecular weight of copolymer A2 was 69000.

Production example 3[ production of copolymer A3 ]

(step 1)

94.46g of ethanol was put into a four-necked flask having an internal volume of 1000mL, and the mixture was refluxed by raising the temperature to 78 ℃. Separately, a solution of a mixture of 267.52g of 2- (dimethylamino) ethyl methacrylate, 147.20g of 2- (dimethylamino) ethyldiethylsulfate methacrylate and 78.29g of ethanol, and a solution of a mixture of 4.09g of 2,2' -azobis (2-methylbutyronitrile) and 9.54g of ethanol were added dropwise thereto over 2 hours, and polymerization was carried out. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.

(step 2)

Into a four-necked flask having an internal volume of 1000mL were added 307.82g of the obtained polymer solution, 7.15g of sodium hydrogencarbonate and 394.56g of water, and the temperature was raised to 50 ℃. 111.20g of 1, 3-propane sultone was added dropwise thereto over 1 hour to effect a reaction. After aging for 3 hours, the resulting mixture was heated at 90 ℃ under 20kPa for 2 hours under reduced pressure to distill off ethanol, thereby obtaining an aqueous polymer solution containing copolymer A3.

In the copolymer A3, the structural units (a1) and (a2) were the same as in the copolymer a1, and the molar ratio of the structural unit (a 1)/the structural unit (a2) was 80/20.

The weight-average molecular weight of copolymer A3 was 78000.

Production example 4[ production of copolymer A4 ]

(step 1)

33.27g of ethanol was put into a four-necked flask having an internal volume of 1000mL, and the mixture was refluxed by raising the temperature to 78 ℃. Separately, a solution of a mixture of 81.13g of 2- (dimethylamino) ethyl methacrylate, 76.52g of 2- (dimethylamino) ethyldiethylsulfate methacrylate and 29.76g of ethanol and a solution of a mixture of 1.42g of 2,2' -azobis (2-methylbutyronitrile) and 3.31g of ethanol were added dropwise thereto over 2 hours to polymerize. After aging for 4 hours, the mixture was cooled to obtain a polymer solution. (step 2)

Into a four-necked flask having an internal volume of 1000mL were added 230.77g of the obtained polymer solution, 4.34g of sodium hydrogencarbonate and 285.67g of water, and the temperature was raised to 50 ℃. 67.45g of 1, 3-propane sultone was added dropwise thereto over 1 hour to effect a reaction. After aging for 3 hours, the resulting mixture was heated at 90 ℃ under 20kPa under reduced pressure for 2 hours to distill off ethanol, thereby obtaining an aqueous polymer solution containing a copolymer.

In the copolymer a4, the structural units (a1) and (a2) were the same as in the copolymer a1, and the molar ratio of the structural unit (a 1)/the structural unit (a2) was 70/30.

The weight-average molecular weight of copolymer A4 was 81000.

Production example 5[ production of Polymer A'1 ]

(step 1)

53.23g of ethanol was put into a four-necked flask having an internal volume of 500mL, and the mixture was refluxed by raising the temperature to 78 ℃. A mixture of 150.00g of 2- (dimethylamino) ethyl methacrylate and 16.60g of ethanol and a mixture of 0.92g of 2,2' -azobis (2-methylbutyronitrile) and 10.00g of ethanol were added dropwise over 2 hours to polymerize each. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.

(step 2)

Into a four-necked flask having an internal volume of 1000mL were added 75.76g of the obtained polymer solution, 3.47g of sodium hydrogencarbonate and 150.00g of water, and the temperature was raised to 50 ℃. 42.73g of 1, 3-propane sultone was added dropwise thereto over 1 hour to effect a reaction. After aging for 3 hours, the polymer aqueous solution containing the polymer A'1 was obtained by distilling off ethanol by heating under reduced pressure at 90 ℃ under 20kPa for 2 hours.

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%).

The weight-average molecular weight of the polymer A'1 was 40000.

The weight average molecular weights of the copolymers a1 to a4 were measured by gel permeation chromatography (pullulan) under the following conditions.

Pipe column: 2 TSKgel α -M (manufactured by Tosoh) were used in tandem.

Temperature of the pipe column: 40 deg.C

Eluent: 0.15mol of Na₂SO₄/1％CH₃COOH/water

Flow rate: 1.0 ml/min

A detector: differential refractometer

The weight average molecular weight of the polymer a'1 was measured by SLS (Static light scattering). That is, the static light scattering was measured under the following conditions using a light scattering photometer "DLS-7000" (manufactured by tsukamur electronics corporation), and Zimm-plot was prepared and calculated. The refractive index increase necessary for calculating the molecular weight was measured by using a differential refractometer "DRM 3000" (manufactured by tsukamur electronics corporation).

Wavelength: 632.8nm (helium-neon laser)

Scattering angle: the measurement was carried out at every 10 ° within the range of 30 ° to 150 °.

Temperature: 25 deg.C

Solvent: trifluoroethanol

Examples 1a to 17a and comparative examples 1a to 8a

Liquid detergent compositions for hard surfaces shown in tables 1 and 2 were prepared using the following compounding ingredients, and the following items were evaluated. The results are shown in tables 1 and 2. For convenience, the mass ratio of (a)/(b) is shown in the table with the component (a') as the component (a).

In tables 1 and 2, the mass% of the components to be blended is a numerical value based on the active ingredient. The anionic surfactant of component (c) represents mass% based on the amount of sodium salt.

The pH value is adjusted by using trace sodium hydroxide and hydrochloric acid.

< formulation >

(a) Composition (I)

Copolymers A1 to A4 were used.

(a') component (comparative component to (a))

Use of the polymer A' 1.

(b) Composition (I)

Cationic surfactant: alkyl dimethyl benzyl ammonium chloride: c8 of alkyl group (product name "Sanisol 08", manufactured by Kao corporation)

(c) Composition (I)

Nonionic surfactants: alkyl polyglycoside: alkyl (C12-16) polyglucose (average degree of sugar condensation 1-2) (product name "AG 124" manufactured by Kao corporation)

Amphoteric surfactants: lauramidopropyl carboxybetaine (product name "Amphitol 20 AB", manufactured by Kao corporation)

Anionic surfactants: sodium polyoxyethylene alkyl ether sulfate, alkyl having 12 to 16 carbon atoms, and ethylene oxide added in an average molar amount of 4.0 (product name "ES-4K", manufactured by Kao corporation)

< contact Angle >

A glass plate (76 mm. times.26 mm. times.1 mm in shape, manufactured by Songlanzi Kogyo Co., Ltd.) was coated with 1mL of the liquid detergent composition for hard surface application, left to stand for 5 minutes, and then rinsed with 25 ℃ tap water (flow rate 50 mL/sec) for 20 seconds. The static contact angle of the glass plate subjected to the above treatment with ion-exchanged water was measured in a measuring chamber adjusted to 25 ℃ and 40% RH. In the measurement, 20. mu.l of water droplets of ion-exchanged water were dropped on the surface to be treated using a full-automatic contact angle meter DM-500 manufactured by Kyowa Kagaku K.K., and after dropping for 3 seconds, contact angles were measured 10 times at 1 second intervals, and the average value was recorded as data. The static contact angle of the glass plate before treatment was 25 °. A lower contact angle, i.e., a smaller static contact angle with respect to the glass sheet before treatment, indicates a more hydrophilic property.

< antifouling Property (dirt adhesion prevention) >

The following substances were used in the following evaluations: 1mL of a liquid detergent composition for hard surface was applied to one surface of a glass plate (76 mm. times.26 mm. times.1 mm in shape, manufactured by Songlanzi Kogyo Co., Ltd.) and left for 5 minutes, and then rinsed with 25 ℃ tap water (flow rate 50 mL/sec) for 20 seconds.

450ml of water and 50ml of a model oil solution (model oil: oleic acid, pigment: Sudan III (0.1 part by mass relative to 100 parts by mass of oleic acid)) were mixed in a 500ml beaker having a diameter of 10cm, and a liquid separated into 2 layers, the lower layer of which was water and the upper layer of which was oil, was prepared.

The glass sheet was pulled out after passing through the upper layer and being immersed in the lower layer in a full immersion manner for 10 seconds.

Thereafter, the immersed glass plate was dried, a photograph of the glass plate was taken, image processing was performed on the photograph (using ImageJ), the remaining area of the oil on the glass plate was measured, and the remaining rate of the oil was calculated based on the processed area of the glass plate (first time). Thereafter, the glass plate was immersed again for 10 seconds and then pulled up, and the residual ratio was calculated by the same method (second time). The residual ratio (%) was calculated from how much oil (degree of coating) was coated on the surface of the glass, assuming that the treated area of the glass was 100.

< foaming ability >

The liquid detergent composition for hard surfaces was filled in a trigger spray container (manufactured by toiletmagi clean spray, kao corporation), and sprayed into a 200mL measuring cylinder (inner diameter 40mm) 10 times in a bubble spreading mode of the container. The mass of the 200mL measuring cylinder after spraying was measured using a four-position balance, and the difference from the mass of the measuring cylinder before spraying was defined as the bubble application amount (g) (a). The bubble volume (mL) (b) in the measuring cylinder after spraying was visually checked. The specific volume of bubbles was calculated by the following equation. The results are shown in tables 1 and 2.

Specific volume of bubble (mL/g) ═ b)/(a)

The larger the specific bubble volume, the more excellent the foaming ability.

< degerming power >

Staphylococcus aureus (strain NBRC12732) was cultured on Nutrient Agar medium (Nutrient Agar reagent manufactured by Difco corporation prepared according to the efficacy instruction) repeatedly for 2 times at 37 ℃/24 hours, and then scraped off to be suspended and dispersed in1/2 nutrient solution culture medium (manufactured by Difco corporation, Nuturint Broth reagent prepared at 1/2 concentration of efficacy instruction) is prepared by using 1/2 nutrient solution culture medium to prepare bacteria concentration of 2.5-13 × 10⁸cfu/mL was mixed with a3 mass% bovine serum albumin aqueous solution in the same volume to prepare a test bacterial solution. A disk made of stainless steel having a diameter of 20mm, a thickness of 1mm and a surface grade of 2B was sterilized, and then placed in a glass petri dish having an inner diameter of 75mm, and 10. mu.L of the test bacterial solution was inoculated onto the surface of the disk by using a micropipette (GILSON, trade name PIPEMAN) and applied. After the bacterial solution was allowed to dry under the condition of 25. + -. 1 ℃ without covering the lid of the glass petri dish, the liquid in which the hard surface was diluted to 100 times with water adjusted to 4 ℃ dH in hardness was quickly attached. The liquid diluted 100 times with the liquid detergent composition for hard surface was attached to the surface of a stainless steel disk having a diameter of 20mm by a micropipette (GILSON, trade name PIPEMAN) of 3.14cm by using water having a hardness adjusted to 4 DEG dH²Inoculation 10. mu.L (equivalent to 0.32g/100 cm) of a liquid for hard surface diluted to 100 times with water adjusted to 4 ℃ dH in hardness²) And coating. After 5 minutes of the deposition, a predetermined amount of the diluted LP water (prepared by a product manufactured by japan water pharmaceutical industries, inc.) was poured into the diluted LP water so as to inactivate the sterilization performance of the composition without paying attention to the composition deposited without causing the composition to flow down, and the bacterial concentration in the diluted LP water was counted by the decantation culture method. The same procedure (10. mu.L of the disk surface was inoculated and spread by the above-mentioned micropipette inoculation, and the plate surface was put into the LP dilution 5 minutes after inoculation) was performed using physiological saline instead of the composition as a control, and the logarithmic difference between the number of bacteria in the LP dilution and the number of bacteria in the control was calculated, and the indicator of the sterilization performance was set according to the following criteria.

Evaluation criteria for degerming ability

A: the logarithmic difference of the number of bacteria is more than 2

B: the logarithmic difference of the number of bacteria is less than 2

< stability of coordination >

The appearance of the liquid detergent composition for hard surface immediately after production was visually observed at a liquid temperature of 20 ℃ and evaluated according to the following criteria.

Evaluation criteria for stability of compounding

A: dissolve uniformly.

B: slightly cloudy.

C: turbidity was evident.

[ Table 2]

Examples 1b to 9b and comparative examples 1b to 4b

Liquid detergent compositions for hard surfaces shown in table 3 were prepared using the following compounding ingredients, and the following items were evaluated. The results are shown in Table 3. In table 3, the mass% of the components to be blended is a numerical value based on the effective component. For convenience, the mass ratio of (a)/(b) is shown in the table with the component (a') as the component (a). The mass ratio of (b)/(d) is a value calculated based on the mass% of the component (d) in terms of acid.

The pH value is adjusted by a small amount of sodium hydroxide or hydrochloric acid.

< formulation >

(a) Composition (I)

The copolymer a1 of production example 1 and the copolymer a4 of production example 4 were used.

(a') component (comparative component to (a))

The polymer A'1 of production example 5 was used.

(b) Composition (I)

Cationic surfactant: alkyl dimethyl benzyl ammonium chloride: c8 of alkyl group (product name "Sanisol 08", manufactured by Kao corporation)

(d) Composition (I)

EDTA: ethylenediaminetetraacetic acid and tetrasodium salt (the numbers in the table are% by mass in terms of sodium salt, and the numbers in the parentheses are% by mass in terms of acid)

Other ingredients

Nonionic surfactants: alkyl polyglycoside: alkyl (C12-16) polyglucose (average degree of sugar condensation 1-2) (product name "AG 124" manufactured by Kao corporation)

Amphoteric surfactants: lauramidopropyl carboxybetaine (product name "Amphitol 20 AB", manufactured by Kao corporation)

< contact Angle >

The static contact angle was measured in the same manner as in example 1a and the like.

< antifouling Property (dirt adhesion prevention) >

The following substances were used in the following evaluations: 1mL of a liquid detergent composition for hard surface was applied to one surface of a glass plate (76 mm. times.26 mm. times.1 mm in shape, manufactured by Songlanzi Kogyo Co., Ltd.) and left for 5 minutes, and then rinsed with 25 ℃ tap water (flow rate 50 mL/sec) for 20 seconds.

450ml of water and 50ml of a model oil solution (model oil: oleic acid, pigment: Sudan III (0.1 part by mass relative to 100 parts by mass of oleic acid)) were mixed in a 500ml beaker having a diameter of 10cm, and a liquid separated into 2 layers, the lower layer of which was water and the upper layer of which was oil, was prepared.

The glass sheet was pulled out after passing through the upper layer and being immersed in the lower layer in a full immersion manner for 10 seconds.

After the glass plate after the immersion was dried, a photograph of the glass plate was taken, Image processing was performed on the photograph (using Image J), the remaining area of the oil on the glass plate was measured, and the remaining rate of the oil was calculated based on the processed area of the glass plate. The residual ratio (%) was calculated from how much oil (degree of coating) was coated on the surface of the glass, assuming that the treated area of the glass was 100. The antifouling property was evaluated based on the residual ratio in the following manner.

Evaluation criteria for antifouling Properties

A: the residue rate is less than 10 percent

B: the residual rate is more than 10 percent

< cleaning power (removal of scale) >

2ml of a 0.5% aqueous solution of monocalcium phosphate were uniformly coated on black ceramic plates (10 cm. times.10 cm tiles) as a mold for fouling and allowed to dry at 120 ℃ for 30 minutes. This operation was repeated 10 times to produce a model contaminated board, which was used for a cleaning force test.

The composition was dropped (0.3ml) onto the above mold contamination plate which was horizontally fixed, left to stand for 1 minute, and then wiped 10 times with a cotton swab to clean the plate. Images were taken of the pottery plate without being coated with the stains, the pottery plate before being cleaned (mold fouling plate) after being coated with the stains, and the pottery plate after being cleaned under the same conditions for image pickup such as brightness, and the gradation of each pottery plate was measured from the obtained images. The cleaning efficiency of the pottery plate before cleaning was 0%, the cleaning efficiency of the pottery plate without the stains applied thereto was 100%, and the state of the pottery plate after cleaning was compared to calculate the cleaning efficiency of the pottery plate. Image j1.47v of Image processing software was used for measuring the gradation.

< degerming power >

The degerming ability was evaluated in the same manner as in example 1a and the like.

< stability of coordination >

The compounding stability was evaluated in the same manner as in example 1 a.

< foaming ability >

The liquid detergent composition for hard surfaces was filled in a trigger spray container (manufactured by toiletmagirald spray, kaowang), and sprayed into a 200mL measuring cylinder (inner diameter: 40mm) 10 times in a bubble spreading mode of the container. The mass of the 200mL measuring cylinder after spraying was measured using a four-position balance, and the difference from the mass of the measuring cylinder before spraying was defined as the bubble application amount (g) (a). The bubble volume (mL) (b) in the measuring cylinder after spraying was visually checked. The specific volume of bubbles was calculated by the following equation. The results are shown in Table 3.

Specific volume of bubble (mL/g) ═ b)/(a)

The larger the specific bubble volume, the more excellent the foaming ability. Foaming properties were evaluated according to the following criteria based on specific bubble volume.

Evaluation basis of foaming Properties

A: the specific volume of the bubbles is more than 10mL/g

B: the specific volume of bubbles is more than 5mL/g and less than 10mL/g

C: the specific volume of bubbles is less than 5mL/g

Claims (62)

1. A liquid detergent composition for hard surfaces, wherein,

comprises the following components: (a) a copolymer which contains a structural unit (a1) represented by the following formula (1) and a structural unit (a2) represented by the following formula (2), and in which the molar ratio of the structural unit (a1) to the structural unit (a2) (structural unit (a 1)/structural unit (a2) is 30/70 or more and 99.9/0.1 or less, and which is hereinafter referred to as component (a); (b) a cationic surfactant hereinafter referred to as component (b); and (c) at least one surfactant selected from amphoteric surfactants, nonionic surfactants and anionic surfactants, hereinafter referred to as component (c),

in the formula (I), the compound is shown in the specification,

R¹～R³the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

R⁴is an alkylene group having 1 to 4 carbon atoms, or-Y¹-OPO₃ ^--Y²-，

Y¹、Y²The same or different alkylene groups having 1 to 4 carbon atoms,

R⁵、R⁶the same or different hydrocarbon groups having 1 to 4 carbon atoms,

X¹is O or NR⁷，R⁷A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

X²represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R¹⁷SO₃ ^-Or R¹⁷COO^-Wherein, in R⁴When the alkylene group has 1 to 4 carbon atoms, X²Is R¹⁷SO₃ ^-Or R¹⁷COO^-，R¹⁷An alkylene group having 1 to 4 carbon atoms; at R⁴is-Y¹-OPO₃ ^--Y²When is, X²A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

in the formula (I), the compound is shown in the specification,

R⁸～R¹⁰the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

X³is a compound of the formula (I) O,

R¹¹an alkylene group having 1 to 4 carbon atoms,

X⁴is N⁺R¹²R¹³R¹⁴X⁵Or NR¹⁵R¹⁶，R¹²～R¹⁶The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X⁵Represents an anion.

2. The liquid detergent composition for hard surfaces according to claim 1,

(a) the weight average molecular weight of the component (A) is 500 to 20 ten thousand.

3. The liquid detergent composition for hard surfaces according to claim 1,

(a) the content of the structural unit (a1) in the component (a) is 30 to 99 mol%.

4. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(a) the content of the structural unit (a2) in component (a) is 1 mol% or more and 70 mol% or less.

5. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(a) the content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is 10 mol% or less.

6. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(a) the total content of the structural unit (a1) and the structural unit (a2) in the component (a) is 90 mol% or more.

7. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(b) the component is a cationic surfactant selected from mono-or di-long-chain alkyl quaternary ammonium salt.

8. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(b) a cationic surfactant selected from the group consisting of a compound represented by the following general formula (b1) and a compound represented by the following general formula (b2),

in the formula, is selected from R^1bAnd R^2bAt least one of the above groups represents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 18 carbon atoms, and the others represent an alkyl group, a hydroxyalkyl group or a polyoxyethylene group having 10 or less average molar numbers of addition, wherein R represents^3bAnd R^4bThe same or different, each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a polyoxyethylene group having an average molar number of addition of 10 or less, and Y^-Represents a halogen atom or a carbon atom having 1 to 5 carbon atomsThe anionic residue of the sulfonate or sulfate ester of (a),

in the formula, R^5bRepresents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 18 carbon atoms, R^6b、R^7bThe same or different, each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a polyoxyethylene group having an average molar number of addition of 10 or less, R^8bRepresents an alkylene group having 1 to 3 carbon atoms; z^-Represents a halogen atom, or an anionic residue of a sulfonic acid ester or sulfuric acid ester having 1 to 5 carbon atoms.

9. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(c) the component (A) is at least one surfactant selected from amphoteric surfactant and nonionic surfactant.

10. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the amphoteric surfactant is at least 1 selected from amine oxide, sulfobetaine and carboxybetaine.

11. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the content of 1 or more amphoteric surfactants selected from amine oxide, sulfobetaine, and carboxybetaine in the amphoteric surfactant is 50 to 100% by mass.

12. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the content of 1 or more amphoteric surfactants selected from sulfobetaines and carboxybetaines in the amphoteric surfactants is 50 to 100% by mass.

13. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the nonionic surfactant is 1 or more nonionic surfactants selected from the group consisting of (c1) monoalkyl glyceryl ether referred to as (c1) component below, (c2) polyoxyalkylene monoalkyl or alkenyl ether referred to as (c2) component below, (c3) alkyl polyglycoside as a glycoside type nonionic surfactant referred to as (c3) component below, a (c4) sorbitan type nonionic surfactant referred to as (c4) component below, a (c5) aliphatic alkanolamide referred to as (c5) component below, a (c6) fatty acid monoglyceride referred to as (c6) component below, and a (c7) sucrose fatty acid ester referred to as (c7) component below.

14. The liquid detergent composition for hard surfaces according to claim 13,

the nonionic surfactant is at least 1 nonionic surfactant selected from the group consisting of component (c1), component (c2), and component (c 3).

15. The liquid detergent composition for hard surfaces according to claim 13,

the content of the component (c3) in the nonionic surfactant is 50 to 100 mass%.

16. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the anionic surfactant is an anionic surfactant having a sulfate group, a phosphate group, a phosphonic acid group, a sulfonic acid group, or a carboxyl group.

17. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the anionic surfactant has a hydrocarbon group having 5 to 21 carbon atoms, and the hydrocarbon group is a linear or branched alkyl group, alkylene group, or aryl group.

18. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the anionic surfactant is 1 or more anionic surfactants selected from the group consisting of (c8) a sulfosuccinate having a hydrocarbon group having 5 to 18 carbon atoms or a salt thereof, which is hereinafter referred to as (c8), an anionic surfactant having a sulfate group or a sulfonic acid group, which is hereinafter referred to as (c9) and in which (c9) other than (c8) has a hydrocarbon group having 8 to 21 carbon atoms, an anionic surfactant having a carboxyl group, which is hereinafter referred to as (c10) and which is hereinafter referred to as (c10), and an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a phosphate group, which is hereinafter referred to as (c11) of (c 11).

19. The liquid detergent composition for hard surfaces according to claim 18,

the anionic surfactant is 1 or more kinds selected from the group consisting of the component (c8) and the component (c 9).

20. The liquid detergent composition for hard surfaces according to claim 18,

the content of the component (c9) in the anionic surfactant is 50 mass% or more and 100 mass% or less.

21. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(a) the content of the component (B) is 0.01-3 mass%.

22. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(b) the content of the component (B) is 0.01-5% by mass.

23. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(c) the content of the component (B) is 0.05-10% by mass.

24. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(a) the mass ratio of (a) to (b) is 0.01 to 5.

25. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

(b) the mass ratio of (c) is 0.05 to 30 inclusive.

26. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the water content is 30 to 95 mass%.

27. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the hard surface is a hydrophilic hard surface.

28. The liquid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein,

the hard surface treated with the liquid detergent composition for hard surfaces has a static contact angle with water of 20 DEG or less.

29. A method for preventing the adhesion of dirt to a hard surface,

treating a hard surface with a liquid detergent composition for hard surfaces according to any one of claims 1 to 28.

30. The method for preventing the adhesion of stains to a hard surface according to claim 29,

the hard surface is a hydrophilic hard surface.

31. The method for preventing the adhesion of stains to a hard surface according to claim 29,

the hard surface is a solid hard surface selected from the group consisting of glass, ceramics, magnets, enamels, ceramic tiles, ceramics, metals, synthetic resins, natural fibers, and synthetic fibers.

32. The method for preventing adhesion of dirt to a hard surface according to any one of claims 29 to 31,

treating an article having a hard surface selected from a toilet, a bathtub, a sink in a kitchen, a window glass, a mirror, and a faucet.

33. The method for preventing adhesion of dirt to a hard surface according to any one of claims 29 to 31,

the hard surface treated with the liquid detergent composition for hard surfaces has a static contact angle with water of 20 DEG or less.

34. Use of a composition according to any one of claims 1 to 28 as a liquid cleaner for hard surfaces.

35. A liquid detergent composition for hard surfaces, wherein,

comprises the following components: (a) a copolymer which contains a structural unit (a1) represented by the following formula (1) and a structural unit (a2) represented by the following formula (2), and in which the molar ratio of the structural unit (a1) to the structural unit (a2) (structural unit (a 1)/structural unit (a2) is 30/70 or more and 99.9/0.1 or less, and which is hereinafter referred to as component (a); (b) a cationic surfactant hereinafter referred to as component (b); and (d) a chelating agent, hereinafter referred to as component (d),

in the formula (I), the compound is shown in the specification,

R¹～R³the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

R⁴is an alkylene group having 1 to 4 carbon atoms, or-Y¹-OPO₃ ^--Y²-，

Y¹、Y²The same or different alkylene groups having 1 to 4 carbon atoms,

R⁵、R⁶the same or different hydrocarbon groups having 1 to 4 carbon atoms,

X¹is O or NR⁷，R⁷A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

X²represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R¹⁷SO₃ ^-Or R¹⁷COO^-Wherein, in R⁴When the alkylene group has 1 to 4 carbon atoms, X²Is R¹⁷SO₃ ^-Or R¹⁷COO^-，R¹⁷An alkylene group having 1 to 4 carbon atoms; at R⁴is-Y¹-OPO₃ ^--Y²When is, X²A hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,

in the formula (I), the compound is shown in the specification,

R⁸～R¹⁰the same or different, are hydrogen atoms or alkyl groups of 1 or 2 carbon atoms,

X³is a compound of the formula (I) O,

R¹¹an alkylene group having 1 to 4 carbon atoms,

X⁴is N⁺R¹²R¹³R¹⁴X⁵Or NR¹⁵R¹⁶，R¹²～R¹⁶The same or differentRepresents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X⁵Represents an anion.

36. The liquid detergent composition for hard surfaces according to claim 35, wherein,

(a) the weight average molecular weight of the component (A) is 500 to 20 ten thousand.

37. The liquid detergent composition for hard surfaces according to claim 35, wherein,

(a) the content of the structural unit (a1) in the component (a) is 30 to 99 mol%.

38. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(a) the content of the structural unit (a2) in component (a) is 1 mol% or more and 70 mol% or less.

39. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(a) the content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is 10 mol% or less.

40. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(a) the total content of the structural unit (a1) and the structural unit (a2) in the component (a) is 90 mol% or more.

41. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(b) the component is mono-or di-long chain alkyl quaternary ammonium salt.

42. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(b) a cationic surfactant selected from the group consisting of a compound represented by the following general formula (b1) and a compound represented by the following general formula (b2),

in the formula, is selected from R^1bAnd R^2bAt least one of the above groups represents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 18 carbon atoms, and the others represent an alkyl group, a hydroxyalkyl group or a polyoxyethylene group having 10 or less average molar numbers of addition, wherein R represents^3bAnd R^4bThe same or different, each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a polyoxyethylene group having an average molar number of addition of 10 or less, and Y^-Represents a halogen atom, or an anionic residue of a sulfonic acid ester or sulfuric acid ester having 1 to 5 carbon atoms,

in the formula, R^5bRepresents an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 18 carbon atoms, R^6b、R^7bThe same or different, each represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a polyoxyethylene group having an average molar number of addition of 10 or less, R^8bRepresents an alkylene group having 1 to 3 carbon atoms; z^-Represents a halogen atom, or an anionic residue of a sulfonic acid ester or sulfuric acid ester having 1 to 5 carbon atoms.

43. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(d) the component (B) is at least 1 compound selected from aminocarboxylic acids, hydroxycarboxylic acids, and salts thereof.

44. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(a) the content of the component (B) is 0.01-3 mass%.

45. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(b) the content of the component (B) is 0.01-5% by mass.

46. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(d) the content of the component (B) is 0.01-10% by mass.

47. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(a) the mass ratio of (a) to (b) is 0.01 to 5.

48. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

(b) the mass ratio of/(d) is 0.01 to 10 inclusive.

49. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

the surfactant other than the component (b) is contained, and hereinafter referred to as a component (c).

50. The liquid detergent composition for hard surfaces according to claim 49, wherein,

(c) the component (A) is at least one surfactant selected from amphoteric surfactant, nonionic surfactant and anionic surfactant.

51. The liquid detergent composition for hard surfaces according to claim 50,

the amphoteric surfactant is at least 1 selected from amine oxide, sulfobetaine and carboxybetaine.

52. The liquid detergent composition for hard surfaces according to claim 50,

the nonionic surfactant is at least one nonionic surfactant selected from the group consisting of (c1) monoalkyl glycerol ethers, (c2) polyoxyalkylene monoalkyl or alkenyl ethers, (c3) alkyl polyglycosides as glycoside type nonionic surfactants, (c4) sorbitan type nonionic surfactants, (c5) aliphatic alkanolamides, (c6) fatty acid monoglycerides, and (c7) sucrose fatty acid esters.

53. The liquid detergent composition for hard surfaces according to claim 50,

the anionic surfactant is 1 or more anionic surfactants selected from the group consisting of (c8) sulfosuccinates having a hydrocarbon group of 5 to 18 carbon atoms or salts thereof, (c9) anionic surfactants having a hydrocarbon group of 8 to 21 carbon atoms and a sulfate group or a sulfonate group, excluding (c8), (c10) anionic surfactants having a hydrocarbon group of 7 to 21 carbon atoms and a carboxyl group, and (c11) anionic surfactants having a hydrocarbon group of 8 to 21 carbon atoms and a phosphate group.

54. The liquid detergent composition for hard surfaces according to claim 49, wherein,

(c) the content of the component (B) is 0.05-10% by mass.

55. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

the water content is 30 to 95 mass%.

56. The liquid detergent composition for hard surfaces according to any one of claims 35 to 37, wherein,

the hard surface is a hydrophilic hard surface.

57. A method for preventing the adhesion of dirt to a hard surface,

treating a hard surface with a liquid detergent composition for hard surfaces according to any one of claims 35 to 56.

58. The method for preventing the adhesion of stains to a hard surface according to claim 57,

the hard surface is a hydrophilic hard surface.

59. The method for preventing the adhesion of stains to a hard surface according to claim 57,

the hard surface is a solid hard surface selected from the group consisting of glass, ceramics, magnets, enamels, ceramic tiles, ceramics, metals, synthetic resins, natural fibers, and synthetic fibers.

60. The method for preventing adhesion of dirt to a hard surface according to any one of claims 57 to 59,

treating an article having a hard surface selected from a toilet, a bathtub, a sink in a kitchen, a window glass, a mirror, and a faucet.

61. The method for preventing adhesion of dirt to a hard surface according to any one of claims 57 to 59,

the hard surface treated with the liquid detergent composition for hard surfaces has a static contact angle with water of 20 DEG or less.

62. Use of a composition according to any one of claims 35 to 56 as a liquid cleaner for hard surfaces.